WO2009122149A1 - Procédé de préparation d'un catalyseur supporté à l'aide de nanoparticules de métal noble et catalyseur ainsi obtenu - Google Patents

Procédé de préparation d'un catalyseur supporté à l'aide de nanoparticules de métal noble et catalyseur ainsi obtenu Download PDF

Info

Publication number
WO2009122149A1
WO2009122149A1 PCT/GB2009/000821 GB2009000821W WO2009122149A1 WO 2009122149 A1 WO2009122149 A1 WO 2009122149A1 GB 2009000821 W GB2009000821 W GB 2009000821W WO 2009122149 A1 WO2009122149 A1 WO 2009122149A1
Authority
WO
WIPO (PCT)
Prior art keywords
noble metal
metal nanoparticles
catalyst
ionic liquid
sol
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/GB2009/000821
Other languages
English (en)
Inventor
Jairton Dupont
Sandra Shirley Ximeno Chiaro
Marcos Alexandre Geleysky
Flavio André PAVAN
João Henrique ZIMNOCH DOS SANTOS
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.)
Petroleo Brasileiro SA Petrobras
BENSON JOHN EVERETT
Original Assignee
Petroleo Brasileiro SA Petrobras
BENSON JOHN EVERETT
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 Petroleo Brasileiro SA Petrobras, BENSON JOHN EVERETT filed Critical Petroleo Brasileiro SA Petrobras
Publication of WO2009122149A1 publication Critical patent/WO2009122149A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/923—Compounds thereof with non-metallic elements
    • 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
    • Y02E60/50—Fuel cells

Definitions

  • This invention relates to the field of the preparation of a supported catalyst comprising nanoparticles of a noble metal.
  • the method includes dispersion of the particles into an ionic liquid and incorporation into a matrix by a sol-gel process, in a single stage.
  • the usual methods for stabilising metal nanoparticles involve the use of protective agents, such as binders with functional groups, surfactants and polymers, which have the disadvantage of causing the loss of catalytic activity as they can occupy the active catalytic sites, apart from the difficulty of removing them from the reaction medium, suggesting improvements such as those obtained through the use of ionic liquids, as will be described below.
  • protective agents such as binders with functional groups, surfactants and polymers
  • Ionic liquids as defined in Patent US 7,252,791, are salts or mixtures of salts having a melting point below 100 0 C. Salts of this type known in the literature are derived from ammonium, phosphonium, pyridine or imidazolium cations associated with anions, such as halogen-stannates, halogen-aluminates, hexafluoro- phosphates or tetrafluoroborates .
  • the most investigated and used ionic liquids are those based on 1, 3-dialkyl-imidazolium cations, because they have unique physical and chemical properties such as low vapour pressure, a liquid state over a wide temperature range (close to ambient temperature) , sufficiently low viscosity ( ⁇ 800 mm 2 /s at 20 0 C); they are non-flammable, thermal and electrochemical stability are more favourable than for common solvents, there is the possibility of a wide range of organic and inorganic compounds whose solubilities can be adjusted by selecting the alkyl groups bound to the imidazolium ring or the nature of the ion, typically non- coordinating liquids which are easily prepared from commercial reagents using conventional processes of synthesis . These unique properties confer operational advantages in a large number of industrial applications such as for example their use as a "green" solvent to replace conventional organic solvents, and in catalytic processes which are selective at ambient temperature under more economical energy conditions.
  • metal nanoparticles dispersed in ionic liquids show significant improvements in stability when applied in catalytic systems, in some cases they still tend to aggregate. On the other hand the nanoparticles can be easily incorporated into matrices to produce more stable catalysts having greater catalytic activity.
  • the sol-gel process is based on the preparation of a "network" of oxides created by reactions involving the hydrolysis and condensation of molecular precursors, generally alkoxides or inorganic salts, both reactions being affected by the presence of acid or basic catalysts.
  • Homogeneous catalysts whose catalytic activity takes place at molecular level, and heterogeneous catalysts in which catalytic activity is governed by surface phenomena, have been incorporated into matrices by sol-gel processes using ionic liquids and metal precursors such as [RhCl (PPh 3 ) 3 ] and Rh (AcAc) 3 .
  • ionic liquids and metal precursors such as [RhCl (PPh 3 ) 3 ] and Rh (AcAc) 3 .
  • Rh (AcAc) 3 Rh
  • These catalysts are prepared by covalent bonding of the ionic liquids to the surface of the matrix, or simply depositing catalytically active species on the surface of the matrix, usually silica or polymer materials.
  • Patent US 2007/0101824 describes a method for producing nanoparticles incorporated in a matrix, preferably carbon, using a metal precursor dispersed in an ionic liquid, in which the particle size is reduced through heating by microwaves.
  • the compositions so produced can be used as catalysts, fuel cells, super- capacitors, and components for batteries and the like.
  • Patent US 6,686,308 describes a method for the preparation of a supported catalyst comprising metal nanoparticles having a mean size of 3 nm or less, supported in a matrix, preferably carbon.
  • the metal nanoparticles content of the supported catalyst is 30% m/m.
  • the metals may be selected from: palladium, platinum, ruthenium, rhodium, iridium, osmium, molybdenum, tungsten, iron, nickel and tin.
  • this invention relates to a method for the preparation of a supported catalyst comprising noble metal nanoparticles, the particles being dispersed in an ionic liquid and incorporated in a matrix by a sol-gel process, in a single stage.
  • the method comprises taking noble metal nanoparticles, dispersing the nanoparticles in an ionic liquid and a co-solvent, and encapsulating the nanoparticles in a solid matrix through the sol-gel process .
  • the method provides a supported catalyst having a proportion of noble metal nanoparticles within the range between 0.10% and 0.15% m/m in relation to the supported catalyst.
  • the supported catalysts so obtained are quite homogeneous and have a regular distribution of noble metal nanoparticles in the solid matrix and have greater catalytic activity than isolated noble metal nanoparticles .
  • Figure 1 shows a typical diffractogram of Rh(O) nanoparticles obtained by reducing the RhCl 3 .nH 2 ⁇ precursor in BMI. BF 4 ionic liquid as described in Example 1.
  • Figure 2 shows a diffractogram of Rh(O) nanoparticles encapsulated in a silica matrix, prepared by the acid route, using BMI. BF 4 as the ionic liquid and a quantity of Rh(O) less than 2% in relation to the silica, as described in Example 2.
  • Figure 3 shows a micrograph of Rh(O) /SiO 2 synthesised using BMI. BF 4 by the sol-gel method in acid medium, a synthesis according to the method described in Example 2.
  • Figure 4 shows a micrograph of Rh(O) /Si ⁇ 2 synthesised using BMI. BF 4 by the sol-gel method in basic medium, a synthesis according to the method described in Example 3.
  • Figure 5 illustrates the chemical mapping of Rh(O) /SiO 2 synthesised using ' BMLBF 4 by the sol-gel method in acid medium, a synthesis according to the method described in Example 2.
  • Figure 6 illustrates the chemical mapping of Rh(O) /SiO 2 synthesised using BMLBF 4 by the sol-gel method in basic medium, a synthesis according to the method described in Example 3.
  • Figure 7 illustrates transmission electron microscopy and a size distribution histogram for the Rh(O) /SiO 2 catalyst synthesised using BMLBF 4 by the sol-gel method in acid medium, a synthesis according to the method described in Example 2.
  • Figure 8 illustrates the hydrogenation reaction of 1-hexene (-•-) and cyclohexene (-!-) catalysed by Rh(O) /SiO 2 /HF under a pressