WO2019191034A1 - Method of making confined nanocatalysts within mesoporous materials and uses thereof - Google Patents

Method of making confined nanocatalysts within mesoporous materials and uses thereof Download PDF

Info

Publication number
WO2019191034A1
WO2019191034A1 PCT/US2019/023989 US2019023989W WO2019191034A1 WO 2019191034 A1 WO2019191034 A1 WO 2019191034A1 US 2019023989 W US2019023989 W US 2019023989W WO 2019191034 A1 WO2019191034 A1 WO 2019191034A1
Authority
WO
WIPO (PCT)
Prior art keywords
mof
mesoporous
metal
mpm
confined
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2019/023989
Other languages
French (fr)
Inventor
Ignacio LUZ MINGUEZ
Mustapha Soukri
Marty Lail
John R. Carpenter
Sameer PARVATHIKAR
Michael Carpenter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RTI International Inc
Original Assignee
RTI International Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by RTI International Inc filed Critical RTI International Inc
Priority to KR1020207030458A priority Critical patent/KR102747349B1/en
Priority to ES19776162T priority patent/ES2980683T3/en
Priority to US17/041,944 priority patent/US11406971B2/en
Priority to EP19776162.0A priority patent/EP3774038B1/en
Priority to JP2020551555A priority patent/JP7281478B2/en
Priority to CN201980032699.0A priority patent/CN112218716A/en
Priority to CA3095128A priority patent/CA3095128A1/en
Priority to AU2019242630A priority patent/AU2019242630B2/en
Publication of WO2019191034A1 publication Critical patent/WO2019191034A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B01J35/77—Compounds characterised by their crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
    • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
    • C01B3/0015—Organic compounds, e.g. liquid organic hydrogen carriers [LOHC] or metalorganic compounds; Solutions thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/12—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/22—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis
    • C01C1/0405—Preparation of ammonia by synthesis from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis from N2 and H2 in presence of a catalyst characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/12—Gold compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present disclosure provides methods of making confined nanocatalysts within mesoporous materials (MPMs).
  • the methods utilize solid state growth of nanocrystalline metal organic frameworks (MOFs) followed by controlled transformation to generate nanocatalysts in situ within the mesoporous material.
  • MOFs nanocrystalline metal organic frameworks
  • the disclosure also provides applications of the nanocatalysts to a wide variety of fields including, but not limited to, liquid organic hydrogen carriers, synthetic liquid fuel preparation, and nitrogen fixation.
  • Metal organic frameworks have been widely used as versatile precursors for the preparation of catalytically active materials upon applying certain conditions, such as controlled pyrolysis under nitrogen, calcination under oxygen or reduction under hydrogen - .
  • MOFs Metal organic frameworks
  • MOFs as precursors
  • the versatility of MOFs as precursors is mainly due to their unique and highly tunable features, such as well-defined metal sites spaced by organic struts displayed along a crystalline structure with permanent porosity, which can play two simultaneous roles acting as template and precursor.
  • MOFs can lead to well defined nanostructured catalytically active species, which are monodispersed within hierarchical scaffolds, depending on the conversion conditions, i.e., microporous metal oxide under oxidant conditions or microporous carbonaceous matrix under inert conditions.
  • the resulting nanostructured catalysts can be composed by metals, metal oxides, heteroatom-doped carbon and combinations thereof (Wei, J.; Ge, Q.; Yao, R.; Wen, Z.; Fang, C.; Guo, L.; Xu, H.; Sun, J.: Directly converting C0 2 into a gasoline fuel Nat. Commun 2017, 8, 15174 doi: l0. l038/ncommsl5l74).
  • nano-sized MOF domains (5-50 nm) as precursor instead of bulkier particles can offer some advantages from the catalytic point of view after transformation, as they can lead to the isolation of a reduced number of metallic or metal oxide atoms, and even forming sub nanometric crystalline domains or denominated clusters (Liu, L. C.; Diaz, U.; Arenal, R.; Agostini, G.; Concepcion, P.; Corma, A.: Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nature Materials 2017, 16, 132-138).
  • MOF nanocrystals are problematic due to their poor stability under high temperatures that may promote their fusion into larger aggregates under the required transformation conditions, thereby leading to the same scenario than starting from bulkier MOF precursors. Therefore, novel synthetic routes are highly demanded to avoid MOF nanocrystalline precursors from sintering during high temperature treatments, thus paving the way to the development of new generation of MOF-derived nanocatalysts.
  • Li et al. disclosed the direct conversion of single MOF nanocrystals supported on the external surface of a layered double hydroxide (LDH) into single metal or metal oxide nanocrystals by heating in air or heating under a reductive atmosphere, respectively (Li, P.; Zeng, H. C.: Immobilization of Metal-Organic Framework Nanocrystals for Advanced Design of Supported Nanocatalysts. ACS Applied Materials & Interfaces 2016, 8, 29551-29564). The authors note the benefits dispersing and stabilizing effects of the LDH support for obtaining well- dispersed single metal or metal oxide nanocrystals. Li et al.
  • the present disclosure provides a method of preparing a confined metallic nanocatalyst within a mesoporous material (MPM) which comprises: (a) impregnating at least one or more organic compound, comprising one or more multidentate ligand(s) [A X (L X )] capable of forming coordination bonds with at least one metal ion, on the mesoporous material to form a first intermediate [(A X (L X )/MPM)] ; (b) exposing the first intermediate [(A X (L X ) /MPM)] to an acid in gas phase to form a second intermediate [(H X (L X )/MPM)] ; (c) adding to the second intermediate [(H X (L X )/MPM)] a solvent solution of one or more metal ions (Mi +y , M 2 +y , M 3 +y ) so as to form coordination bonds with the one or more multidentate lig
  • step (d) further may comprise step (d)(1) comprising contacting the precursor of step (c) [MOF /MPM] with one or more organic compounds (Z) to make a second multidentate ligand capable of forming coordination bonds [Z/MOF /MPM]; and step (d)(2) adding a solvent solution of one or more additional metal ion to form a modified MOF precursor with additional metals confined within the mesoporous material [MOF/MPM].
  • the chelating ligand (Z) in step (d)(1) comprises a metal binding site for complexing a second metal ion.
  • the controlled transformation conditions cause greater than 90% of the carbon in the MOF to be released from the MOF/MPM. In some cases, nearly 100% of the carbon may be released, e.g., greater than 95%, greater than 97%, greater than 99%.
  • the controlled transformation conditions lead to 50% ⁇ 10% of the carbon in the MOF to be released from the MOF/MPM.
  • 30% ⁇ 10%, 40% ⁇ 10%, 60% ⁇ 10% or 70% ⁇ 10% may be released.
  • the treating under controlled transformation conditions is pyrolysis at a temperature of about 300 °C to about 1000 °C in an inert gas atmosphere. More specifically, the inert atmosphere pyrolysis may be at 350 °C ⁇ 50 °C, 400 °C ⁇ 50 °C, 450 °C ⁇ 50 °C, 500 °C ⁇ 50 °C, 550 °C ⁇ 50 °C, 600 °C ⁇ 50 °C, 650 °C ⁇ 50 °C, 700 °C ⁇ 50 °C, 750 °C ⁇ 50 °C, 800 °C ⁇ 50 °C, 850 °C ⁇ 50 °C, 900 °C ⁇ 50 °C, or 950 °C ⁇ 50 °C.
  • the treating under controlled transformation conditions is calcination at a temperature of about 300 °C to about 600 °C in an atmosphere containing oxygen gas. More specifically, the calcination may be at 350 °C ⁇ 50 °C, 400 °C ⁇ 50 °C, 450 °C ⁇ 50 °C, 500 °C ⁇ 50 °C, or 550 °C ⁇ 50 °C.
  • the calcination atmosphere may be air.
  • the calcination atmosphere may be enriched with oxygen or air depleted in oxygen but still containing a sufficient concentration of oxygen to react with the carbon in the MOF/MPM.
  • the treating under controlled transformation conditions is treatment in a reductive atmosphere, such as reduction with hydrogen at a temperature of about 25 °C to about 300 °C. More specifically, the calcination may be at 50 °C ⁇ 25 °C, 75 °C ⁇ 25 °C, 100 °C ⁇ 25 °C, 125 °C ⁇ 25 °C, 150 °C ⁇ 25 °C, 175 °C ⁇ 25 °C, 200 °C ⁇ 25 °C, 225 °C ⁇ 25 °C 250 °C ⁇ 50 °C, or 275 °C ⁇ 25 °C.
  • the reductive atmosphere may be 100% hydrogen, 90 ⁇ 5% hydrogen, 80 ⁇ 5% hydrogen, 70 ⁇ 5% hydrogen, 60 ⁇ 5% hydrogen, 50 ⁇ 5% hydrogen, 40 ⁇ 5% hydrogen, 30 ⁇ 5% hydrogen, 20 ⁇ 5% hydrogen, or 10 ⁇ 5% hydrogen.
  • the confined nanocatalyst is monometallic (Mi).
  • the confined nanocatalyst is bimetallic (M I +M 2 ).
  • the confined nanocatalyst has 3 or more metals.
  • the confined nanocatalyst within the mesoporous material has a diameter of less than 10 nm. In other embodiments, the nanocatalyst has a diameter of about 2 to about 4 nm, about 3 to about 5 nm, about 4 to about 6 nm, about 5 to about 7 nm, about 6 to about 8 nm, about 7 to about 9 nm, or about 8 to about 10 nm.
  • the mesoporous material is a mesoporous metal oxide, a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, or a mesoporous aluminophosphate.
  • the mesoporous metal oxide may be aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, or magnesium oxide.
  • the mesoporous material has a surface area of about 100 m 2 /g to about 1000 m 2 /g.
  • the metal ions are selected from the group consisting of Al, Au, Ce, Co, Fe, Ir, Mo, Ni, Pd, Rh, Ru, Ti, V and Zr or combinations thereof. Specific reactions and metal catalyst combinations are as follows:
  • Electrocatalytic ammonia oxidation (Ru-Zr, Pt-Ir, Pt-Pd) Denver Cheddie “Ammonia as a Hydrogen Source for Fuel Cells: A Review” Chapter 13 from a book edited by Dragica Minic called“Hydrogen Energy - Challenges and Perspectives”.
  • Catalytic converters for internal combustion engines (Pt-Rh, Ce-Pt-Rh) Farrauto and Heck, Catalytic converters: state of the art and perspectives, Catalysis Today , 1999, 51(3-4), 351-360.
  • the multidentate ligand for the MOF is selected from the group consisting of, terephthalate, benzene-l,3,5-tricarboxylate, 2,5-dioxibenzene dicarboxylate, biphenyl-4,4’-dicarboxylate, imidazolate, pyrimidine-azolate, triazolate, tetrazolate, derivatives or combinations thereof.
  • the MOF may be HKUST-l, M 2 (dobpdc), MIF-100, MIF-101, MIF-53, MOF-74, NU-1000, PCN-222, PCN-224, UiO-66, UiO-67, ZIF-8, ZIFs, or derivatives thereof.
  • mesoporous material is selected from the group consisting of, MCM-41, SBA-15, or commercially available silica.
  • the free functional groups at the organic ligand of the MOF are selected from amino, bipyridine, chloride, hydroxyl, porphyrin, ester, amide, ketone, acid, hydrazine, or oxime.
  • the chelating ligand (Z) is selected from salicyl aldehyde, ethyl chloro-oxoacetate, pyridine aldehyde, hydroxymethylphosphine, pyrrole aldehyde, ethylenediamine, picolinate, dimethylglyoximate, 2,2’ ,2”-terpyridine, 1,4,7,10- triethylenetetramine, 1,4,8, l l-triethylenetetramine, phenanthroline and bisdiphenylphospinoethane or phosphine aldehyde.
  • the nanocatalyst confined within mesoporous material is further reacted with additional organometallic metal complexes or metal salts with polymers, organometallic ligand precursors, nitrogen-containing organic compounds, phosphorous- containing organic compounds, sulfur-containing organic compounds, boron-containing organic compounds, halide salts, organic halides, or metal atoms added via atomic layer deposition or chemical vapor deposition.
  • the disclosure also provides a catalyst made by the methods described above.
  • the catalyst may further comprise an added metal promotor.
  • the disclosure also provides uses.
  • the catalysts described above may be used to catalyze alkene ammoxidation reactions, alkene epoxidation, ammonia synthesis, carboxylation reactions , C0 2 methanation reactions, conversion of C0 2 to fuel, direct methanol synthesis from methane, dry-methane reforming, electrocatalytic ammonia oxidation, electrocatalytic oxygen reduction reactions, Fischer-Tropsch synthesis, hydro-/dehydrogenation of liquid organic hydrogen carriers, hydrotreating and hydroprocessing esterification reactions, methanol synthesis from syngas, reverse water-gas shift reactions, or water-gas shift reactions.
  • Fig. 1 Scheme describing a general approach of single-nanocry stal-to- single nanocatalyst conversion of MOF nanocrystals into bimetallic oxide nanocatalysts.
  • TEM images (a) SBA-15 and (b) (Zr)UiO-66(NH 2 )/SBA-l5.
  • STEM images for (c) PdCl-SI-(Zr)UiO- 66(NH 2 )/SBA-l5 and (d) Pd N c/SI-(Zr)UiO-66(NH 2 )/SBA-l5.
  • FIG. 2 A scheme showing a two-step post-synthesis modification (PSM) for transition metal complex incorporation on MOF nanocrystals and subsequently controlled transformation treatment for preparing bimetallic nanocatalysts.
  • This controlled transformation treatment scheme is valid for monometallic MOF nanocrystals containing only one metal oxide at the SBU.
  • Low MOF loading (below 15 wt%) has been found to be a determinant for obtaining sufficient initial spacing between MOF nanocrystals.
  • Higher MOF loadings (20-40 wt.%) lead to shorter distances between crystallites, and thereby, higher tendency to form aggregates during the transformation treatment.
  • Fig. 3 Typical characterization routine for bimetallic [M 2 -Z-(MI)MOF/MPM] precursor materials: FTIR, XRD, surface area and pore distribution.
  • Fig. 4a STEM images and EDS for carbon-free PdZr0 2 nanocatalysts confined within SBA-15 prepared from Pd-ST(Zr)UiO-66(NH 2 )/SBA-l5 treated via pyrolysis under nitrogen at 650 °C.
  • Fig. 4b STEM images and EDS for PdZr0 2 nanocatalysts confined within SBA-15 prepared from Pd-SI-(Zr)UiO-66(NH 2 )/SBA-l5 treated via calcination under oxygen at 500 °C.
  • Fig. 4c STEM images and EDS for Pd N c/(Zr)UiO-66(NH 2 ) nanocatalysts confined within SBA-15 prepared from Pd-SI-(Zr)UiO-66(NH 2 )/SBA-l5 treated via reduction under hydrogen at 200 °C.
  • FIG. 5 (left) TGA profiles for sample PdCl-ST(Zr)UiO-66(NH 2 )/SBA-l5 under nitrogen and air. (right) FTIR spectra of consecutive steps for the preparation of PdZr0 2 /SBA-l5 sample via pyrolysis under nitrogen at 900 C, as shown in Fig. 1.
  • Fig. 7 Application example of some results for C0 2 to fuels reaction catalyzed by Fe 3 0 4 /Si0 2 and FeC/Si0 2 catalysts at varying loadings prepared from (Fe)MIL-l00/SiO 2 compared to Clariant commercial catalysts.
  • Fig. 8 Application example of different C0 2 to fuels reaction catalyzed by FeC/Si0 2 at various ratio of H 2 /C0 2 .
  • This disclosure provides a novel strategy to prepare nano-sized catalyst via controlled transformation of MOF nanocrystals.
  • These catalysts may be optionally decorated with additional organometallic metal complexes or metal salts previously or afterwards confined within mesoporous materials and or optionally decorated with polymers, organometallic ligand precursors, nitrogen-containing organic compounds, phosphorous-containing organic compounds, sulfur-containing organic compounds, boron-containing organic compounds, halide salts, organic halides, metal atoms added via atomic layer deposition or chemical vapor deposition or other compounds previously or afterwards confined within mesoporous materials.
  • This general method preserves the dispersion, nano-sized dimension, and 3-D distribution along the mesoporous matrix of the pristine support precursor into the resulting catalysts, thus favoring the formation of nanometric and subnanometric active species (such as metals, metal oxides, N-doped carbons, P- doped carbons, S-doped carbons, B-doped carbons, halide-doped carbons, and combinations thereof) with high precision by using proper selection of the hybrid precursors, (i.
  • organometallic metal complex e., organometallic metal complex, metal salt, polymer, organometallic ligand precursor, nitrogen- containing organic, phosphorous-containing organic, sulfur-containing organic, boron-containing organic, halide salts, organic halides, MOF and mesoporous scaffold).
  • the transformation treatment can be done at three different conditions: pyrolysis, calcination or reduction. Additional properties are conferred by confining the resulting supported nanocatalysts in the mesoporous scaffold, such as enhanced diffusion, improved chemical stability, excellent attrition resistance as well as feasible handling, as recently reported for the hybrid MOF/MPMs materials (Luz, I.; Soukri, M.; Lail, M.: Confining Metal- Organic Framework Nanocrystals within Mesoporous Materials: A General Approach via“Solid- State” Synthesis. Chemistry of Materials 2017 29 9628-9638).
  • MOFs have been widely used as versatile precursors for preparation of catalytically active materials upon applying certain conditions, such as controlled pyrolysis under nitrogen or other inert gas, calcination under oxygen or reduction under hydrogen or other reducing gas.
  • the resulting solid catalysts can be composed of metals, metal oxides, nitrogen-doped carbon, phosphorous-doped carbon, sulfur-doped carbon, boron-doped carbon, halide-doped carbon, and combinations thereof (Wei et al. 2017).
  • nano-sized MOF domains (5-50 nm diameter) as precursor instead of bulkier particles can offer some advantages from the catalytic point of view, as they can lead to the isolation of a reduced number of metallic atoms in a single crystal, or cluster (Liu, L. C.; Diaz, U.; Arenal, R.; Agostini, G.; Concepcion, P.; Corma, A.: Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nature Materials 2017, 16, 132-138), upon one of the treatments mentioned above.
  • an aqueous solution of an organic ligand salt of the formula A X (L X ) is contacted with a mesoporous material (MPM) present at a concentration in the range of 10-300 mg/mL, preferably 25-275 mg/mL, preferably 50-250 mg/mL to form an impregnated mesoporous salt material of the formula A X (L X )/MPM.
  • MPM mesoporous material
  • Exemplary salts include, but are not limited to, mineral or organic acid salts of basic groups such as amines, and alkali or organic salts of acidic groups such as carboxylic acids.
  • the salts include, but are not limited to, the conventional non-toxic salts or the quaternary ammonium salts of the parent compound formed, for example, from non-toxic inorganic or organic acids.
  • Salts of carboxylic acid containing ligands may include cations such as lithium, sodium, potassium, magnesium, additional alkali metals, and the like.
  • the salts include, but are not limited to, the conventional non-toxic salts or the quaternary ammonium salts of the parent compound formed, for example, from non-toxic inorganic or organic acids.
  • the salts are alkali metal salts, most preferably sodium salts.
  • the contacting is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a contacting time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2- 12 hours, preferably 2.5-8 hours, preferably 3-6 hours.
  • the ligand i.e. acid form; 2,6-dihydoxyterephthalic acid
  • organic solvents include, but are not limited to, methanol, ethanol, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, acetone, and the like.
  • the impregnated mesoporous salt material present at a concentration in the range of 10-300 mg/mL, preferably 25-275 mg/mL, preferably 50-250 mg/mL is treated with a gas phase acid to form an impregnated mesoporous acid material of the formula H X (L X )/MPM.
  • the gas phase acid may be an inorganic acid such as HC1.
  • the gas treatment is performed at a temperature of up to 150 °C, preferably 10-120 °C, preferably 15-110 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a treating time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2-12 hours, preferably 2.5-8 hours, preferably 3-6 hours.
  • the temperature will depend on the choice of the acid.
  • An organic acid may be at a temperature of 100 °C ⁇ 50 °C, preferably 100 °C ⁇ 20 °C, preferably 100 °C ⁇ 10 °C, preferably 100 °C ⁇ 5 °C.
  • treatment with nitrogen saturated with HC1 might be a 30 °C ⁇ 20 °C, preferably 30 °C ⁇ 10 °C, preferably 30 °C ⁇ 5 °C.
  • the bound ligand may be treated with an aqueous acidic solution of 0.05- 10.0 M in concentration, preferably 0.1-9.0 M, preferably 1.0-8.0M, preferably 2.0-6.0 M, or about 4.0 M to form an impregnated mesoporous acid material of the formula H X (L X )/MPM.
  • Strong acids including, but not limited to, HC1, H 2 S0 4 , and HN0 3 are preferred, but organic acids and weak acids (i.e. acetic acid) may also be used in the treating, most preferably HC1.
  • the solution treatment is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a treating time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2- 12 hours, preferably 2.5-8 hours, preferably 3-6 hours.
  • the impregnated mesoporous acid material present at a concentration in the range of 10-300 mg/mL, preferably 25-275 mg/mL, preferably 50-250 mg/mL, is contacted with an aqueous solution of a metal precursor of the formula M +y to form an impregnated mesoporous metal organic framework precursor.
  • the contacting is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a contacting time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2-12 hours, preferably 2.5-8 hours, preferably 3-6 hours.
  • the impregnated mesoporous metal organic framework precursor is heated in the absence of a solvent or exposed to a volatile vapor (i.e. and amine such as methylamine or controlled moisture such as steam) in the absence of a solvent to form a hybrid material of the formula (M +y L x )/MPM, or hereafter called MOF/MPM.
  • the metal ions form coordinate bonds with the one or more organic ligands, preferably multidentate organic ligands to form a nano-crystalline metal organic framework in the pore spaces of the mesoporous material.
  • the heating is performed at a temperature of up to 300 °C, preferably 40-250 °C, preferably 60-220 °C, preferably 100-200 °C, preferably 120-190 °C, and has a heating time of up to 60 hours, preferably 12-48 hours, preferably 24-36 hours.
  • the exposing to a vapor is performed at a temperature of up to 80 °C, preferably 10- 80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a heating time of up to 48 hours, preferably 6-36 hours, preferably 12-24 hours.
  • a catalytic amount of a specific additive including (preferably 15 %), but not limited to, methanol, ethanol, tetrahydrofuran, N,N-dimethylformamide, and the like may be employed to assist the crystal formation within the hybrid material.
  • the MOF/MPM is treated with an organic compound to form another ligand and then treated with at least one or multiple additional metal to create a bound with the MOF.
  • the MOF/MPM (mono-, bi-, tri-, polymetallic) is contacted with a solution containing salts of additional metal catalysts or promoters. The modified MOF/MPM is then dried and treated with the controlled transformation conditions described below.
  • the embedded MOF or MOF/MPM is subjected to controlled transformation conditions to generate the confined nanocatalyst.
  • the controlled transformation may be (1) pyrolysis under nitrogen or other inert gas: where nanocrystals are obtained when the transformation is carried out under nitrogen (or other inert gas such as Ar or a reactive gas such as acetylene) for temperatures ranging from 300 °C to 1000 °C.
  • the temperatures ranging from 300 °C to 500 °C, preferably 400 - 600 °C, preferably 500 - 700 °C, preferably 600 - 800 °C, preferably 700 - 900 °C, preferably 800 - 1000 °C.
  • the controlled transformation may be (2) calcination in an oxygen containing atmosphere. All organic materials are released at lower temperatures when an oxygen containing atmosphere is present in the transformation treatment. Carbon-free nanocatalysts are obtained for temperatures of 300 - 600 °C, preferably 300 - 350 °C, preferably 400 - 450 °C, preferably 450 - 500 °C, preferably 500 - 550 °C, preferably 550 - 600 °C.
  • the controlled transformation may be (3) reduction with an atmosphere containing hydrogen.
  • the temperatures are still milder (from room temperature to 300 °C).
  • the MOF carbon micro structure is not completely decomposed, although the transition metal cations decorating the MOF nanocrystal are reduced to form a metallic nanocrystal confined within the microporous cavities of the MOF and/or MPM.
  • the temperature for the reductive transformation is from 25 - 50 °C, preferably 50 - 75 °C, preferably 75 - 100 °C, preferably 100 - 125 °C, preferably 125 - 150 °C, preferably 150 - 175 °C, preferably 175 - 200 °C, preferably 200 - 225 °C, preferably 225 - 250 °C, preferably 250 - 275 °C, preferably 275 - 300 °C.
  • the confined metallic nanocrystal is present only within the mesopores or void spaces of the mesoporous material and homogeneously dispersed within the mesopores or void spaces of the mesoporous material.
  • “disposed on”,“embedded” or“impregnated” describes being completely or partially filled throughout, saturated, permeated and/or infused.
  • the confined metallic nanocrystal may be affixed substantially within the pore space of the mesoporous material.
  • the confined metallic nanocrystal may be affixed to the mesoporous material in any reasonable manner, such as physisorption or chemisorption and mixtures thereof.
  • greater than 10% of the pore spaces of the mesoporous material is occupied by the confined metallic nanocrystal, preferably greater than 15%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%, preferably greater than 45%, preferably greater than 50%, preferably greater than 55%, preferably greater than 60%, preferably greater than 65%, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 85%, preferably greater than 90%, preferably greater than 95%, preferably greater than 96%, preferably greater than 97%, preferably greater than 98%, preferably greater than 99%.
  • 5-10% of the pore spaces of mesoporous material may be occupied.
  • the confined metallic nanocrystal is substantially present only within the mesopores or void spaces of the mesoporous material and homogeneously dispersed on the external surface of the mesoporous material, preferably greater than 60% of the confined metallic nanocrystal is located in the pore spaces and not at the surface of the mesoporous material, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 85%, preferably greater than 90%, preferably greater than 95%, preferably greater than 96%, preferably greater than 97%, preferably greater than 98%, preferably greater than 99%.
  • homogeneous dispersion refers to dispersion in a similar or the same manner and may refer to uniform structure and composition.
  • the coefficient of variation of the nanocatalysts are distributed in the MPM is less than 10%, preferably less than 8%, preferably less than 6%, preferably less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%.
  • the surface of the MPM is generally substantially free from the nanocatalysts.
  • the method further comprises drying at least one selected from the group consisting of the impregnated mesoporous salt material, the impregnated mesoporous acid material, the impregnated mesoporous metal organic framework precursor, and the hybrid material at a temperature in the range of 25-160 °C, preferably 85-150 °C, preferably 90-140 °C, preferably 100-130 °C, or about 120 °C under a vacuum and with a drying time of up to 24 hours, preferably 0.5-18 hours, preferably 1-12 hours, preferably 1.5-6 hours, or about 2 hours.
  • the method further comprises washing the hybrid material with distilled water or other polar protic solvent and extracting water from the hybrid material in a Soxhlet system recycling methanol or other polar protic solvent.
  • the mesoporous material is at least one selected from the group consisting of a mesoporous metal oxide (aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, magnesium oxide, etc.), a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, and a mesoporous aluminophosphate, etc.).
  • a mesoporous metal oxide aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, magnesium oxide, etc.
  • a mesoporous silica a mesoporous carbon
  • zeolite me
  • a mesoporous material may refer to a material containing pores with diameters between 2-50 nm, porous materials are classified into several kinds by their pore size.
  • the mesoporous material has a percent porosity of greater than 10%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%
  • the organic ligand (L x ) of the organic ligand salt is at least one selected from the group consisting of polycarboxylate ligands, azaheterocyclic ligands, and derivatives thereof.
  • ligand refers to a mono-dentate or polydentate compound that bind a transition metal or a plurality of transition metals, respectively.
  • a linking moiety comprises a substructure covalently linked to an alkyl or cycloalkyl group, comprising 1 to 20 carbon atoms, an aryl group comprising 1 to 5 phenyl rings, or an alkyl or aryl amine comprising alkyl or cycloalkyl groups having from 1 to 20 carbon atoms or aryl groups comprising 1 to 5 phenyl rings, and in which a linking cluster (e.g., a multidentate function groups) are covalently bound to the substructure.
  • a linking cluster e.g., a multidentate function groups
  • a cycloalkyl or aryl substructure may comprise 1 to 5 rings that comprise either of all carbon or a mixture of carbon with nitrogen, oxygen, sulfur, boron, phosphorus, silicon and/or aluminum atoms making up the ring.
  • the linking moiety will comprise a substructure having one or more carboxylic acid linking clusters covalently attached.
  • the organic ligand (L x ) of the organic ligand salt is at least one selected from the group consisting of, terephthalate, benzene-l,3,5-tricarboxylate, 2,5- dioxibenzene dicarboxylate, biphenyl-4,4’ -dicarboxylate and derivatives thereof.
  • the organic ligand (L x ) of the organic ligand salt is at least one selected from the group consisting of imidazolate, pyrimidine-azolate, triazolate, tetrazolate and derivatives thereof. Additional suitable exemplary ligands include, but are not limited to, bidentate carboxylics (i.e.
  • the metal (M +y ) of the metal precursor is at least one transition metal selected from the group consisting of Mg, V, Cr, Mo, Zr, Hf, Mn, Fe, Co, Cu, Ni, Zn, Ru, Al, and Ga.
  • metal ion is selected from the group consisting of elements of groups la, Ila, Ilia, IVa to Villa and IB to VIb of the periodic table of the elements.
  • the metal precursor may comprise clusters of metal oxides.
  • the metal organic framework is at least one selected from the group consisting of MIL-101, MIL-100, MIL-53, MOF-74, UiO-66, UiO-67, ZIF-8, ZIFs, HKUST-l, M 2 (dobpdc), NU-1000, PCN-222, PCN-224, and derivatives thereof.
  • a metal organic framework may refer to compounds consisting of metal ions or clusters coordinated to organic ligands to form one-, two- or three-dimensional structures, with the special feature of porosity. More formally, a metal organic framework is a coordination network with organic ligands containing potential voids.
  • the nano-crystalline MOF has a percent porosity of greater than 10%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%.
  • MOFs are composed of two major components: a metal ion or cluster of metal ions and an organic molecule often termed a linker. The organic units are typically mono-, di-, tri-, or tetravalent ligands. The choice of metal and linker will dictate the structure and hence properties of the MOF. For example, the metal's coordination preference influences the size and shape of pores by dictating how many ligands can bind to the metal and in which orientation.
  • the hybrid material has a weight percentage of the metal organic framework in the range of 5-50% relative to the total weight of the hybrid material, preferably 15-45%, preferably 25-40%, preferably 30-35%, or at least 20%, preferably at least 25%, preferably at least 30%, preferably at least 35%, preferably at least 40%, preferably at least 45%.
  • the mesoporous material comprises mesopores with an average diameter in the range of 2-50 nm, preferably 4-45 nm, preferably 6-40 nm and micropores with an average diameter in the range of 0.5-5.0 nm, preferably 1.0-4.5 nm, preferably 2.0-4.0 nm.
  • the mesopores, the micropores, or both are monodisperse having a coefficient of variation of less than 10%, preferably less than 8%, preferably less than 6%, preferably less than 5%, preferably less than 4%, preferably less than 3%.
  • the hybrid material has a percent porosity of greater than 10%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%. In a preferred embodiment, the hybrid material has a reduced mesoporosity relative to the bare mesoporous material and an increased microporosity relative to the bare mesoporous material.
  • the confined metallic nanocrystal has an average longest linear dimension of less than 10 nm, preferably less than 8 nm, preferably less than 5 nm, preferably less than 2.5 nm.
  • the MPM has a surface area in the range of 100-1200 m 2 /g, preferably 200-1100 m 2 /g, preferably 300-1000 m 2 /g, preferably 400-900 m 2 /g, preferably 500- 950 m 2 /g, preferably 600-900 m 2 /g, preferably 700-850 m 2 /g, or at least 400 m 2 /g, preferably at least 600 m 2 /g, preferably at least 800 m 2 /g, preferably at least 1000 m 2 /g.
  • the terms“about” and/or“approximately” may be used in conjunction with numerical values and/or ranges.
  • the term“about” is understood to mean those values near to a recited value.
  • “about 40 [units]” may mean within ⁇ 25% of 40 (e.g., from 30 to 50), within ⁇ 20%, ⁇ 15%, ⁇ 10%, ⁇ 9%, ⁇ 8%, ⁇ 7%, ⁇ 6%, ⁇ 5%, ⁇ 4%, ⁇ 3%, ⁇ 2%, ⁇ 1%, less than ⁇ 1%, or any other value or range of values therein or there below.
  • the phrases“less than about [a value]” or“greater than about [a value]” should be understood in view of the definition of the term“about” provided herein.
  • the terms “about” and“approximately” may be used interchangeably.
  • ranges are provided for certain quantities. It is to be understood that these ranges comprise all subranges therein. Thus, the range “from 50 to 80” includes all possible ranges therein (e.g., 51-79, 52-78, 53-77, 54-76, 55-75, 60- 70, etc.). Furthermore, all values within a given range may be an endpoint for the range encompassed thereby (e.g., the range 50-80 includes the ranges with endpoints such as 55-80, 50- 75, etc.).
  • the verb“comprise” as is used in this description and in the claims and its conjugations are used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded.
  • the word“comprising,” or variations such as“comprises” or“comprising,” will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
  • the present disclosure may suitably“comprise”,“consist of’, or“consist essentially of’, the steps, elements, and/or reagents described in the claims.
  • PLTBAPy l,3,6,8-tetrakis(p-benzoic acid)pyrene
  • MCM-41 was provided by Claytec (East Lansing, MI), g-A1 2 0 3 by Sasol (Houston, TX), Ti0 2 by Sachtleben (Hausach, Germany) and Zr0 2 by Mel Chemicals (Manchester, UK).
  • Mesoporous carbon and HayeSep A (Supelco) [100-120 pm] were supplied by Sigma-Aldrich. All mesoporous materials were degassed at 120 °C overnight under vacuum to remove the adsorbed water.
  • Ligand salt precursors Na 2 BDC and Na 3 BTC ligand salt precursors were prepared from their acid form in water with the stoichiometric amount of NaOH necessary to deprotonate the carboxylic acid of the organic linker followed by a purification step via precipitation in acetone.
  • ligand salt precursor solutions for H 2 BDC(NH 2 ), H 2 BpyDC, H 4 TCPP and H 4 TBAPy were directly prepared with the stoichiometric amount of TEA, thereby skipping the step of isolating the ligand salt.
  • H 2 BDC(S0 3 Na) and HMelM were directly dissolved in water.
  • H 4 DOBDC was dissolved in hot THF due to the insolubility in water of sodium 2,5- dioxyterephthalate coordination polymers. The use of triethylammonium salts did not give rise the targeted MOF-74 structure.
  • TEM Transmission Electron Microscopy
  • TGA Thermogravimetric Analyzer
  • N2 sorption isotherms The samples were analyzed in a Micromeritics ASAP (Accelerated Surface Area and Porosimetry) 2020 System. Samples were weighted into tubes with seal frits and degassed under vacuum ( ⁇ 500 pm Hg) with heating. They were initially heated at 150 °C and held for 4 hours, and finally cooled to room temperature and backfilled with N 2 . The samples were re-weighted before analysis. The analysis adsorptive was N 2 at 77K. A multi-point BET surface area was determined from 6 measurements at relative pressures (P/Po) ranging from 0.050 to 0.300 satisfying the four criteria suggested by Rouquerol. See Gomez-Gualdron, D. A., Moghadam, P.
  • FTIR ATR and DRIFTS cell.
  • ATR absorption spectroscopy measurements were performed in the range of 4000-400 cm-l with a Perkin Elmer Spectrum 100 FTIR spectrometer.
  • The‘in situ’ DRIFTS experiments were carried out in a Praying Mantis cell by injecting a nitrogen flow saturated with water for assisting the vapor-phase crystallization at 120 °C.
  • single metal and metal oxide nanocrystals have been prepared via controlled transformation procedures by using selected supported MOF nanocrystals on mesoporous silica as precursors.
  • bimetallic metal oxide nanocrystals have also been prepared by an additional multistep post-synthesis modification (PSM) of the MOF hybrid precursors carried out before controlled transformation, which includes a gas-phase functionalization (see Table 1 and Fig. 1 and 2) (Servalli, M.; Ranocchiari, M.; Van Bokhoven, J. A.: Fast and high yield post-synthetic modification of metal-organic frameworks by vapor diffusion.
  • PSM post-synthesis modification
  • Bimetallic [PdCl-SI-(Zr)UiO-66(NH 2 )/SBA-15] precursor was prepared via solid- state synthesis by following this general procedure: 1) multi-step incipient wetness impregnation of MOF precursor solutions on SBA-15, 2) treatment at specific conditions, 3) general washing treatment, 4) vapor phase post-synthesis functionalization (solid state), and 5) liquid phase post synthesis metalation.
  • All bimetallic [M2-Z-(MI)MOF/MPM] precursors can be prepared by the following general procedure (steps 1 to 5) as described previously (Cirujano et al. 2017 and PCT Patent Appn. PCT/US2017/046231).
  • Monometallic [(Mi)MOF/MPM] precursors are prepared by following only the three first steps (1-3).
  • a ligand salt precursor solution (TEA) 2 BDC(NH 2 ) was prepared by dissolving H 2 BDC(NH 2 ) (1.5 g) loading and TEA (2.5 mL) in 35 mL of water.
  • the resulting dry intermediate [(TEA) 2 BDC(NH 2 )/SBA-l5] was placed in a fluidized bed reactor where it was first treated with a nitrogen flow saturated with concentrated HC1 (37%) for 2 hours at room temperature and eventually purged with a nitrogen flow for 2 h to remove the excess HC1.
  • the metal salt precursor solution prepared by dissolving 2.5 g of Zr0Cl 2 - 8H 2 0 in 30 mL of water, was used to impregnate the [H 2 BDC(NH 2 )/SBA- 15] mesoporous silica.
  • the metal cation was chelated to the intermediate material containing the Schiff base [ST(Zr)UiO-66(NH 2 )/SBA-l5] by soaking for 2-3 hours at room temperature in a solution containing PdCl 2 (CH 3 CN) (200 mg) in THF (5mL). Afterwards the material was washed with MeOH and dried at 80 °C under vacuum to obtain the precursor [PdCl-SI-(Zr)UiO-66(NH 2 )/SBA- 15] containing 1.7 wt.% of Pd, according to XRF.
  • a selective PSM of the free amino groups located at the ligands of numerous MOF structures such as (Zr)UiO-66(NH 2 ), (Al)MIL-53(NH 2 ), (Ti)MIL-l25(NH 2 ), (Zn)IRMOF-3(NH 2 ), (V)MIL- 101(NH 2 ), (Fe)MIL-53(NH 2 ), among others, have been functionalized via gas phase treatment with salicylaldehyde vapor at 110 °C to fully convert amino groups into Schiff-base ligands (salicyclidene-imine, SI) (see Fig.
  • SI Schiff-base ligands
  • Fig. 5 shows FTIR characterization of the conversion of amino groups into Schiff-base ligands (SI) during subsequent steps of the synthesis. Subsequently, numerous metal cations have been selectively chelated to the resulting Schiff base by soaking the solid material in a solution containing a metal salt, such as Pd, Pt, Au, Cu, Ni, Mo, Ir, Rh, among others.
  • a metal salt such as Pd, Pt, Au, Cu, Ni, Mo, Ir, Rh, among others.
  • the faster functionalization rates observed for MOF hybrids compared to bulk MOFs is mainly due to the smaller particle size, excellent dispersion of the MOF nanocrystals within mesoporous silicas, and concentration of MOF nanocrystal on the surface of the support.
  • Metallic nanocrystals are obtained when the transformation is carried out under nitrogen or other inert gas for temperatures ranging from 300 to 1000 °C. In some embodiments, this treatment transforms the organic composition of MOF nanocrystals into carbonaceous species. Nevertheless, TGA and elemental analysis data reveals the complete‘de-carbonization’ of MOF nanocrystals leading to carbon- or graphene-free bimetallic nanocatalysts takes place for temperatures of pyrolysis above 600-700 °C. This is in contrast to the bulk MOF (above 100 nm) (see Fig. 5 TGA FTIR comparison), in which microporous carbonaceous structures are remaining upon treatment. See Tang, J.; Salunkhe, R.
  • a hydrogen containing atmosphere When a hydrogen containing atmosphere is used, controlled transformation occurs at milder temperatures (from room temperature to 300 °C). Under these conditions, the MOF carbon microstructure is not completely decomposed, although the transition metal cations decorating the MOF nanocrystal are reduced to form a monometallic nanocrystal confined within the microporous cavities of the MOF. Formation of subnanometric metal nanocrystals are confined within the microporous MOF.
  • Fig. 4c shows STEM images of the nanocatalyst prepared by reduction in a hydrogen containing atmosphere.
  • Ru/Si0 2 was synthesized with good yield, providing material for testing in a 2- gram fixed-bed micro-reactor. Before being converted into nanocatalysts, the structure of Ru- HKUST-l was confirmed by matching X-ray Diffraction (XRD), Fourier Transformed Infrared Spectroscopy (FTIR), and BET surface area measurement showing increase in surface area of the silica composite correlated to the presence of MOF. Ru-HKUST-l was then converted into ruthenium nanoparticles using a 900 °C heat treatment with a slow temperature ramp.
  • XRD X-ray Diffraction
  • FTIR Fourier Transformed Infrared Spectroscopy
  • BET surface area measurement showing increase in surface area of the silica composite correlated to the presence of MOF.
  • Ru-HKUST-l was then converted into ruthenium nanoparticles using a 900 °C heat treatment with a slow temperature ramp.
  • the high surface area and long-range structure of the MOF breaks down as certain components of the organic linker are gasified and released as C0 2 .
  • Monoatomic ruthenium is released from complexation and deposited on the surface among the residual organic fragments. Ruthenium atom agglomeration occurs at high temperature, and small, well-dispersed, ruthenium nanoparticles are formed on the surface of the support.
  • FNHCs Fluidized-Nanoreactor Hydrogen Carriers
  • FNHCs Fluidized-Nanoreactor Hydrogen Carriers
  • OHCs consist on the chemical hydrogen storage by binding H 2 to hydrogen-lean molecules by catalytic hydrogenation reactions, which can release via catalytic dehydrogenation.
  • the bound-H 2 may be used as fuel for several applications, ranging from realistic‘off-board’ hydrogen filling stations to futuristic‘on-board’ hydrogen generation on mobile platforms, such as in cars or space ships (Preuster, P.; Papp, C.; Wasserscheid, P.: Liquid Organic Hydrogen Carriers (LOHCs): Toward a Hydrogen -free Hydrogen Economy. Accounts of Chemical Research 2017, 50, 74-85.)
  • LOHCs Liquid Organic Hydrogen Carriers
  • H X -FNHC hydrogen-loaded FNHC
  • Fe catalysts were prepared via direct conversion of (Fe)MIL-l00/SiO 2 by using two different transformation conditions at 500 C, air and nitrogen, to form Fe 3 0 4 /Si0 2 and FeC/Si0 2 , respectively. These two catalysts were evaluated for thermal transformation of CO2 to fuels using hydrogen. An example of some of the results obtained by these catalysts containing varying loading of Fe at 320 °C, 30 bar and GHSV of 4000 h 1 are shown in Fig.7 and 8. (Wei, J.; Ge, Q.; Yao, R.; Wen, Z.; Fang, C.; Guo, L.; Xu, H.; Sun, J.: Directly converting CO2 into a gasoline fuel. Nature Communications 2017, 8, 15174-82.)
  • a method of preparing a confined metallic nanocatalyst within a mesoporous material which comprises: (a) impregnating at least one or more organic compound, comprising one or more multidentate ligand(s) [A X (L X )] capable of forming coordination bonds with at least one metal ion, on the mesoporous material to form a first intermediate [(A X (L X )/MPM)] ; (b) exposing the first intermediate [(A X (L X ) /MPM)] to an acid in gas phase to form a second intermediate [(H X (L X )/MPM)] ; (c) adding to the second intermediate [(H X (L X )/MPM)] a solvent solution of one or more metal ions (Mi +y , M2 +y , M 3 +y ) so as to form coordination bonds with the one or more multidentate ligand(
  • step (d) further comprises step (d)(1) comprising contacting the precursor of step (c) [MOF /MPM] with one or more organic compounds (Z) to make a second multidentate ligand capable of forming coordination bonds [Z/MOF /MPM]; and step (d)(2) adding a solvent solution of one or more additional metal ion to form a modified MOF precursor with additional metals confined within the mesoporous material [MOF/MPM]
  • Statement 3 The method of Statements 1 or 2, wherein the chelating ligand (Z) in step (d)(1) comprises a metal binding site for complexing a second metal ion.
  • Statement 4 The method of Statements 1-3, wherein the controlled transformation conditions cause greater than 90% of the carbon in the MOF to be released from the MOF/MPM.
  • Statement 5 The method of Statements 1-4, wherein the controlled transformation conditions cause 50% ⁇ 10% of the carbon in the MOF to be released from the MOF/MPM.
  • Statement 6 The method of Statements 1-5, wherein the treating under controlled transformation conditions is pyrolysis at a temperature of about 300 °C to about 1000 °C in an inert gas atmosphere.
  • Statement 7 The method of Statements 1-6, wherein the treating under controlled transformation conditions is calcination at a temperature of about 300 °C to about 600 °C in an atmosphere containing oxygen gas.
  • Statement 8 The method of Statements 1-7, wherein the treating under controlled transformation conditions is reduction with hydrogen at a temperature of about 25 °C to about 300 °C.
  • Statement 10 The method of Statements 1-8, wherein the confined nanocatalyst is bimetallic (MI+M 2 ).
  • Statement 11 The method of Statements 1-8, wherein the confined nanocatalyst has 3 or more metals.
  • Statement 12 The method of Statements 1-11, wherein the confined nanocatalyst within the mesoporous material has a diameter of less than 10 nm.
  • Statement 13 The method of Statements 1-12, wherein the mesoporous material is a mesoporous metal oxide, a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, or a mesoporous aluminopho sphate .
  • the mesoporous material is a mesoporous metal oxide, a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, or a meso
  • Statement 14 The method of Statement 12, wherein the mesoporous metal oxide is aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, or magnesium oxide.
  • Statement 15 The method of Statements 1-13, wherein the mesoporous material has a surface area of about 100 m 2 /g to about 1000 m 2 /g.
  • Statement 17 The method of Statements 1-16, wherein the multidentate ligand for the MOF is selected from the group consisting of, terephthalate, benzene-l,3,5-tricarboxylate, 2,5- dioxibenzene dicarboxylate, biphenyl-4,4’ -dicarboxylate, imidazolate, pyrimidine-azolate, triazolate, tetrazolate, derivatives or combinations thereof.
  • the multidentate ligand for the MOF is selected from the group consisting of, terephthalate, benzene-l,3,5-tricarboxylate, 2,5- dioxibenzene dicarboxylate, biphenyl-4,4’ -dicarboxylate, imidazolate, pyrimidine-azolate, triazolate, tetrazolate, derivatives or combinations thereof.
  • Statement 18 The method of Statements 1-16, wherein the MOF is selected from HKUST-l, M 2 (dobpdc), MIL-100, MIL-101, MIL-53, MOF-74, NU-1000, PCN-222, PCN-224, UiO-66, UiO-67, ZIF-8, ZIFs, or derivatives thereof.
  • Statement 19 The method of Statements 1-18, wherein the mesoporous material is selected from the group consisting of, MCM-41, SBA-15, or commercially available silica.
  • Statement 20 The method of Statements 1-19, wherein the confined nanocatalyst confined within mesoporous material is further reacted with additional organometallic metal complexes or metal salts with polymers, organometallic ligand precursors, nitrogen-containing organic compounds, phosphorous-containing organic compounds, sulfur-containing organic compounds, boron-containing organic compounds, halide salts, organic halides, or metal atoms added via atomic layer deposition or chemical vapor deposition.
  • Statement 20 A catalyst made by the method of Statements 1-19.
  • Statement 21 The catalyst of Statement 20, further comprising an added metal promotor.
  • Statement 22 The use of the catalyst of Statements 20 or 21, to catalyze alkene ammoxidation reactions, alkene epoxidation, ammonia synthesis, carboxylation reactions, C0 2 methanation reactions, conversion of C0 2 to fuel, direct methanol synthesis from methane, dry- methane reforming, electrocatalytic ammonia oxidation, electrocatalytic oxygen reduction reactions, Fischer-Tropsch synthesis, hydro -/dehydrogenation of liquid organic hydrogen carriers, hydrotreating and hydroprocessing esterification reactions, methanol synthesis from syngas, reverse water-gas shift reactions, or water-gas shift reactions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Toxicology (AREA)
  • Plasma & Fusion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Optics & Photonics (AREA)
  • Analytical Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present disclosure provides methods of making confined nanocatalysts within mesoporous materials (MPMs). The methods utilize solid state growth of nanocrystalline metal organic frameworks (MOFs) followed by controlled transformation to generate nanocatalysts in situ within the mesoporous material. The disclosure also provides applications of the nanocatalysts to a wide variety of fields including, but not limited to, liquid organic hydrogen carriers, synthetic liquid fuel preparation, and nitrogen fixation.

Description

METHOD OF MAKING CONFINED NANOCATALYSTS WITHIN MESOPOROUS
MATERIALS AND USES THEREOF
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0001] This invention was made with government support under DE-AR0000811 awarded by the Department of Energy and DE-FE0026432 awarded by the Department of Energy. The government has certain rights in the invention.
Cross Reference to Related Applications
[0002] This application is related to and claims priority to U.S. Provisional Patent Application No. 62/647,949, filed on March 26, 2018, entitled“METHOD OF MAKING CONFINED NANOCATALYSTS WITHIN MESOPOROUS MATERIALS AND USES THEREOF,” the entire contents of which are incorporated herein by reference.
1. FIELD
[0003] The present disclosure provides methods of making confined nanocatalysts within mesoporous materials (MPMs). The methods utilize solid state growth of nanocrystalline metal organic frameworks (MOFs) followed by controlled transformation to generate nanocatalysts in situ within the mesoporous material. The disclosure also provides applications of the nanocatalysts to a wide variety of fields including, but not limited to, liquid organic hydrogen carriers, synthetic liquid fuel preparation, and nitrogen fixation.
2. BACKGROUND
2.1. Introduction
[0004] The “background” description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against the present disclosure.
[0005] Metal organic frameworks (MOFs) have been widely used as versatile precursors for the preparation of catalytically active materials upon applying certain conditions, such as controlled pyrolysis under nitrogen, calcination under oxygen or reduction under hydrogen - . Lee, K. J.; Lee, J. H.; Jeoung, S.; Moon, H. R.: Transformation of Metal-Organic Frameworks/Coordination Polymers into Functional Nanostructured Materials: Experimental Approaches Based on Mechanistic Insights, Accounts of Chemical Research 2017, 50, 2684-2692. The versatility of MOFs as precursors is mainly due to their unique and highly tunable features, such as well-defined metal sites spaced by organic struts displayed along a crystalline structure with permanent porosity, which can play two simultaneous roles acting as template and precursor. Upon transformation, MOFs can lead to well defined nanostructured catalytically active species, which are monodispersed within hierarchical scaffolds, depending on the conversion conditions, i.e., microporous metal oxide under oxidant conditions or microporous carbonaceous matrix under inert conditions. The resulting nanostructured catalysts can be composed by metals, metal oxides, heteroatom-doped carbon and combinations thereof (Wei, J.; Ge, Q.; Yao, R.; Wen, Z.; Fang, C.; Guo, L.; Xu, H.; Sun, J.: Directly converting C02 into a gasoline fuel Nat. Commun 2017, 8, 15174 doi: l0. l038/ncommsl5l74).
[0006] The use of nano-sized MOF domains (5-50 nm) as precursor instead of bulkier particles can offer some advantages from the catalytic point of view after transformation, as they can lead to the isolation of a reduced number of metallic or metal oxide atoms, and even forming sub nanometric crystalline domains or denominated clusters (Liu, L. C.; Diaz, U.; Arenal, R.; Agostini, G.; Concepcion, P.; Corma, A.: Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nature Materials 2017, 16, 132-138). However, the use of free-standing MOF nanocrystals as precursors is problematic due to their poor stability under high temperatures that may promote their fusion into larger aggregates under the required transformation conditions, thereby leading to the same scenario than starting from bulkier MOF precursors. Therefore, novel synthetic routes are highly demanded to avoid MOF nanocrystalline precursors from sintering during high temperature treatments, thus paving the way to the development of new generation of MOF-derived nanocatalysts.
[0007] A general method for selective confinement of MOF nanocrystals within mesoporous materials (MPMs) via ‘solid-state’ synthesis was recently reported. This versatile approach provides high level of design over the resulting hybrid material formulation and nanoarchitecture, such as composition, loading and dispersion of the MOF guest as well as composition, pore size distribution and particle size of the mesoporous material host. MOF crystalline domains are always restricted to the dimensions delimited by the hosting cavity of the mesoporous material. In the same way, their superior performance as heterogeneous catalysts for synthesis of testosterone derivatives was recently demonstrated (Cirujano, F. G.; Luz, L; Soukri, M.; Van Goethem, C.; Vankelecom, I. F. J.; Lail, M.; De Vos, D. E.: Boosting the Catalytic Performance of Metal- Organic Frameworks for Steroid Transformations by Confinement within a Mesoporous Scaffold. Angewandte Chemie International Edition, 2017, 56, 13302-13306). In addition, C02 capture capacity as fluidized hybrid sorbents for post-combustion flue gas of these hybrid MOF/MPM materials compared to the‘state-of-the-art’, as well as other applications. See PCT Patent Appn. PCT/US2017/046231, Research Triangle Institute.
[0008] Recently, Li et al. disclosed the direct conversion of single MOF nanocrystals supported on the external surface of a layered double hydroxide (LDH) into single metal or metal oxide nanocrystals by heating in air or heating under a reductive atmosphere, respectively (Li, P.; Zeng, H. C.: Immobilization of Metal-Organic Framework Nanocrystals for Advanced Design of Supported Nanocatalysts. ACS Applied Materials & Interfaces 2016, 8, 29551-29564). The authors note the benefits dispersing and stabilizing effects of the LDH support for obtaining well- dispersed single metal or metal oxide nanocrystals. Li et al. approach does not show nanocatalysts, mesoporous materials as supports or bimetallic MOFs. On page 29552, Li et al. acknowledge that “nanoscale MOFs are unstable and prone to agglomeration and/or deterioration.” In addition, the resulting metal and metal oxide nanocrystals supported on this non-porous materials tend to suffer from sintering or fusion into a bulk phase.
3. SUMMARY OF THE DISCLOSURE
[0009] The present disclosure provides a method of preparing a confined metallic nanocatalyst within a mesoporous material (MPM) which comprises: (a) impregnating at least one or more organic compound, comprising one or more multidentate ligand(s) [AX(L X)] capable of forming coordination bonds with at least one metal ion, on the mesoporous material to form a first intermediate [(AX(L X)/MPM)] ; (b) exposing the first intermediate [(AX(L X) /MPM)] to an acid in gas phase to form a second intermediate [(HX(L X)/MPM)] ; (c) adding to the second intermediate [(HX(L X)/MPM)] a solvent solution of one or more metal ions (Mi+y, M2 +y, M3 +y) so as to form coordination bonds with the one or more multidentate ligand(s) forming a metal organic framework (MOF) precursor confined within a mesoporous material [MOF/MPM], and (d) treating the precursor of step (c) [MOF/MPM] under controlled transformation conditions so as to form the metallic nanocatalyst confined within the mesoporous material. [0010] In the method above, step (d) further may comprise step (d)(1) comprising contacting the precursor of step (c) [MOF /MPM] with one or more organic compounds (Z) to make a second multidentate ligand capable of forming coordination bonds [Z/MOF /MPM]; and step (d)(2) adding a solvent solution of one or more additional metal ion to form a modified MOF precursor with additional metals confined within the mesoporous material [MOF/MPM].
[0011] In the method above, the chelating ligand (Z) in step (d)(1) comprises a metal binding site for complexing a second metal ion.
[0012] In some embodiments, the controlled transformation conditions cause greater than 90% of the carbon in the MOF to be released from the MOF/MPM. In some cases, nearly 100% of the carbon may be released, e.g., greater than 95%, greater than 97%, greater than 99%.
[0013] In other embodiments, the controlled transformation conditions lead to 50% ± 10% of the carbon in the MOF to be released from the MOF/MPM. Alternatively, 30% ± 10%, 40% ± 10%, 60% ± 10% or 70% ± 10% may be released.
[0014] In some embodiments, the treating under controlled transformation conditions is pyrolysis at a temperature of about 300 °C to about 1000 °C in an inert gas atmosphere. More specifically, the inert atmosphere pyrolysis may be at 350 °C ± 50 °C, 400 °C ± 50 °C, 450 °C ± 50 °C, 500 °C ± 50 °C, 550 °C ± 50 °C, 600 °C ± 50 °C, 650 °C ± 50 °C, 700 °C ± 50 °C, 750 °C ± 50 °C, 800 °C ± 50 °C, 850 °C ± 50 °C, 900 °C ± 50 °C, or 950 °C ± 50 °C.
[0015] In other embodiments, the treating under controlled transformation conditions is calcination at a temperature of about 300 °C to about 600 °C in an atmosphere containing oxygen gas. More specifically, the calcination may be at 350 °C ± 50 °C, 400 °C ± 50 °C, 450 °C ± 50 °C, 500 °C ± 50 °C, or 550 °C ± 50 °C. The calcination atmosphere may be air. Alternatively, the calcination atmosphere may be enriched with oxygen or air depleted in oxygen but still containing a sufficient concentration of oxygen to react with the carbon in the MOF/MPM.
[0016] In still other embodiments, the treating under controlled transformation conditions is treatment in a reductive atmosphere, such as reduction with hydrogen at a temperature of about 25 °C to about 300 °C. More specifically, the calcination may be at 50 °C ± 25 °C, 75 °C ± 25 °C, 100 °C ± 25 °C, 125 °C ± 25 °C, 150 °C ± 25 °C, 175 °C ± 25 °C, 200 °C ± 25 °C, 225 °C ± 25 °C 250 °C ± 50 °C, or 275 °C ± 25 °C. The reductive atmosphere may be 100% hydrogen, 90 ± 5% hydrogen, 80 ± 5% hydrogen, 70 ± 5% hydrogen, 60 ± 5% hydrogen, 50 ± 5% hydrogen, 40 ± 5% hydrogen, 30 ± 5% hydrogen, 20 ± 5% hydrogen, or 10 ± 5% hydrogen. [0017] In some embodiments, the confined nanocatalyst is monometallic (Mi).
[0018] In other embodiments, the confined nanocatalyst is bimetallic (MI+M2).
[0019] In still other embodiments, the confined nanocatalyst has 3 or more metals.
[0020] In one embodiment, the confined nanocatalyst within the mesoporous material has a diameter of less than 10 nm. In other embodiments, the nanocatalyst has a diameter of about 2 to about 4 nm, about 3 to about 5 nm, about 4 to about 6 nm, about 5 to about 7 nm, about 6 to about 8 nm, about 7 to about 9 nm, or about 8 to about 10 nm.
[0021] In one embodiment, the mesoporous material is a mesoporous metal oxide, a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, or a mesoporous aluminophosphate. The mesoporous metal oxide may be aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, or magnesium oxide.
[0022] In one embodiment, the mesoporous material has a surface area of about 100 m2/g to about 1000 m2/g.
[0023] In one embodiment, the metal ions (Mi+y, M2 +y, M3 +y) are selected from the group consisting of Al, Au, Ce, Co, Fe, Ir, Mo, Ni, Pd, Rh, Ru, Ti, V and Zr or combinations thereof. Specific reactions and metal catalyst combinations are as follows:
[0024] Alkene ammoxidation reactions (Bi-Mo, V-Mo, V-Sb, Fe-Sb, Cr-Sb, Cr-Nb, Fe-Nb), James F. Brazdil Catalysts 2018, 8(3), 103; doi: 10.3390/eatal8030103.
[0025] Alkene epoxidation (Mn-Fe), Vincent Escande, Eddy Petit, Laetitia Garoux, Clotilde Boulanger, and Claude Grison ACS Sustainable Chem. Eng., 2015, 3 (11), pp 2704-2715.
[0026] Ammonia synthesis (Co-Mo, Fe-Mo), Yuki Tsuji, Masaaki Kitano, Kazuhisa Kishida, Masato Sasase, Toshiharu Yokoyama, Michikazu Hara and Hideo Hosono Chem. Commun., 2016, 52, 14369-14372.
[0027] Carboxylation reactions (Ni-Zn), Qiang Liu, Lipeng Wu, Ralf Jackstell & Matthias Beller Nature Communications, 2015, 6, 5933.
[0028] CO2 methanation reactions (Zr-Ce, Ni-Ce, N-Ti), F Ocampo F, B Louis, A Kiennemann, A C Roger IOP Conf. Series: Materials Science and Engineering 19 (2011) 012007.
[0029] Direct methanol synthesis from methane (Fe-Mo, Ni-Mg, Co-Mo), Manoj Ravi, Marco Ranocchiari and Jeroen A. van Bokhovcn Angew. Chem. Int. Ed. 2017, 56, 16464. [0030] Dry-methane reforming (Ni-Mg, Ni-Al), Radoslaw D^bek, Maria Elena Galvez, Franck Launay, Monika Motak, Teresa Grzybek & Patrick Da Costa International Journal of Hydrogen Energy , 2016, 41, 11616-11623.
[0031] Electrocatalytic ammonia oxidation (Ru-Zr, Pt-Ir, Pt-Pd) Denver Cheddie “Ammonia as a Hydrogen Source for Fuel Cells: A Review” Chapter 13 from a book edited by Dragica Minic called“Hydrogen Energy - Challenges and Perspectives".
[0032] Catalytic converters for internal combustion engines, (Pt-Rh, Ce-Pt-Rh) Farrauto and Heck, Catalytic converters: state of the art and perspectives, Catalysis Today , 1999, 51(3-4), 351-360.
[0033] In one embodiment, the multidentate ligand for the MOF is selected from the group consisting of, terephthalate, benzene-l,3,5-tricarboxylate, 2,5-dioxibenzene dicarboxylate, biphenyl-4,4’-dicarboxylate, imidazolate, pyrimidine-azolate, triazolate, tetrazolate, derivatives or combinations thereof.
[0034] In some embodiments, the MOF may be HKUST-l, M2(dobpdc), MIF-100, MIF-101, MIF-53, MOF-74, NU-1000, PCN-222, PCN-224, UiO-66, UiO-67, ZIF-8, ZIFs, or derivatives thereof.
[0035] In one embodiment, wherein the mesoporous material is selected from the group consisting of, MCM-41, SBA-15, or commercially available silica.
[0036] In one embodiment, wherein the free functional groups at the organic ligand of the MOF are selected from amino, bipyridine, chloride, hydroxyl, porphyrin, ester, amide, ketone, acid, hydrazine, or oxime.
[0037] In one embodiment, wherein the chelating ligand (Z) is selected from salicyl aldehyde, ethyl chloro-oxoacetate, pyridine aldehyde, hydroxymethylphosphine, pyrrole aldehyde, ethylenediamine, picolinate, dimethylglyoximate, 2,2’ ,2”-terpyridine, 1,4,7,10- triethylenetetramine, 1,4,8, l l-triethylenetetramine, phenanthroline and bisdiphenylphospinoethane or phosphine aldehyde.
[0038] In some embodiments, the nanocatalyst confined within mesoporous material is further reacted with additional organometallic metal complexes or metal salts with polymers, organometallic ligand precursors, nitrogen-containing organic compounds, phosphorous- containing organic compounds, sulfur-containing organic compounds, boron-containing organic compounds, halide salts, organic halides, or metal atoms added via atomic layer deposition or chemical vapor deposition.
[0039] The disclosure also provides a catalyst made by the methods described above.
[0040] The catalyst may further comprise an added metal promotor.
[0041] The disclosure also provides uses. The catalysts described above may be used to catalyze alkene ammoxidation reactions, alkene epoxidation, ammonia synthesis, carboxylation reactions , C02 methanation reactions, conversion of C02 to fuel, direct methanol synthesis from methane, dry-methane reforming, electrocatalytic ammonia oxidation, electrocatalytic oxygen reduction reactions, Fischer-Tropsch synthesis, hydro-/dehydrogenation of liquid organic hydrogen carriers, hydrotreating and hydroprocessing esterification reactions, methanol synthesis from syngas, reverse water-gas shift reactions, or water-gas shift reactions.
4. BRIEF DESCRIPTION OF THE FIGURES
[0042] Fig. 1. Scheme describing a general approach of single-nanocry stal-to- single nanocatalyst conversion of MOF nanocrystals into bimetallic oxide nanocatalysts. TEM images (a) SBA-15 and (b) (Zr)UiO-66(NH2)/SBA-l5. STEM images for (c) PdCl-SI-(Zr)UiO- 66(NH2)/SBA-l5 and (d) PdNc/SI-(Zr)UiO-66(NH2)/SBA-l5.
[0043] Fig. 2. A scheme showing a two-step post-synthesis modification (PSM) for transition metal complex incorporation on MOF nanocrystals and subsequently controlled transformation treatment for preparing bimetallic nanocatalysts. This controlled transformation treatment scheme is valid for monometallic MOF nanocrystals containing only one metal oxide at the SBU. Low MOF loading (below 15 wt%) has been found to be a determinant for obtaining sufficient initial spacing between MOF nanocrystals. Higher MOF loadings (20-40 wt.%) lead to shorter distances between crystallites, and thereby, higher tendency to form aggregates during the transformation treatment.
[0044] Fig. 3. Typical characterization routine for bimetallic [M2-Z-(MI)MOF/MPM] precursor materials: FTIR, XRD, surface area and pore distribution.
[0045] Fig. 4a. STEM images and EDS for carbon-free PdZr02 nanocatalysts confined within SBA-15 prepared from Pd-ST(Zr)UiO-66(NH2)/SBA-l5 treated via pyrolysis under nitrogen at 650 °C. [0046] Fig. 4b. STEM images and EDS for PdZr02 nanocatalysts confined within SBA-15 prepared from Pd-SI-(Zr)UiO-66(NH2)/SBA-l5 treated via calcination under oxygen at 500 °C.
[0047] Fig. 4c. STEM images and EDS for PdNc/(Zr)UiO-66(NH2) nanocatalysts confined within SBA-15 prepared from Pd-SI-(Zr)UiO-66(NH2)/SBA-l5 treated via reduction under hydrogen at 200 °C.
[0048] Fig. 5. (left) TGA profiles for sample PdCl-ST(Zr)UiO-66(NH2)/SBA-l5 under nitrogen and air. (right) FTIR spectra of consecutive steps for the preparation of PdZr02/SBA-l5 sample via pyrolysis under nitrogen at 900 C, as shown in Fig. 1.
[0049] Fig. 6. Application example, results for hydro -/dehydrogenation of liquid organic hydrogen carriers in solid state.
[0050] Fig. 7. Application example of some results for C02 to fuels reaction catalyzed by Fe304/Si02 and FeC/Si02 catalysts at varying loadings prepared from (Fe)MIL-l00/SiO2 compared to Clariant commercial catalysts.
[0051] Fig. 8. Application example of different C02 to fuels reaction catalyzed by FeC/Si02 at various ratio of H2/C02.
5. DETAILED DESCRIPTION OF THE DISCLOSURE
[0052] This disclosure provides a novel strategy to prepare nano-sized catalyst via controlled transformation of MOF nanocrystals. These catalysts may be optionally decorated with additional organometallic metal complexes or metal salts previously or afterwards confined within mesoporous materials and or optionally decorated with polymers, organometallic ligand precursors, nitrogen-containing organic compounds, phosphorous-containing organic compounds, sulfur-containing organic compounds, boron-containing organic compounds, halide salts, organic halides, metal atoms added via atomic layer deposition or chemical vapor deposition or other compounds previously or afterwards confined within mesoporous materials. This general method preserves the dispersion, nano-sized dimension, and 3-D distribution along the mesoporous matrix of the pristine support precursor into the resulting catalysts, thus favoring the formation of nanometric and subnanometric active species (such as metals, metal oxides, N-doped carbons, P- doped carbons, S-doped carbons, B-doped carbons, halide-doped carbons, and combinations thereof) with high precision by using proper selection of the hybrid precursors, (i. e., organometallic metal complex, metal salt, polymer, organometallic ligand precursor, nitrogen- containing organic, phosphorous-containing organic, sulfur-containing organic, boron-containing organic, halide salts, organic halides, MOF and mesoporous scaffold).
[0053] In preferred embodiments, the transformation treatment can be done at three different conditions: pyrolysis, calcination or reduction. Additional properties are conferred by confining the resulting supported nanocatalysts in the mesoporous scaffold, such as enhanced diffusion, improved chemical stability, excellent attrition resistance as well as feasible handling, as recently reported for the hybrid MOF/MPMs materials (Luz, I.; Soukri, M.; Lail, M.: Confining Metal- Organic Framework Nanocrystals within Mesoporous Materials: A General Approach via“Solid- State” Synthesis. Chemistry of Materials 2017 29 9628-9638).
[0054] MOFs have been widely used as versatile precursors for preparation of catalytically active materials upon applying certain conditions, such as controlled pyrolysis under nitrogen or other inert gas, calcination under oxygen or reduction under hydrogen or other reducing gas. The resulting solid catalysts can be composed of metals, metal oxides, nitrogen-doped carbon, phosphorous-doped carbon, sulfur-doped carbon, boron-doped carbon, halide-doped carbon, and combinations thereof (Wei et al. 2017). The use of nano-sized MOF domains (5-50 nm diameter) as precursor instead of bulkier particles can offer some advantages from the catalytic point of view, as they can lead to the isolation of a reduced number of metallic atoms in a single crystal, or cluster (Liu, L. C.; Diaz, U.; Arenal, R.; Agostini, G.; Concepcion, P.; Corma, A.: Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nature Materials 2017, 16, 132-138), upon one of the treatments mentioned above. However, the use of free-standing bulk MOF nanocrystals as precursors is problematic due to the large amount of inaccessible metal sites concentrated deep in sub-surface regions of the resulting material and their poor stability under high temperatures that gives rise their fusion into larger aggregates upon applying those required transformation treatments. Therefore, novel synthetic routes are highly demanded to confine the concentration of nanocatalysts derived from MOF to the catalyst surface and to avoid MOF nanocrystals from sintering during high temperature treatments, thus paving the way to the development of new generation of MOF-derived nanocatalysts.
[0055] Our group recently reported a novel method for selectively supporting MOF nanocrystals within mesoporous materials via‘solid-state’ crystallization. This versatile approach provides a high level of design over the resulting hybrid material formulation and nanoarchitecture, such as composition, loading and dispersion of the MOF guest as well as composition, pore size distribution and particle size of the mesoporous material host. MOF nanocrystal size is always restricted to the dimensions delimited by the hosting cavity of the mesoporous material. In the same way, we have recently demonstrated the superior catalytic activity as heterogeneous catalysts for synthesis of testosterone derivatives (Cirujano et al. 2017) In addition, these materials have C02 capture capacity as fluidized hybrid sorbents for post-combustion flue gas of hybrid MOF/MPM materials compared to the‘state-of-the-art’, as well as other applications, such as chromatography. See PCT Patent Appn. PCT/US2017/046231, Research Triangle Institute.
[0056] Herein, we demonstrate that those supported and well-dispersed MOF nanocrystals can be used as optimal precursor for preparing either nanosized mono-, bi-, or multimetallic metal oxides through a single-nanocrystal-to-single-nanocatalyst transformation, which can be done upon 1) pyrolysis under nitrogen or other inert gas (from 500 to 1000 °C), 2) calcination in the presence of oxygen (400-800 °C) or 3) chemical reduction under hydrogen or other suitable reducing gas (from room temperature to 300 °C). This approach preserves the initial 3D distribution of the MOF precursors on the resulting nanocatalysts along the surface area of the mesoporous material, thus avoiding the tendency of nanocrystals to fuse into larger crystallites (Prieto, G.; Zecevic, J.; Friedrich, H.; de Jong, K. P.; de Jongh, P. E.: Towards stable catalysts by controlling collective properties of supported metal nanoparticles. Nature Materials 2013, 12, 34- 39), which is one of the major causes of deactivation for supported catalysts. Therefore, more stable and highly active subnanometric catalysts (<l nm) have been prepared by our general strategy and tested for some catalytic reactions of highly industrial interest, such as hydro- /dehydrogenation of liquid organic hydrogen carriers, direct methanol synthesis from methane, methanol synthesis from syngas, C02 methanation, ammonia synthesis, Fischer-Tropsch synthesis, dry-methane reforming, alkene epoxidation, water-gas shift, reverse water-gas shift, hydrotreating and hydroprocessing esterification, carboxylation, electrocatalytic oxygen reduction reaction, electrocatalytic ammonia oxidation, alkene ammoxidation, catalytic combustion, and C02 to fuels, among others.
[0057] In a first step, an aqueous solution of an organic ligand salt of the formula AX(L X) is contacted with a mesoporous material (MPM) present at a concentration in the range of 10-300 mg/mL, preferably 25-275 mg/mL, preferably 50-250 mg/mL to form an impregnated mesoporous salt material of the formula AX(L X)/MPM. Exemplary salts include, but are not limited to, mineral or organic acid salts of basic groups such as amines, and alkali or organic salts of acidic groups such as carboxylic acids. The salts include, but are not limited to, the conventional non-toxic salts or the quaternary ammonium salts of the parent compound formed, for example, from non-toxic inorganic or organic acids. Salts of carboxylic acid containing ligands may include cations such as lithium, sodium, potassium, magnesium, additional alkali metals, and the like. The salts include, but are not limited to, the conventional non-toxic salts or the quaternary ammonium salts of the parent compound formed, for example, from non-toxic inorganic or organic acids. In a preferred embodiment, the salts are alkali metal salts, most preferably sodium salts. In a preferred embodiment, the contacting is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a contacting time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2- 12 hours, preferably 2.5-8 hours, preferably 3-6 hours. In some embodiments, the ligand (i.e. acid form; 2,6-dihydoxyterephthalic acid) may be dissolved and impregnated in water or organic solvents. Exemplary organic solvents include, but are not limited to, methanol, ethanol, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, acetone, and the like.
[0058] In a second step, the impregnated mesoporous salt material present at a concentration in the range of 10-300 mg/mL, preferably 25-275 mg/mL, preferably 50-250 mg/mL is treated with a gas phase acid to form an impregnated mesoporous acid material of the formula HX(L X)/MPM. The gas phase acid may be an inorganic acid such as HC1. In a preferred embodiment, the gas treatment is performed at a temperature of up to 150 °C, preferably 10-120 °C, preferably 15-110 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a treating time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2-12 hours, preferably 2.5-8 hours, preferably 3-6 hours. The temperature will depend on the choice of the acid. An organic acid may be at a temperature of 100 °C ± 50 °C, preferably 100 °C ± 20 °C, preferably 100 °C ± 10 °C, preferably 100 °C ± 5 °C. Whereas treatment with nitrogen saturated with HC1 might be a 30 °C ± 20 °C, preferably 30 °C ± 10 °C, preferably 30 °C ± 5 °C.
[0059] Alternatively, the bound ligand may be treated with an aqueous acidic solution of 0.05- 10.0 M in concentration, preferably 0.1-9.0 M, preferably 1.0-8.0M, preferably 2.0-6.0 M, or about 4.0 M to form an impregnated mesoporous acid material of the formula HX(L X)/MPM. Strong acids including, but not limited to, HC1, H2S04, and HN03 are preferred, but organic acids and weak acids (i.e. acetic acid) may also be used in the treating, most preferably HC1. In a preferred embodiment, the solution treatment is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a treating time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2- 12 hours, preferably 2.5-8 hours, preferably 3-6 hours.
[0060] In a third step, the impregnated mesoporous acid material, present at a concentration in the range of 10-300 mg/mL, preferably 25-275 mg/mL, preferably 50-250 mg/mL, is contacted with an aqueous solution of a metal precursor of the formula M+y to form an impregnated mesoporous metal organic framework precursor. In a preferred embodiment, the contacting is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a contacting time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2-12 hours, preferably 2.5-8 hours, preferably 3-6 hours.
[0061] In a next step the impregnated mesoporous metal organic framework precursor is heated in the absence of a solvent or exposed to a volatile vapor (i.e. and amine such as methylamine or controlled moisture such as steam) in the absence of a solvent to form a hybrid material of the formula (M+yL x)/MPM, or hereafter called MOF/MPM. In this step, the metal ions form coordinate bonds with the one or more organic ligands, preferably multidentate organic ligands to form a nano-crystalline metal organic framework in the pore spaces of the mesoporous material. In a preferred embodiment, the heating is performed at a temperature of up to 300 °C, preferably 40-250 °C, preferably 60-220 °C, preferably 100-200 °C, preferably 120-190 °C, and has a heating time of up to 60 hours, preferably 12-48 hours, preferably 24-36 hours. In a preferred embodiment, the exposing to a vapor is performed at a temperature of up to 80 °C, preferably 10- 80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a heating time of up to 48 hours, preferably 6-36 hours, preferably 12-24 hours. In certain embodiments, a catalytic amount of a specific additive including (preferably 15 %), but not limited to, methanol, ethanol, tetrahydrofuran, N,N-dimethylformamide, and the like may be employed to assist the crystal formation within the hybrid material.
[0062] In some embodiments, the MOF/MPM is treated with an organic compound to form another ligand and then treated with at least one or multiple additional metal to create a bound with the MOF. Collectively, whether mono-metallic, bimetallic, trimetallic or multimetallic, those metals will become part of the MOF confined with the MPM for the next step. In other embodiments, the MOF/MPM (mono-, bi-, tri-, polymetallic) is contacted with a solution containing salts of additional metal catalysts or promoters. The modified MOF/MPM is then dried and treated with the controlled transformation conditions described below.
[0063] In a final step, the embedded MOF or MOF/MPM is subjected to controlled transformation conditions to generate the confined nanocatalyst. The controlled transformation may be (1) pyrolysis under nitrogen or other inert gas: where nanocrystals are obtained when the transformation is carried out under nitrogen (or other inert gas such as Ar or a reactive gas such as acetylene) for temperatures ranging from 300 °C to 1000 °C. In some embodiments, the temperatures ranging from 300 °C to 500 °C, preferably 400 - 600 °C, preferably 500 - 700 °C, preferably 600 - 800 °C, preferably 700 - 900 °C, preferably 800 - 1000 °C.
[0064] Alternatively, the controlled transformation may be (2) calcination in an oxygen containing atmosphere. All organic materials are released at lower temperatures when an oxygen containing atmosphere is present in the transformation treatment. Carbon-free nanocatalysts are obtained for temperatures of 300 - 600 °C, preferably 300 - 350 °C, preferably 400 - 450 °C, preferably 450 - 500 °C, preferably 500 - 550 °C, preferably 550 - 600 °C.
[0065] Alternatively, the controlled transformation may be (3) reduction with an atmosphere containing hydrogen. When hydrogen is present in the atmosphere for transformation the temperatures are still milder (from room temperature to 300 °C). The MOF carbon micro structure is not completely decomposed, although the transition metal cations decorating the MOF nanocrystal are reduced to form a metallic nanocrystal confined within the microporous cavities of the MOF and/or MPM. In some embodiments, the temperature for the reductive transformation is from 25 - 50 °C, preferably 50 - 75 °C, preferably 75 - 100 °C, preferably 100 - 125 °C, preferably 125 - 150 °C, preferably 150 - 175 °C, preferably 175 - 200 °C, preferably 200 - 225 °C, preferably 225 - 250 °C, preferably 250 - 275 °C, preferably 275 - 300 °C.
[0066] In certain embodiments, the confined metallic nanocrystal is present only within the mesopores or void spaces of the mesoporous material and homogeneously dispersed within the mesopores or void spaces of the mesoporous material. As used herein,“disposed on”,“embedded” or“impregnated” describes being completely or partially filled throughout, saturated, permeated and/or infused. The confined metallic nanocrystal may be affixed substantially within the pore space of the mesoporous material. The confined metallic nanocrystal may be affixed to the mesoporous material in any reasonable manner, such as physisorption or chemisorption and mixtures thereof. In one embodiment, greater than 10% of the pore spaces of the mesoporous material is occupied by the confined metallic nanocrystal, preferably greater than 15%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%, preferably greater than 45%, preferably greater than 50%, preferably greater than 55%, preferably greater than 60%, preferably greater than 65%, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 85%, preferably greater than 90%, preferably greater than 95%, preferably greater than 96%, preferably greater than 97%, preferably greater than 98%, preferably greater than 99%. Alternatively, 5-10% of the pore spaces of mesoporous material may be occupied.
[0067] In certain embodiments, the confined metallic nanocrystal is substantially present only within the mesopores or void spaces of the mesoporous material and homogeneously dispersed on the external surface of the mesoporous material, preferably greater than 60% of the confined metallic nanocrystal is located in the pore spaces and not at the surface of the mesoporous material, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 85%, preferably greater than 90%, preferably greater than 95%, preferably greater than 96%, preferably greater than 97%, preferably greater than 98%, preferably greater than 99%. As used herein, homogeneous dispersion refers to dispersion in a similar or the same manner and may refer to uniform structure and composition. The coefficient of variation of the nanocatalysts are distributed in the MPM is less than 10%, preferably less than 8%, preferably less than 6%, preferably less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%. The surface of the MPM is generally substantially free from the nanocatalysts.
[0068] In certain embodiments, the method further comprises drying at least one selected from the group consisting of the impregnated mesoporous salt material, the impregnated mesoporous acid material, the impregnated mesoporous metal organic framework precursor, and the hybrid material at a temperature in the range of 25-160 °C, preferably 85-150 °C, preferably 90-140 °C, preferably 100-130 °C, or about 120 °C under a vacuum and with a drying time of up to 24 hours, preferably 0.5-18 hours, preferably 1-12 hours, preferably 1.5-6 hours, or about 2 hours.
[0069] In certain embodiments, the method further comprises washing the hybrid material with distilled water or other polar protic solvent and extracting water from the hybrid material in a Soxhlet system recycling methanol or other polar protic solvent. [0070] In a preferred embodiment, the mesoporous material is at least one selected from the group consisting of a mesoporous metal oxide (aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, magnesium oxide, etc.), a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, and a mesoporous aluminophosphate, etc.). As used herein, a mesoporous material may refer to a material containing pores with diameters between 2-50 nm, porous materials are classified into several kinds by their pore size. In a preferred embodiment, the mesoporous material has a percent porosity of greater than 10%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%
[0071] In a preferred embodiment, the organic ligand (L x) of the organic ligand salt is at least one selected from the group consisting of polycarboxylate ligands, azaheterocyclic ligands, and derivatives thereof. As used herein, "ligand" refers to a mono-dentate or polydentate compound that bind a transition metal or a plurality of transition metals, respectively. Generally, a linking moiety comprises a substructure covalently linked to an alkyl or cycloalkyl group, comprising 1 to 20 carbon atoms, an aryl group comprising 1 to 5 phenyl rings, or an alkyl or aryl amine comprising alkyl or cycloalkyl groups having from 1 to 20 carbon atoms or aryl groups comprising 1 to 5 phenyl rings, and in which a linking cluster (e.g., a multidentate function groups) are covalently bound to the substructure. A cycloalkyl or aryl substructure may comprise 1 to 5 rings that comprise either of all carbon or a mixture of carbon with nitrogen, oxygen, sulfur, boron, phosphorus, silicon and/or aluminum atoms making up the ring. Typically, the linking moiety will comprise a substructure having one or more carboxylic acid linking clusters covalently attached.
[0072] In a preferred embodiment, the organic ligand (L x) of the organic ligand salt is at least one selected from the group consisting of, terephthalate, benzene-l,3,5-tricarboxylate, 2,5- dioxibenzene dicarboxylate, biphenyl-4,4’ -dicarboxylate and derivatives thereof. In a preferred embodiment, the organic ligand (L x) of the organic ligand salt is at least one selected from the group consisting of imidazolate, pyrimidine-azolate, triazolate, tetrazolate and derivatives thereof. Additional suitable exemplary ligands include, but are not limited to, bidentate carboxylics (i.e. oxalic acid, malonic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terepthalic acid), tridentate carboxylates (i.e. citric acid, trimesic acid), azoles (i.e. 1,2, 3-triazole, pyrrodiazole), squaric acid and mixtures thereof. [0073] In preferred embodiments, the metal (M+y) of the metal precursor is at least one transition metal selected from the group consisting of Mg, V, Cr, Mo, Zr, Hf, Mn, Fe, Co, Cu, Ni, Zn, Ru, Al, and Ga. As used herein,“metal ion” is selected from the group consisting of elements of groups la, Ila, Ilia, IVa to Villa and IB to VIb of the periodic table of the elements. In certain other embodiments, the metal precursor may comprise clusters of metal oxides.
[0074] In a preferred embodiment, the metal organic framework is at least one selected from the group consisting of MIL-101, MIL-100, MIL-53, MOF-74, UiO-66, UiO-67, ZIF-8, ZIFs, HKUST-l, M2(dobpdc), NU-1000, PCN-222, PCN-224, and derivatives thereof. As used herein, a metal organic framework may refer to compounds consisting of metal ions or clusters coordinated to organic ligands to form one-, two- or three-dimensional structures, with the special feature of porosity. More formally, a metal organic framework is a coordination network with organic ligands containing potential voids. In a preferred embodiment, the nano-crystalline MOF has a percent porosity of greater than 10%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%. MOFs are composed of two major components: a metal ion or cluster of metal ions and an organic molecule often termed a linker. The organic units are typically mono-, di-, tri-, or tetravalent ligands. The choice of metal and linker will dictate the structure and hence properties of the MOF. For example, the metal's coordination preference influences the size and shape of pores by dictating how many ligands can bind to the metal and in which orientation.
[0075] In a preferred embodiment, the hybrid material has a weight percentage of the metal organic framework in the range of 5-50% relative to the total weight of the hybrid material, preferably 15-45%, preferably 25-40%, preferably 30-35%, or at least 20%, preferably at least 25%, preferably at least 30%, preferably at least 35%, preferably at least 40%, preferably at least 45%.
[0076] In a preferred embodiment, the mesoporous material (MPM) comprises mesopores with an average diameter in the range of 2-50 nm, preferably 4-45 nm, preferably 6-40 nm and micropores with an average diameter in the range of 0.5-5.0 nm, preferably 1.0-4.5 nm, preferably 2.0-4.0 nm. In a preferred embodiment, the mesopores, the micropores, or both are monodisperse having a coefficient of variation of less than 10%, preferably less than 8%, preferably less than 6%, preferably less than 5%, preferably less than 4%, preferably less than 3%. In a preferred embodiment, the hybrid material has a percent porosity of greater than 10%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%. In a preferred embodiment, the hybrid material has a reduced mesoporosity relative to the bare mesoporous material and an increased microporosity relative to the bare mesoporous material.
[0077] In a preferred embodiment, the confined metallic nanocrystal has an average longest linear dimension of less than 10 nm, preferably less than 8 nm, preferably less than 5 nm, preferably less than 2.5 nm.
[0078] In a preferred embodiment, the MPM has a surface area in the range of 100-1200 m2/g, preferably 200-1100 m2/g, preferably 300-1000 m2/g, preferably 400-900 m2/g, preferably 500- 950 m2/g, preferably 600-900 m2/g, preferably 700-850 m2/g, or at least 400 m2/g, preferably at least 600 m2/g, preferably at least 800 m2/g, preferably at least 1000 m2/g.
[0079] While the following terms are believed to be well understood by one of ordinary skill in the art, the following definitions are set forth to facilitate explanation of the presently disclosed subject matter.
[0080] Throughout the present specification, the terms“about” and/or“approximately” may be used in conjunction with numerical values and/or ranges. The term“about” is understood to mean those values near to a recited value. For example,“about 40 [units]” may mean within ± 25% of 40 (e.g., from 30 to 50), within ± 20%, ± 15%, ± 10%, ± 9%, ± 8%, ± 7%, ± 6%, ± 5%, ± 4%, ± 3%, ± 2%, ± 1%, less than ± 1%, or any other value or range of values therein or there below. Furthermore, the phrases“less than about [a value]” or“greater than about [a value]” should be understood in view of the definition of the term“about” provided herein. The terms “about” and“approximately” may be used interchangeably.
[0081] Throughout the present specification, numerical ranges are provided for certain quantities. It is to be understood that these ranges comprise all subranges therein. Thus, the range “from 50 to 80” includes all possible ranges therein (e.g., 51-79, 52-78, 53-77, 54-76, 55-75, 60- 70, etc.). Furthermore, all values within a given range may be an endpoint for the range encompassed thereby (e.g., the range 50-80 includes the ranges with endpoints such as 55-80, 50- 75, etc.).
[0082] As used herein, the verb“comprise” as is used in this description and in the claims and its conjugations are used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. [0083] Throughout the specification the word“comprising,” or variations such as“comprises” or“comprising,” will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps. The present disclosure may suitably“comprise”,“consist of’, or“consist essentially of’, the steps, elements, and/or reagents described in the claims.
[0084] It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as "solely", "only" and the like in connection with the recitation of claim elements, or the use of a "negative" limitation.
[0085] Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Preferred methods, devices, and materials are described, although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure. All references cited herein are incorporated by reference in their entirety.
[0086] The following Examples further illustrate the disclosure and are not intended to limit the scope. In particular, it is to be understood that this disclosure is not limited to particular embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.
6. EXAMPLES
6.1. Materials and Methods
[0087] Chemicals. All chemicals were used as received from Sigma- Aldrich without further purification. Cr(N03)3-9H20, CrCl3-6H20, Al(N03)3-9H20, AlCl3 xH20, Co(N03)2-6H20, Ni(N03)2-6H20, Zr0Cl2- 8H20, RuCl3 xH20, Zn(N03)3-9H20, l,4-benzenedicarboxylic acid (H2BDC), l,3,5-benzenetricarboxylic acid (H3BTC), 2-aminoterephthalic acid (H2BDC(NH2)), monosodium 2-sulfoterephthalate (H2BDC(S03Na)), 2,5-dihydroxyterephthalic acid (H4DOBDC), 2,2'-Bipyridine-5,5'-dicarboxylic acid (H2BpyDC), 2-methylimidazol (HMelM), tetrakis(4-carboxy-phenyl)-porphyrin (H4TCPP). l,3,6,8-tetrakis(p-benzoic acid)pyrene (PLTBAPy) was synthesized according to the published procedure. See Deria, P.; Bury, W.; Hupp, J. T.; Farha, O. K.: Versatile functionalization of the NU-1000 platform by solvent-assisted ligand incorporation. Chem. Commun. 2014, 50, 1965-1968. Triethylamine (TEA), NN- dimethylformamide (DMF), tetrahydrofuran (THF) and methanol (MeOH) were of analytical grade (Sigma-Aldrich).
[0088] Mesoporous materials. Silica(A) [75-250 pm], Silica(B) [200-500 pm], Silica(C) [75- 200 pm] and Silica(D) [75-150 pm] were kindly supplied by our commercial partner. SBA-15 was prepared according to the published procedure. Zhao, D. Y.; Feng, J. L.; Huo, Q. S.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G. D.: Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 1998, 279, 548-552. MCM-41 was provided by Claytec (East Lansing, MI), g-A1203 by Sasol (Houston, TX), Ti02 by Sachtleben (Hausach, Germany) and Zr02 by Mel Chemicals (Manchester, UK). Mesoporous carbon and HayeSep A (Supelco) [100-120 pm] were supplied by Sigma-Aldrich. All mesoporous materials were degassed at 120 °C overnight under vacuum to remove the adsorbed water.
[0089] Ligand salt precursors. Na2BDC and Na3BTC ligand salt precursors were prepared from their acid form in water with the stoichiometric amount of NaOH necessary to deprotonate the carboxylic acid of the organic linker followed by a purification step via precipitation in acetone. Alternatively, ligand salt precursor solutions for H2BDC(NH2), H2BpyDC, H4TCPP and H4TBAPy were directly prepared with the stoichiometric amount of TEA, thereby skipping the step of isolating the ligand salt. H2BDC(S03Na) and HMelM were directly dissolved in water. H4DOBDC was dissolved in hot THF due to the insolubility in water of sodium 2,5- dioxyterephthalate coordination polymers. The use of triethylammonium salts did not give rise the targeted MOF-74 structure.
[0090] Bulk-type MOFs. For comparison purposes, the following MOFs were prepared and activated according to the reported literature: (Cr)MIL-lOl(Ferey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surble, S.; Margiolaki, I.: A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science 2005, 309, 2040-2042 and Serre, C.; Millange, F.; Thouvenot, C.; Nogues, M.; Marsolier, G.; Louer, D.; Ferey, G.: Very Large Breathing Effect in the First Nanoporous Chromium(III)-Based Solids: MIL-53 or Crlll(OH)· {02C-C6H4-C02} {H02C-C6H4-C02H}x H20y. J. Am. Chem. Soc. 2002, 124, 13519-13526), (Cr)MIL-lOO (Long, P. P.; Wu, H. W.; Zhao, Q.; Wang, Y. X.; Dong, J. X.; Li, J. P.: Solvent effect on the synthesis of MIL-96(Cr) and MIL-lOO(Cr). Microporous Mesoporous Mater. 2011, 142, 489-493), (Cr)MIL-l0l(SO3H)( Juan-Alcaniz, J.; Gielisse, R.; Lago, A. B.; Ramos-Feman-dez, E. V.; Serra-Crespo, P.; Devic, T.; Guillou, N.; Serre, C.; Kapteijn, F.; Gascon, J.: Towards acid MOFs - catalytic performance of sulfonic acid functionalized architectures. Catal. Sci. Technol. 2013, 3, 2311-2318), (Al)MIL-lOO(Volkringer, C.; Popov, D.; Loiseau, T.; Ferey, G.; Burghammer, M.; Riekel, C.; Haouas, M.; Taulelle, F.: Synthesis, Single-Crystal X-ray Microdiffraction, and NMR Characterizations of the Giant Pore Metal-Organic Framework Aluminum Trimesate MIL- 100. Chem. Mater. 2009, 21, 5695-5697), (Al)MIL-53(NH2)(Couck, S.; Denayer, J. F. M.; Baron, G. V.; Remy, T.; Gas-con, J.; Kapteijn, F.: An Amine-Functionalized MIL-53 Metal-Organic Framework with Large Separation Power for C02 and CFL. J. Am. Chem. Soc. 2009, 131, 6326-+), (Co, Ni)MOF-74 (Dietzel, P. D. C.; Morita, Y.; Blom, R.; Fjellvag, H.: An In Situ High-Temperature Single-Crystal Investigation of a Dehydrated Metal-Organic Framework Compound and Field-Induced Magnetization of One-Dimensional Metal-Oxygen Chains. Angew. Chem., Int. Ed. 2005, 44, 6354-6358 and Dietzel, P. D. C.; Panella, B.; Hirscher, M.; Blom, R.; Fjell-vag, H.: Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated frame-work. Chem. Commun. 2006, 959-961), (Zr)UiO-66(H,NH2)( Kandiah, M.; Nilsen, M. H.; Usseglio, S.; Jakobsen, S.; Ols-bye, U.; Tilset, M.; Larabi, C.; Quadrelli, E. A.; Bonino, F.; Lillerud, K. P.: Synthesis and Stability of Tagged UiO-66 Zr-MOFs. Chem. Ma-ter. 2010, 22, 6632-6640), (Zr)UiO-67(Bpy)(Fei, H.; Cohen, S. M.: A robust, catalytic metal-organic framework with open 2,2-bipyridine sites. Chem. Commun. 2014, 50, 4810-4812), (Ru)HKUST-l(Kozachuk, O.; Luz, I.; Llabres i Xamena, F. X.; Noei, H.; Kauer, M.; Albada, H. B.; Bloch, E. D.; Marler, B.; Wang, Y.; Muhler, M.; Fischer, R. A.: Multifunctional, Defect-Engineered Metal-Organic Frameworks with Ruthenium Centers: Sorption and Catalytic Properties. Angew. Chem., Int. Ed. 2014, 53, 7058-7062), (Zn)ZIF- 8(Cravillon, J.; Miinzer, S.; Lohmeier, S.-L; Feldhoff, A.; Huber, K.; Wiebcke, M.: Rapid Room- Temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework. Chem. Mater. 2009, 21, 1410-1412), (Zr)PCN-222(Dawei Feng; Zhi-Yuan Gu; Jian- Rong Li; Hai-Long Jiang; ZhangwenWei; Zhou, H.-C.: Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts. Angew. Chem., Int. Ed. 2012, 51, 10307 -10310), (Zr)NU-lOOO (Deria et al. 2014) and Co2(dobpdc)(McDonald et al. Cooperative insertion of C02 in diamine- appended metal-organic frameworks. Nature 2015, 519, 303-+). FTIR spectra of these MOFs was used as reference for MOF/MPM hybrid materials. N2 isotherms and pore distribution for (Cr)MIL-l0l(SO3H) were included in Figures.
[0091] Transmission Electron Microscopy (TEM). Transmission electron microscopy (TEM) experiments were performed in a JEOL JEM-2000FX S/TEM microscope with LaB6 emitter at 200kV with a 120 pm condenser lens aperture and 80 pm objective lens aperture inserted.
[0092] Thermogravimetric Analyzer (TGA). Thermal stability measurements were conducted on a Mettler Toledo thermogravimetric analyzer (TGA) using a 5 °C/min step to 1000 °C under an air atmosphere.
[0093] N2 sorption isotherms. The samples were analyzed in a Micromeritics ASAP (Accelerated Surface Area and Porosimetry) 2020 System. Samples were weighted into tubes with seal frits and degassed under vacuum (<500 pm Hg) with heating. They were initially heated at 150 °C and held for 4 hours, and finally cooled to room temperature and backfilled with N2. The samples were re-weighted before analysis. The analysis adsorptive was N2 at 77K. A multi-point BET surface area was determined from 6 measurements at relative pressures (P/Po) ranging from 0.050 to 0.300 satisfying the four criteria suggested by Rouquerol. See Gomez-Gualdron, D. A., Moghadam, P. Z., Hupp, J. T., Farha, O. K., Snurr, R. Q.: Application of Consistency Criteria To Calculate BET Areas of Micro- And Mesoporous Metal-Organic Frameworks. J. Am. Chem. Soc., 2016, 138, 215-224. Single point adsorption total pore volume was measured near saturation pressure (Po ~ 770 mmHg). Adsorption average pore width was also calculated. Pore size distribution plot was determined by BJH method with Halsey thickness curve equation and Faas BJH correction.
[0094] FTIR: ATR and DRIFTS cell. ATR absorption spectroscopy measurements were performed in the range of 4000-400 cm-l with a Perkin Elmer Spectrum 100 FTIR spectrometer. The‘in situ’ DRIFTS experiments were carried out in a Praying Mantis cell by injecting a nitrogen flow saturated with water for assisting the vapor-phase crystallization at 120 °C.
6.2. Examples of a single nanocrystal to single nanocatalyst transformation
[0095] As examples of the scope of the approach disclosed herein, single metal and metal oxide nanocrystals have been prepared via controlled transformation procedures by using selected supported MOF nanocrystals on mesoporous silica as precursors. Moreover, bimetallic metal oxide nanocrystals have also been prepared by an additional multistep post-synthesis modification (PSM) of the MOF hybrid precursors carried out before controlled transformation, which includes a gas-phase functionalization (see Table 1 and Fig. 1 and 2) (Servalli, M.; Ranocchiari, M.; Van Bokhoven, J. A.: Fast and high yield post-synthetic modification of metal-organic frameworks by vapor diffusion. Chemical Communications 2012, 48, 1904-1906) followed by a selective metalation (Zhang, X.; Llabres i Xamena, F. X.; Corma, A.: Gold(III) - Metal Organic Framework Bridges the Gap between Homogeneous and Heterogeneous Gold Catalysts. Journal of Catalysis 2009, 265, 155-160).
6.3. Example of the synthesis approach: bimetallic rPdCl-SI-(Zr)UiO-66(NH2)/SBA-15l precursor for the catalyst
[0096] Bimetallic [PdCl-SI-(Zr)UiO-66(NH2)/SBA-15] precursor was prepared via solid- state synthesis by following this general procedure: 1) multi-step incipient wetness impregnation of MOF precursor solutions on SBA-15, 2) treatment at specific conditions, 3) general washing treatment, 4) vapor phase post-synthesis functionalization (solid state), and 5) liquid phase post synthesis metalation. All bimetallic [M2-Z-(MI)MOF/MPM] precursors can be prepared by the following general procedure (steps 1 to 5) as described previously (Cirujano et al. 2017 and PCT Patent Appn. PCT/US2017/046231). Monometallic [(Mi)MOF/MPM] precursors are prepared by following only the three first steps (1-3).
[0097] Multi-step incipient wetness impregnation of MOF precursor solution on SBA-15:
[0098] First, a ligand salt precursor solution (TEA)2BDC(NH2) was prepared by dissolving H2BDC(NH2) (1.5 g) loading and TEA (2.5 mL) in 35 mL of water. Second, 10 g of evacuated SBA-15 (overnight under vacuum at 120 °C) were impregnated with the (TEA)2BDC(NH2) solution and then dried at 50 °C under vacuum in a rotavapor for 2 h. Subsequently, the resulting dry intermediate [(TEA)2BDC(NH2)/SBA-l5] was placed in a fluidized bed reactor where it was first treated with a nitrogen flow saturated with concentrated HC1 (37%) for 2 hours at room temperature and eventually purged with a nitrogen flow for 2 h to remove the excess HC1. Afterwards, the metal salt precursor solution, prepared by dissolving 2.5 g of Zr0Cl2- 8H20 in 30 mL of water, was used to impregnate the [H2BDC(NH2)/SBA- 15] mesoporous silica. The resulting [ZrOCl2/H2BDC(NH2)/SBA-15] solid was finally dried at 50 °C under vacuum in a rotavapor for 2 h. All the impregnation steps were done via incipient wetness impregnation.
[0099] Treatment at specific conditions. [00100] The dry solid intermediate [ZrOCl2/H2BDC(NH2)/SBA-l5] together with an additive (15 wt.% of H20) was placed either in a scintillation vial or Pyrex glass bottle capped with a Teflon tap and heated in an oven at 120 °C for 2 h.
[00101] General washing procedure :
[00102] After cooling, the resulting [(Zr)UiO-66(NH2)/SBA-l5] precursor, containing 18.6 wt.% of (Zr)UiO-66(NH2) nanocrystals, was thoroughly washed with distillated water in a filtration funnel. Subsequently, the material was further washed overnight in a Soxhlet extractor with MeOH. All materials were activated overnight at 120 °C under vacuum.
[00103] Vapor-phase post-synthesis functionalization:
[00104] The evacuated precursor [(Zr)UiO-66(NH2)/SBA-l5] (1 gram) and a tube containing salicylaldehyde (1 mL) were separately placed into a Schlenk. The Schlenk was subsequently closed under vacuum and heated at 100 °C overnight in an oven. The color of the material shifts from pale yellow to orange upon exposure to the salicylaldehyde vapor, which indicates the formation of the imine covalent bond between the MOF and salicylaldehyde leading to a solid containing salicylideneimine groups (or Schiff base, Z = SI). This material corresponds to the intermediate [SI-(Zr)UiO-66(NH2)/SBA- 15] .
[00105] Liquid-phase post-synthesis metalation:
[00106] The metal cation was chelated to the intermediate material containing the Schiff base [ST(Zr)UiO-66(NH2)/SBA-l5] by soaking for 2-3 hours at room temperature in a solution containing PdCl2(CH3CN) (200 mg) in THF (5mL). Afterwards the material was washed with MeOH and dried at 80 °C under vacuum to obtain the precursor [PdCl-SI-(Zr)UiO-66(NH2)/SBA- 15] containing 1.7 wt.% of Pd, according to XRF. In the same way, several other metal cations can be incorporated into the Schiff base intermediate [SI-(Zr)UiO-66(NH2)/SBA-l5], such as Au, Pt, Ag, Cu, Ni, ... See the examples in Table 1.
[00107] To prepare additional bimetallic nanocatalysts, the steps are as follows. In a first step, a selective PSM of the free amino groups located at the ligands of numerous MOF structures, such as (Zr)UiO-66(NH2), (Al)MIL-53(NH2), (Ti)MIL-l25(NH2), (Zn)IRMOF-3(NH2), (V)MIL- 101(NH2), (Fe)MIL-53(NH2), among others, have been functionalized via gas phase treatment with salicylaldehyde vapor at 110 °C to fully convert amino groups into Schiff-base ligands (salicyclidene-imine, SI) (see Fig. 1 and Fig. 2). Fig. 5 shows FTIR characterization of the conversion of amino groups into Schiff-base ligands (SI) during subsequent steps of the synthesis. Subsequently, numerous metal cations have been selectively chelated to the resulting Schiff base by soaking the solid material in a solution containing a metal salt, such as Pd, Pt, Au, Cu, Ni, Mo, Ir, Rh, among others. The faster functionalization rates observed for MOF hybrids compared to bulk MOFs is mainly due to the smaller particle size, excellent dispersion of the MOF nanocrystals within mesoporous silicas, and concentration of MOF nanocrystal on the surface of the support. For instance, lower functionalization rates have been observed for SBA-15 with 9 nm monodimensional channels than for Silica A, which is a mesoporous silica exhibiting tridimensional 30 nm non-regular cavities. Therefore, our novel approach will give rise to a well- defined, structured catalyst upon transformation by selecting the proper metal oxide on the MOF cluster (Mi = Zr, Al, Ti, Zn, V, Fe, ...) and incorporating another selected metal at the SI (M2 = Pd, Pt, Cu, Ni, Co, Mo, Au, ...). The morphology and composition of the resulting nanocatalysts will depend on the transformation treatment and the mesopore dimensionality of the selected silica.
6.3.1. Example of controlled transformation: Pyrolysis under nitrogen or other inert gas
[00108] Metallic nanocrystals are obtained when the transformation is carried out under nitrogen or other inert gas for temperatures ranging from 300 to 1000 °C. In some embodiments, this treatment transforms the organic composition of MOF nanocrystals into carbonaceous species. Nevertheless, TGA and elemental analysis data reveals the complete‘de-carbonization’ of MOF nanocrystals leading to carbon- or graphene-free bimetallic nanocatalysts takes place for temperatures of pyrolysis above 600-700 °C. This is in contrast to the bulk MOF (above 100 nm) (see Fig. 5 TGA FTIR comparison), in which microporous carbonaceous structures are remaining upon treatment. See Tang, J.; Salunkhe, R. R.; Zhang, H.; Malgras, V.; Ahamad, T.; Alshehri, S. M.; Kobayashi, N.; Tominaka, S.; Ide, Y.; Kim, J. H.; Yamauchi, Y.: Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons. Scientific Reports 2016, <5, 30295; Masoomi, M. Y.; Morsali, A.: Applications of metal-organic coordination polymers as precursors for preparation of nano-materials. Coordination Chemistry Reviews 2012, 256, 2921-2943; Wezendonk, T. A.; Santos, V. P.; Nasalevich, M. A.; Warringa, Q. S. E.; Dugulan, A. I.; Chojecki, A.; Koeken, A. C. J.; Ruitenbeek, M.; Meima, G.; Islam, H. U.; Sankar, G.; Makkee, M.; Kapteijn, F.; Gascon, J.: Elucidating the Nature of Fe Species during Pyrolysis of the Fe-BTC MOF into Highly Active and Stable Fischer-Tropsch Catalysts. ACS Catalysis 2016, <5, 3236-3247. Lower temperature pyrolysis (<500 °C) may be used to avoid the carbon release from the nanocatalysts. Fig. 4a shows STEM images of the nanocatalyst prepared by heating in an inert atmosphere.
6.3.2. Example of controlled transformation: Calcination in an oxygen containing atmosphere
[00109] All organic composition is released at lower temperatures when oxygen is used for the transformation treatment. Carbon-free bimetallic nanocatalysts are obtained for temperatures above 300-600 °C. Fig. 4b shows STEM images of the nanocatalyst prepared by calcination in an oxygen containing atmosphere.
6.3.3. Example of controlled transformation: Reduction with a hydrogen containing atmosphere
[00110] When a hydrogen containing atmosphere is used, controlled transformation occurs at milder temperatures (from room temperature to 300 °C). Under these conditions, the MOF carbon microstructure is not completely decomposed, although the transition metal cations decorating the MOF nanocrystal are reduced to form a monometallic nanocrystal confined within the microporous cavities of the MOF. Formation of subnanometric metal nanocrystals are confined within the microporous MOF. Fig. 4c shows STEM images of the nanocatalyst prepared by reduction in a hydrogen containing atmosphere.
6.4. Examples of the scope of the disclosure
[00111] Some examples of supported nanocrystals prepared via our novel approach are shown in Table 1. The selection of these materials does not limit the preparation of other structures.
[00112] Table 1. Example of mono metallic and bimetallic catalysts prepared via‘single crystals to single nanocatalysts’ approach.
Figure imgf000027_0001
Figure imgf000028_0001
6.5. Example of application: advanced ammonia synthesis
[00113] Experiments demonstrating the application of the invention to ammonia synthesis are described below. Ru/Si02 was synthesized with good yield, providing material for testing in a 2- gram fixed-bed micro-reactor. Before being converted into nanocatalysts, the structure of Ru- HKUST-l was confirmed by matching X-ray Diffraction (XRD), Fourier Transformed Infrared Spectroscopy (FTIR), and BET surface area measurement showing increase in surface area of the silica composite correlated to the presence of MOF. Ru-HKUST-l was then converted into ruthenium nanoparticles using a 900 °C heat treatment with a slow temperature ramp. At temperatures above 400 °C, the high surface area and long-range structure of the MOF breaks down as certain components of the organic linker are gasified and released as C02. Monoatomic ruthenium is released from complexation and deposited on the surface among the residual organic fragments. Ruthenium atom agglomeration occurs at high temperature, and small, well-dispersed, ruthenium nanoparticles are formed on the surface of the support. A promotion procedure was followed from the literature using barium and cesium nitrates, which have been shown to promote ammonia synthesis with ruthenium catalysts (Bielawa, H.; Hinrichsen, O.; Birkner, A.; Muhler, M.: The ammonia- synthesis catalyst of the next generation: Barium-promoted oxide- supported ruthenium. Angewandte Chemie-International Edition 2001, 40, 1061-1063). The promotion was accomplished by wet deposition of barium and cesium nitrate salts from aqueous solutions onto the surface of Ru/Si02, resulting in the barium- and cesium-promoted Ru/SiC catalyst.
[00114] Testing of heat-treated Ru/Si02 catalyst was conducted to gauge activity as compared with a conventional magnetite catalyst used commercially. The catalyst was loaded into a packed bed micro-reactor and following in-situ reduction over a 2-day period, hydrogen and nitrogen were introduced into the reactor at 90 bar total pressure at a gas hourly space velocity (GHSV) of 15,000 h 1. The temperature of the reactor was 470°C. The catalyst was tested for 4 hours after reduction. The catalyst showed an average ammonia production rate of 4.59gNH3/gmetai/h.
[00115] Table 2: Comparison of Ru/Si02 and commercial catalyst characteristics and performance toward ammonia production
Surface Area NH3 production
Material (m2/g) %Ru %Cs %Ba %Si (gNm/gmetai/h)
Figure imgf000029_0001
6.6. Example of application: liquid organic hydrogen carriers
[00116] To illustrate an example of the wide application of the resulting catalysts by taking advantage of their unique features, they are used for a catalytically active platform for a pioneer concept, Fluidized-Nanoreactor Hydrogen Carriers (herein FNHCs), which consists on within fluidized mesoporous silica (herein, Fluidized-Nanoreactors, FN). OHCs consist on the chemical hydrogen storage by binding H2 to hydrogen-lean molecules by catalytic hydrogenation reactions, which can release via catalytic dehydrogenation. The bound-H2 may be used as fuel for several applications, ranging from realistic‘off-board’ hydrogen filling stations to futuristic‘on-board’ hydrogen generation on mobile platforms, such as in cars or space ships (Preuster, P.; Papp, C.; Wasserscheid, P.: Liquid Organic Hydrogen Carriers (LOHCs): Toward a Hydrogen -free Hydrogen Economy. Accounts of Chemical Research 2017, 50, 74-85.)
[00117] In order to evaluate this concept, 33 wt.% of N-ethylcarbazole (C) was impregnated on 1.7 wt.% Pd/Zr02/Si02 prepared from PdC 1 /S I/U i O - 66 (N H 2 )/S i O 2 treated at 900 °C under nitrogen. The resulting hydrogen-lean FNHC (Ho-FNHC) was loaded into a Parr bomb reactor and pressurized to 800 psig with H2 at room temperature. The reactor was heated up to 220 °C and hold until the pressure decreased and subsequently stabilized, thus indicating the end of the hydrogenation step (see Fig. 6). An aliquot (5mg) of hydrogen-loaded FNHC (HX-FNHC) was analyzed by extracting the Fh-loaded N-ethyl carbazole (Hx-C) with CHCl3 and analyzed on a GC. Complete hydrogenation of Ho-C to Hx-C containing 93.0 % of H12-C, 3.6 % of H6-C and 3.4 % of H4-C, according to GC analysis. In order to prove the reversibility, the HX-FNHC was pressurized at 30 psig of Fh and heated up to 220 °C holding until the pressure increased and was stabilized, which indicates the end of the dehydrogenation step. The analysis of the Fh-unload OHC extracted from the FNHC revealed 74.3 % of complete dehydrogenated compound (Ho-C) blended with remaining 22 % of H6-C and 3.7% of H12-C.
6.7. Example of Application: Synthetic Liquid Fuels
[00118] Fe catalysts were prepared via direct conversion of (Fe)MIL-l00/SiO2 by using two different transformation conditions at 500 C, air and nitrogen, to form Fe304/Si02 and FeC/Si02, respectively. These two catalysts were evaluated for thermal transformation of CO2 to fuels using hydrogen. An example of some of the results obtained by these catalysts containing varying loading of Fe at 320 °C, 30 bar and GHSV of 4000 h 1 are shown in Fig.7 and 8. (Wei, J.; Ge, Q.; Yao, R.; Wen, Z.; Fang, C.; Guo, L.; Xu, H.; Sun, J.: Directly converting CO2 into a gasoline fuel. Nature Communications 2017, 8, 15174-82.)
7. GENERALIZED STATEMENTS OF THE DISCLOSURE
[00119] The following numbered statements provide a general description of the disclosure and are not intended to limit the appended claims.
[00120] Statement 1: A method of preparing a confined metallic nanocatalyst within a mesoporous material (MPM) which comprises: (a) impregnating at least one or more organic compound, comprising one or more multidentate ligand(s) [AX(L X)] capable of forming coordination bonds with at least one metal ion, on the mesoporous material to form a first intermediate [(AX(L X)/MPM)] ; (b) exposing the first intermediate [(AX(L X) /MPM)] to an acid in gas phase to form a second intermediate [(HX(L X)/MPM)] ; (c) adding to the second intermediate [(HX(L X)/MPM)] a solvent solution of one or more metal ions (Mi+y, M2+y, M3 +y) so as to form coordination bonds with the one or more multidentate ligand(s) forming a metal organic framework (MOF) precursor confined within a mesoporous material [MOF/MPM], and (d) treating the precursor of step (c) [MOF/MPM] under controlled transformation conditions so as to form the metallic nanocatalyst confined within the mesoporous material.
[00121] Statement 2: The method of Statement 1, wherein step (d) further comprises step (d)(1) comprising contacting the precursor of step (c) [MOF /MPM] with one or more organic compounds (Z) to make a second multidentate ligand capable of forming coordination bonds [Z/MOF /MPM]; and step (d)(2) adding a solvent solution of one or more additional metal ion to form a modified MOF precursor with additional metals confined within the mesoporous material [MOF/MPM]
[00122] Statement 3: The method of Statements 1 or 2, wherein the chelating ligand (Z) in step (d)(1) comprises a metal binding site for complexing a second metal ion.
[00123] Statement 4: The method of Statements 1-3, wherein the controlled transformation conditions cause greater than 90% of the carbon in the MOF to be released from the MOF/MPM.
[00124] Statement 5: The method of Statements 1-4, wherein the controlled transformation conditions cause 50% ± 10% of the carbon in the MOF to be released from the MOF/MPM.
[00125] Statement 6: The method of Statements 1-5, wherein the treating under controlled transformation conditions is pyrolysis at a temperature of about 300 °C to about 1000 °C in an inert gas atmosphere.
[00126] Statement 7: The method of Statements 1-6, wherein the treating under controlled transformation conditions is calcination at a temperature of about 300 °C to about 600 °C in an atmosphere containing oxygen gas.
[00127] Statement 8: The method of Statements 1-7, wherein the treating under controlled transformation conditions is reduction with hydrogen at a temperature of about 25 °C to about 300 °C.
[00128] Statement 9: The method of Statements 1-8, wherein the confined nanocatalyst is monometallic (Mi).
[00129] Statement 10: The method of Statements 1-8, wherein the confined nanocatalyst is bimetallic (MI+M2).
[00130] Statement 11: The method of Statements 1-8, wherein the confined nanocatalyst has 3 or more metals.
[00131] Statement 12: The method of Statements 1-11, wherein the confined nanocatalyst within the mesoporous material has a diameter of less than 10 nm. [00132] Statement 13: The method of Statements 1-12, wherein the mesoporous material is a mesoporous metal oxide, a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, or a mesoporous aluminopho sphate .
[00133] Statement 14: The method of Statement 12, wherein the mesoporous metal oxide is aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, or magnesium oxide.
[00134] Statement 15: The method of Statements 1-13, wherein the mesoporous material has a surface area of about 100 m2/g to about 1000 m2/g.
[00135] Statement 16: The method of Statements 1-15, wherein the metal ions (Mi+y, M2 +y, M3 +y) are selected from the group consisting of Al, Au, Ce, Co, Fe, Ir, Mo, Ni, Pd, Rh, Ru, Ti, V and Zr or combinations thereof.
[00136] Statement 17: The method of Statements 1-16, wherein the multidentate ligand for the MOF is selected from the group consisting of, terephthalate, benzene-l,3,5-tricarboxylate, 2,5- dioxibenzene dicarboxylate, biphenyl-4,4’ -dicarboxylate, imidazolate, pyrimidine-azolate, triazolate, tetrazolate, derivatives or combinations thereof.
[00137] Statement 18: The method of Statements 1-16, wherein the MOF is selected from HKUST-l, M2(dobpdc), MIL-100, MIL-101, MIL-53, MOF-74, NU-1000, PCN-222, PCN-224, UiO-66, UiO-67, ZIF-8, ZIFs, or derivatives thereof.
[00138] Statement 19: The method of Statements 1-18, wherein the mesoporous material is selected from the group consisting of, MCM-41, SBA-15, or commercially available silica.
[00139] Statement 20: The method of Statements 1-19, wherein the confined nanocatalyst confined within mesoporous material is further reacted with additional organometallic metal complexes or metal salts with polymers, organometallic ligand precursors, nitrogen-containing organic compounds, phosphorous-containing organic compounds, sulfur-containing organic compounds, boron-containing organic compounds, halide salts, organic halides, or metal atoms added via atomic layer deposition or chemical vapor deposition.
[00140] Statement 20: A catalyst made by the method of Statements 1-19.
[00141] Statement 21: The catalyst of Statement 20, further comprising an added metal promotor.
[00142] Statement 22: The use of the catalyst of Statements 20 or 21, to catalyze alkene ammoxidation reactions, alkene epoxidation, ammonia synthesis, carboxylation reactions, C02 methanation reactions, conversion of C02 to fuel, direct methanol synthesis from methane, dry- methane reforming, electrocatalytic ammonia oxidation, electrocatalytic oxygen reduction reactions, Fischer-Tropsch synthesis, hydro -/dehydrogenation of liquid organic hydrogen carriers, hydrotreating and hydroprocessing esterification reactions, methanol synthesis from syngas, reverse water-gas shift reactions, or water-gas shift reactions.
[00143] It should be understood that the above description is only representative of illustrative embodiments and examples. For the convenience of the reader, the above description has focused on a limited number of representative examples of all possible embodiments, examples that teach the principles of the disclosure. The description has not attempted to exhaustively enumerate all possible variations or even combinations of those variations described. That alternate embodiments may not have been presented for a specific portion of the disclosure, or that further undescribed alternate embodiments may be available for a portion, is not to be considered a disclaimer of those alternate embodiments. One of ordinary skill will appreciate that many of those undescribed embodiments, involve differences in technology and materials rather than differences in the application of the principles of the disclosure. Accordingly, the disclosure is not intended to be limited to less than the scope set forth in the following claims and equivalents.
[00144] INCORPORATION BY REFERENCE
[00145] All references, articles, publications, patents, patent publications, and patent applications cited herein are incorporated by reference in their entireties for all purposes. However, mention of any reference, article, publication, patent, patent publication, and patent application cited herein is not, and should not be taken as an acknowledgment or any form of suggestion that they constitute valid prior art or form part of the common general knowledge in any country in the world. It is to be understood that, while the disclosure has been described in conjunction with the detailed description, thereof, the foregoing description is intended to illustrate and not limit the scope. Other aspects, advantages, and modifications are within the scope of the claims set forth below. All publications, patents, and patent applications cited in this specification are herein incorporated by reference as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference.

Claims

CLAIMS What is claimed is:
1. A method of preparing a confined metallic nanocatalyst within a mesoporous material (MPM) which comprises: (a) impregnating at least one or more organic compound, comprising one or more multidentate ligand(s) [AX(L X)] capable of forming coordination bonds with at least one metal ion, on the mesoporous material to form a first intermediate [(AX(L X)/MPM)] ; (b) exposing the first intermediate [(AX(L X) /MPM)] to an acid in gas phase to form a second intermediate [(HX(L X)/MPM)] ; (c) adding to the second intermediate [(HX(L X)/MPM)] a solvent solution of one or more metal ions (Mi+y, M2 +y, M3 +y) so as to form coordination bonds with the one or more multidentate ligand(s) forming a metal organic framework (MOF) precursor confined within a mesoporous material [MOF/MPM], and (d) treating the precursor of step (c) [MOF/MPM] under controlled transformation conditions so as to form the metallic nanocatalyst confined within the mesoporous material.
2. The method of claim 1, wherein step (d) further comprises step (d)(1) comprising contacting the precursor of step (d) [MOF /MPM] with one or more organic compounds (Z) to make a second multidentate ligand capable of forming coordination bonds [Z/MOF /MPM]; and step (d)(2) adding a solvent solution of one or more additional metal ion to form a modified MOF precursor with additional metals confined within the mesoporous material [MOF/MPM].
3. The method of claim 2, wherein the chelating ligand (Z) in step (d)(1) comprises a metal binding site for complexing a second metal ion.
4. The method of claim 1 , wherein the controlled transformation conditions cause greater than 90% of the carbon in the MOF to be released from the MOF/MPM.
5. The method of claim 1, wherein the controlled transformation conditions cause 50% ± 10% of the carbon in the MOF to be released from the MOF/MPM.
6. The method of claim 1, wherein the treating under controlled transformation conditions is pyrolysis at a temperature of about 300 °C to about 1000 °C in an inert gas atmosphere.
7. The method of claim 1, wherein the treating under controlled transformation conditions is calcination at a temperature of about 300 °C to about 600 °C in an atmosphere containing oxygen gas.
8. The method of claim 1, wherein the treating under controlled transformation conditions is reduction with hydrogen at a temperature of about 25 °C to about 300 °C.
9. The method of claim 1, wherein the confined nanocatalyst is monometallic (Mi).
10. The method of claim 1, wherein the confined nanocatalyst is bimetallic (MI+M2).
11. The method of claim 1, wherein the confined nanocatalyst has 3 or more metals.
12. The method of claim 1, wherein the confined nanocatalyst within the mesoporous material has a diameter of less than 10 nm.
13. The method of claim 1, wherein the mesoporous material is a mesoporous metal oxide, a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, or a mesoporous aluminophosphate.
14. The method of claim 13, wherein the mesoporous metal oxide is aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, or magnesium oxide.
15. The method of claim 1, wherein the mesoporous material has a surface area of about 100 m2/g to about 1000 m2/g.
16. The method of claim 1, wherein the metal ions (Mi+y, M2 +y, M3 +y) are selected from the group consisting of Al, Au, Ce, Co, Fe, Ir, Mo, Ni, Pd, Rh, Ru, Ti, V and Zr or combinations thereof.
17. The method of claim 1, wherein the multidentate ligand for the MOF is selected from the group consisting of, terephthalate, benzene-l,3,5-tricarboxylate, 2,5-dioxibenzene dicarboxylate, biphenyl-4, 4’-dicarboxylate, imidazolate, pyrimidine-azolate, triazolate, tetrazolate, derivatives or combinations thereof.
18. The method of claim 1, wherein the MOF is selected from HKUST-l, M2(dobpdc), MIL- 100, MIL-101, MIL-53, MOF-74, NU-1000, PCN-222, PCN-224, UiO-66, UiO-67, ZIF- 8, ZIFs, or derivatives thereof.
19. The method of claim 1, wherein the mesoporous material is selected from the group consisting of, MCM-41, SBA-15, or commercially available silica.
20. The method of claim 1, wherein the confined nanocatalyst confined within mesoporous material is further reacted with additional organometallic metal complexes or metal salts with polymers, organometallic ligand precursors, nitrogen-containing organic compounds, phosphorous-containing organic compounds, sulfur-containing organic compounds, boron-containing organic compounds, halide salts, organic halides, or metal atoms added via atomic layer deposition or chemical vapor deposition.
21. A catalyst made by the method of claim 1.
22. The catalyst of claim 21, further comprising an added metal promotor.
23. The use of the catalyst of claim 21 to catalyze alkene ammoxidation reactions, alkene epoxidation, ammonia synthesis, carboxylation reactions, C02 methanation reactions, conversion of C02 to fuel, direct methanol synthesis from methane, dry-methane reforming, electrocatalytic ammonia oxidation, electrocatalytic oxygen reduction reactions, Fischer-Tropsch synthesis, hydro-/dehydrogenation of liquid organic hydrogen carriers, hydrotreating and hydroprocessing esterification reactions, methanol synthesis from syngas, reverse water-gas shift reactions, or water-gas shift reactions.
PCT/US2019/023989 2018-03-26 2019-03-26 Method of making confined nanocatalysts within mesoporous materials and uses thereof Ceased WO2019191034A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
KR1020207030458A KR102747349B1 (en) 2018-03-26 2019-03-26 Method for producing nanocatalyst confined in mesoporous material and use thereof
ES19776162T ES2980683T3 (en) 2018-03-26 2019-03-26 Method for manufacturing nanocatalysts confined within mesoporous materials and their uses
US17/041,944 US11406971B2 (en) 2018-03-26 2019-03-26 Method of making confined nanocatalysts within mesoporous materials and uses thereof
EP19776162.0A EP3774038B1 (en) 2018-03-26 2019-03-26 Method of making confined nanocatalysts within mesoporous materials and uses thereof
JP2020551555A JP7281478B2 (en) 2018-03-26 2019-03-26 Methods for making nanocatalysts confined within mesoporous materials and uses thereof
CN201980032699.0A CN112218716A (en) 2018-03-26 2019-03-26 Methods for preparing confined nanocatalysts within mesoporous materials and their uses
CA3095128A CA3095128A1 (en) 2018-03-26 2019-03-26 Method of making confined nanocatalysts within mesoporous materials and uses thereof
AU2019242630A AU2019242630B2 (en) 2018-03-26 2019-03-26 Method of making confined nanocatalysts within mesoporous materials and uses thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201862647949P 2018-03-26 2018-03-26
US62/647,949 2018-03-26

Publications (1)

Publication Number Publication Date
WO2019191034A1 true WO2019191034A1 (en) 2019-10-03

Family

ID=68058446

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2019/023989 Ceased WO2019191034A1 (en) 2018-03-26 2019-03-26 Method of making confined nanocatalysts within mesoporous materials and uses thereof

Country Status (9)

Country Link
US (1) US11406971B2 (en)
EP (1) EP3774038B1 (en)
JP (1) JP7281478B2 (en)
KR (1) KR102747349B1 (en)
CN (1) CN112218716A (en)
AU (1) AU2019242630B2 (en)
CA (1) CA3095128A1 (en)
ES (1) ES2980683T3 (en)
WO (1) WO2019191034A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111420640A (en) * 2020-04-14 2020-07-17 佛山科学技术学院 HKUST-1 composite material and preparation method thereof
CN111921561A (en) * 2020-08-18 2020-11-13 浙江工业大学 Hierarchical hollow structure NH2Preparation method of-MIL-125 (Ti) desulfurization catalyst
CN111939984A (en) * 2020-08-25 2020-11-17 太原理工大学 Electrochemical catalyst, preparation method and application thereof
CN113398935A (en) * 2021-05-26 2021-09-17 华南理工大学 Ruthenium-nickel/graphene-composite oxide metal aerogel catalyst and preparation method and application thereof
CN114768858A (en) * 2022-03-14 2022-07-22 天津科技大学 A kind of non-precious metal catalyst for nitrogen-containing organic liquid hydrogen storage in fixed bed reactor
CN116253332A (en) * 2023-02-09 2023-06-13 东南大学 A Plasma-Assisted Ammonia Synthesis Method Based on Ni-Co Bimetallic MOF
EP4362146A1 (en) * 2022-10-26 2024-05-01 Umicore AG & Co. KG Phosphorus doped pgm-type catalysts and catalytic system for storing and releasing of hydrogen of organic hydrogen carriers
CN118894994A (en) * 2024-08-19 2024-11-05 广东碳语新材料有限公司 A sponge structure MIL-101 material and its preparation method and application
WO2025196205A1 (en) 2024-03-21 2025-09-25 Casale Sa Method of managing an ammonia synthesis reactor during fluctuating feed rates

Families Citing this family (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2017311400B2 (en) 2016-08-10 2022-07-14 Research Triangle Institute Solid-state crystallization of metal organic frameworks within mesoporous materials methods and hybrid materials thereof
ES2980683T3 (en) 2018-03-26 2024-10-02 Res Triangle Inst Method for manufacturing nanocatalysts confined within mesoporous materials and their uses
CN113092560B (en) * 2019-12-23 2022-03-18 中国科学院生态环境研究中心 A kind of electrode material for detecting nickel ion, preparation method and use thereof
CN113426472B (en) * 2020-03-23 2022-09-09 中国科学院山西煤炭化学研究所 A kind of cobalt-based catalyst, CO2 catalytic hydrogenation method for producing CO
CN112121763B (en) * 2020-09-21 2023-08-04 广东石油化工学院 Carbon-based Mn-MOF-500 adsorption material and preparation method thereof
US12564830B2 (en) 2020-10-07 2026-03-03 Research Triangle Institute Porous metal organic framework-polymer composites for use in detoxifying chemical warfare agents
CN112371188B (en) * 2020-11-03 2022-10-28 宁波诺丁汉新材料研究院有限公司 Preparation method of efficient methanation nano catalyst
KR102472412B1 (en) * 2020-11-30 2022-12-01 한국과학기술연구원 A Catalyst for dehydrogenation of liquid organic hydrogen carriers and method for producing the same
KR20220094044A (en) 2020-12-28 2022-07-05 전남대학교산학협력단 Spinel-derived cobalt- manganese oxide catalyst for electrocatalytic nitrogen reduction and preparation method thereof
CN112892598B (en) * 2021-01-26 2022-05-24 烟台市友利化工科技有限公司 Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst
CN112889841B (en) * 2021-01-26 2022-04-15 张斌翔 A kind of photocatalytic apatite coating technology to kill virus spray
CN113262776B (en) * 2021-04-20 2023-09-22 武汉理工大学 A W-TiO2 single atom supported photocatalyst and its preparation method
CN113351252B (en) * 2021-05-25 2023-04-14 山东能源集团有限公司 A methane conversion catalyst, its preparation method, and a method for synergistically converting methane using plasma and catalyst
CN114315496B (en) * 2021-05-27 2024-04-26 上海科技大学 A preparation method of alkane compound, catalyst and application thereof
CN113480741B (en) * 2021-07-16 2023-09-19 辽宁石油化工大学 Preparation method of chelated Cu2+ metal organic framework material and its application in chitosan composite anionic membrane
CN113559941A (en) * 2021-08-24 2021-10-29 大连工业大学 A catalyst based on MOFs material supported metal nanoparticles and its preparation method and application
CN113663735B (en) * 2021-09-16 2023-07-14 沈阳师范大学 A surface-hydrophobized variable-valence copper-based metal-organic framework catalyst and its preparation method and application
CN113663716B (en) * 2021-09-28 2022-07-05 南京工业大学 Indium oxide supported metal single-atom catalyst and its application
CN115957762B (en) * 2021-10-11 2025-01-17 中国科学院大连化学物理研究所 A bimetallic element doped silicon dioxide composite nanomaterial and its preparation method and application
CN114569718B (en) * 2021-11-19 2023-03-10 兰州大学 A preparation method of nanomaterials for imaging and tumor therapy
CN114082451B (en) * 2021-11-25 2022-12-06 西安交通大学 Preparation method of MOF (metal organic framework) derived nanoreactors with different structures
CN114192193B (en) * 2021-12-09 2023-06-16 中国科学技术大学 Preparation method and application of molybdenum disulfide doped MIL-53 (Al) composite material
CN114558623B (en) * 2021-12-09 2023-06-30 淮阴工学院 Preparation method of Ru-loaded hydroxyl MOF photocatalyst and application of Ru-loaded hydroxyl MOF photocatalyst in nitrogen fixation ammonia synthesis
CN114160115B (en) * 2021-12-10 2023-09-01 福州大学 A method for synthesizing zirconia-based solid solution based on MOF
CN114209831A (en) * 2021-12-29 2022-03-22 齐鲁工业大学 Application of porphyrin metal organic framework derivative mesoporous carbon in preparation of light therapeutic agent
CN114405518B (en) * 2021-12-30 2023-12-05 广东省科学院化工研究所 Solid acid-bimetallic nanoparticle composite material and preparation method and application thereof
CN114349076B (en) * 2022-01-25 2023-12-15 东北电力大学 A synthesis method and application of NiCoMo-LDH composite material
CN114674966B (en) * 2022-03-28 2024-09-13 武汉海关技术中心 Preparation method of beta-receptor blocker and beta 2-receptor agonist extraction material
CN114634628B (en) * 2022-04-18 2023-06-13 佛山科学技术学院 A preparation method of barium-based metal-organic framework material for separating methane and nitrogen
CN114906801B (en) * 2022-05-26 2023-10-10 重庆大学 A kind of MgH2@Fe-ZIF hydrogen storage material and its preparation method
CN115090334B (en) * 2022-07-06 2023-09-29 扬州工业职业技术学院 MOF-derived porous carbon-based nano composite photodegradable material
CN115212875B (en) * 2022-07-10 2023-09-01 华东理工大学 Preparation method of high-efficiency photocatalytic methane dry reforming monoatomic ruthenium doped-porous titanium silicon material
CN115212867B (en) * 2022-08-09 2024-03-29 常州大学 A mesoporous SiO2 confined Ni-MgO composite derivative catalyst and its preparation method and application
CN115716995A (en) * 2022-11-24 2023-02-28 华东师范大学 Preparation method of metal organic framework-gold composite material
CN115980030B (en) * 2022-12-15 2025-05-27 山东大学 Nanometer enzyme for detecting heavy metals and preparation method and application thereof
CN116314876B (en) * 2023-01-09 2026-03-20 中国科学院青岛生物能源与过程研究所 A mesoporous carbon-supported heteroatom-doped metal catalyst and its preparation method
WO2024178359A1 (en) * 2023-02-24 2024-08-29 Northwestern University Methods for non-contact reduction for formation of metal nanostructures
CN116273093B (en) * 2023-03-01 2025-06-10 南京大学 Reverse water gas shift catalyst and preparation method and application thereof
CN116764647B (en) * 2023-04-28 2024-05-14 重庆工商大学 A cubic CoCu spinel/carbon catalyst for efficient hydrogen production and pollutant degradation
CN116590044B (en) * 2023-05-12 2024-09-10 中国科学技术大学 A method for producing bio-aviation fuel using bagasse waste
CN116328849B (en) * 2023-05-12 2024-05-28 郑州大学 A biochar-based MOFs catalyst and its preparation method and application
CN116786170A (en) * 2023-06-25 2023-09-22 天津科技大学 A preparation method of ZIF-based material combined with α-Al2O3 dispersed silver catalyst
CN116803520B (en) * 2023-06-28 2024-04-05 黑龙江省科学院石油化学研究院 Mesoporous SiO2-supported palladium-ruthenium catalyst suitable for both hydrogen storage and hydrogen release in liquid organic hydrogen carrier and preparation method thereof
CN116943707B (en) 2023-07-31 2025-08-22 南京大学 Preparation method and application of reverse water-gas shift reaction catalyst
CN117258792B (en) * 2023-09-19 2026-01-02 江苏扬农化工集团有限公司 A nickel porphyrin carbon-based catalyst, its preparation method and application
CN117399011B (en) * 2023-10-10 2024-05-07 天水师范学院 A method for preparing nickel-copper catalytic material for saturated hydrogenation of hydrocarbons
CN117399074B (en) * 2023-10-17 2025-11-21 太原理工大学 Preparation method and application of MIL-100 (Fe) catalyst rich in defects and nitrogen species
CN117568861B (en) * 2023-10-30 2025-10-21 浙江大学杭州国际科创中心 Covalent organic framework composite carbon nanotube and its preparation method and application
CN119977766B (en) * 2023-11-13 2026-02-06 中国石油化工股份有限公司 Preparation methods of 2-methoxyolefins and metal-organic framework materials and their preparation methods
PL447020A1 (en) * 2023-12-07 2025-06-09 Uniwersytet Warszawski Highly porous alumina-naphthalenedicarboxylic organic frameworks and their composites with nanostructural gold, methods of their production and use in catalytic conversion of CO2 to cyclic esters
CN117861703A (en) * 2023-12-19 2024-04-12 江南大学 A copper-palladium alloy catalyst for synthesizing glycerol carbonate and its preparation method and application
CN118495467A (en) * 2024-05-15 2024-08-16 浙江大学 Borohydride/nitrogen-doped dodecahedron porous carbon composite hydrogen storage material, and preparation and application thereof
CN118719024B (en) * 2024-09-03 2024-12-03 西南石油大学 Core-shell structure carbon dioxide adsorbent and preparation method and application thereof
CN119191281B (en) * 2024-10-10 2025-08-29 中国海洋大学 A two-dimensional ultrathin graphene nanosheet and preparation method thereof
CN119702002B (en) * 2024-12-06 2026-03-20 中国石油化工股份有限公司 A DINP hydrogenation catalyst based on a metal oxide support, its preparation method and application
CN119951586A (en) * 2024-12-12 2025-05-09 浙江大学 Method for synthesizing phenylchlorosilane by ZnCo-ZIF/CeO2 catalysis and catalyst used therein
CN119978407B (en) * 2025-01-08 2025-11-28 三峡大学 Preparation methods of nickel-containing metal-organic framework materials and their application as oxygen evolution materials in electrocatalytic water splitting process
CN119951590B (en) * 2025-01-25 2025-11-21 辽宁大学 A bimetallic metal-organic framework Pd0.2Ni0.8@MIL-101 Pickering emulsion, its preparation method, and its application.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130273461A1 (en) * 2012-04-11 2013-10-17 Uchicago Argonne, Llc Synthesis of electrocatalysts using metal-organic framework materials
WO2018031733A1 (en) * 2016-08-10 2018-02-15 Research Triangle Institute Solid-state crystallization of metal organic frameworks within mesoporous meterials methods and hybrid materials thereof
CN107774331A (en) * 2017-10-25 2018-03-09 宿迁市振兴化工有限公司 A kind of Metal Supported MOFs catalyst and preparation method thereof and the application in PMDPTA synthesis

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19854635A1 (en) 1998-11-26 2000-05-31 Basf Ag Supported catalyst and its use in hydrogenation
CN1798725A (en) 2003-06-05 2006-07-05 伊斯曼化学公司 Supported metal-phosphine-aminophosphine catalysts
WO2008072896A1 (en) 2006-12-13 2008-06-19 Korea Research Institute Of Chemical Technology A porous organic-inorganic hybrid materials and an absorbent comprising the same
KR101034988B1 (en) * 2008-04-17 2011-05-17 한국화학연구원 Superporous organic-inorganic nanoporous complex formed by covalent bonding of organic-inorganic hybrids and macro mesoporous materials
KR101158456B1 (en) 2009-11-19 2012-06-19 한국화학연구원 Porous organic-inorganic hybrid materials with crystallinity and method for preparing thereof
KR101663184B1 (en) 2009-12-15 2016-10-06 삼성전자주식회사 Hybrid porous material and method of preparing same
US20120152845A1 (en) 2010-05-27 2012-06-21 Vanderbilt University Porous silica-metal organic composite adsorbents and methods of making and using the same
CA2826510A1 (en) 2011-02-08 2012-08-16 Institut National De La Recherche Scientifique Catalysts made using thermally decomposable porous supports
US9931623B2 (en) 2012-11-30 2018-04-03 Hiroshima University Method for producing metal nanoparticle complex, and metal nanoparticle complex produced by said method
DE102013105471A1 (en) 2013-04-06 2014-10-09 BLüCHER GMBH Activated carbon impregnated with metal-organic framework material, preferably in the form of activated carbon with reactive, catalytic activity, useful in protection material for civilian or military areas
CN104624160B (en) * 2015-01-21 2017-01-25 北京科技大学 A kind of preparation method of metal-organic framework gas storage material with enhanced thermal conductivity
CN105056895B (en) 2015-08-17 2017-07-28 中国科学院上海高等研究院 A kind of preparation method and applications of metal organic framework mesopore silicon oxide composite
CN107008507B (en) * 2017-06-08 2020-05-22 合肥工业大学 Mesoporous Fe-based MOF @ AgI efficient composite visible light photocatalytic material and preparation method and application thereof
ES2980683T3 (en) 2018-03-26 2024-10-02 Res Triangle Inst Method for manufacturing nanocatalysts confined within mesoporous materials and their uses

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130273461A1 (en) * 2012-04-11 2013-10-17 Uchicago Argonne, Llc Synthesis of electrocatalysts using metal-organic framework materials
WO2018031733A1 (en) * 2016-08-10 2018-02-15 Research Triangle Institute Solid-state crystallization of metal organic frameworks within mesoporous meterials methods and hybrid materials thereof
CN107774331A (en) * 2017-10-25 2018-03-09 宿迁市振兴化工有限公司 A kind of Metal Supported MOFs catalyst and preparation method thereof and the application in PMDPTA synthesis

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KOO, WON-TAE ET AL.: "Metal-organic framework templated synthesis of ultrasmall catalyst loaded Zn0/ZnCo204 hollow spheres for enhanced gas sensing properties", SCIENTIFIC REPORTS, vol. 7, no. 45074, 2017, pages 1 - 10, XP055639106 *
LUZ, IGNACIO ET AL.: "Transformation of single MOF nanocrystals into single nanostructured catalysts within mesoporous supports: a platform for pioneer fluidized-nanoreactor hydrogen carriers", CHEMICAL COMMUNICATIONS, vol. 54, no. 61, 2018, pages 8462 - 8465, XP055639116, [retrieved on 20180703] *
See also references of EP3774038A4 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111420640A (en) * 2020-04-14 2020-07-17 佛山科学技术学院 HKUST-1 composite material and preparation method thereof
CN111420640B (en) * 2020-04-14 2022-12-23 佛山科学技术学院 A kind of HKUST-1 composite material and preparation method thereof
CN111921561A (en) * 2020-08-18 2020-11-13 浙江工业大学 Hierarchical hollow structure NH2Preparation method of-MIL-125 (Ti) desulfurization catalyst
CN111921561B (en) * 2020-08-18 2023-06-23 浙江工业大学 Hierarchical hollow structure NH 2 Preparation method of MIL-125 (Ti) desulfurization catalyst
CN111939984A (en) * 2020-08-25 2020-11-17 太原理工大学 Electrochemical catalyst, preparation method and application thereof
CN113398935A (en) * 2021-05-26 2021-09-17 华南理工大学 Ruthenium-nickel/graphene-composite oxide metal aerogel catalyst and preparation method and application thereof
CN114768858A (en) * 2022-03-14 2022-07-22 天津科技大学 A kind of non-precious metal catalyst for nitrogen-containing organic liquid hydrogen storage in fixed bed reactor
CN114768858B (en) * 2022-03-14 2024-06-11 天津科技大学 Non-noble metal catalyst for nitrogen-containing organic liquid hydrogen storage of fixed bed reactor
WO2024089176A1 (en) * 2022-10-26 2024-05-02 Umicore Ag & Co. Kg Phosphorus doped pgm-type catalysts and catalytic system for storing and releasing of hydrogen of organic hydrogen carriers
EP4362146A1 (en) * 2022-10-26 2024-05-01 Umicore AG & Co. KG Phosphorus doped pgm-type catalysts and catalytic system for storing and releasing of hydrogen of organic hydrogen carriers
CN116253332A (en) * 2023-02-09 2023-06-13 东南大学 A Plasma-Assisted Ammonia Synthesis Method Based on Ni-Co Bimetallic MOF
WO2025196205A1 (en) 2024-03-21 2025-09-25 Casale Sa Method of managing an ammonia synthesis reactor during fluctuating feed rates
CN118894994A (en) * 2024-08-19 2024-11-05 广东碳语新材料有限公司 A sponge structure MIL-101 material and its preparation method and application

Also Published As

Publication number Publication date
JP2021519204A (en) 2021-08-10
CA3095128A1 (en) 2019-10-03
EP3774038A1 (en) 2021-02-17
AU2019242630B2 (en) 2024-05-23
US11406971B2 (en) 2022-08-09
KR20200127038A (en) 2020-11-09
KR102747349B1 (en) 2024-12-26
AU2019242630A1 (en) 2020-10-15
EP3774038C0 (en) 2024-05-22
JP7281478B2 (en) 2023-05-25
US20210008529A1 (en) 2021-01-14
EP3774038A4 (en) 2021-12-29
CN112218716A (en) 2021-01-12
ES2980683T3 (en) 2024-10-02
EP3774038B1 (en) 2024-05-22

Similar Documents

Publication Publication Date Title
US11406971B2 (en) Method of making confined nanocatalysts within mesoporous materials and uses thereof
AU2022203682B2 (en) Solid-State Crystallization Of Metal Organic Frameworks Within Mesoporous Materials Methods And Hybrid Materials Thereof
Alamgholiloo et al. Formation and stabilization of colloidal ultra-small palladium nanoparticles on diamine-modified Cr-MIL-101: Synergic boost to hydrogen production from formic acid
KR101936493B1 (en) Mof-derived porous carbon materials for carbon dioxide capture
Koh et al. Formic acid dehydrogenation over Pd NPs supported on amine-functionalized SBA-15 catalysts: structure–activity relationships
Jiang et al. Porous metal–organic frameworks as platforms for functional applications
Choi et al. Mercaptosilane-assisted synthesis of metal clusters within zeolites and catalytic consequences of encapsulation
Gong et al. Main-chain poly (ionic liquid)-derived nitrogen-doped micro/mesoporous carbons for CO2 capture and selective aerobic oxidation of alcohols
Montazerolghaem et al. A metal–organic framework MIL-101 doped with metal nanoparticles (Ni & Cu) and its effect on CO 2 adsorption properties
Luz et al. Confining metal–organic framework nanocrystals within mesoporous materials: a general approach via “solid-state” synthesis
Xu et al. PdAg alloy nanoparticles immobilized on functionalized MIL-101-NH 2: effect of organic amines on hydrogenation of carbon dioxide into formic acid
Ky et al. Mg2+ embedded MIL‐101 (Cr)‐NH2 framework for improved CO2 adsorption and CO2/N2 selectivity
Hengne et al. Selective Production of Oxygenates from Carbon Dioxide Hydrogenation over a Mesoporous‐Silica‐Supported Copper‐Gallium Nanocomposite Catalyst
HK40043285B (en) Method of making confined nanocatalysts within mesoporous materials and uses thereof
HK40043285A (en) Method of making confined nanocatalysts within mesoporous materials and uses thereof
KR102123793B1 (en) A carbon monoxide adsorbents with carbon monoxide selectivity and manufacturing method of the same
Wang Study of Metal Nanoparticle Catalysts for High-Performance Hydrogen Generation from Chemical Hydrides
Kossmann Controlled condensation to functional materials–synergetic effect of nitrogen content and pore structure
Koh Design and synthesis of nanocatalysts enabling hydrogen storage, release and electrocatalysis
Rao et al. Metal Organic Framework Composites with High Interfacial Porosity for Enhanced Carbon Dioxide Capture

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19776162

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3095128

Country of ref document: CA

Ref document number: 2020551555

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2019242630

Country of ref document: AU

Date of ref document: 20190326

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20207030458

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2019776162

Country of ref document: EP

Effective date: 20201026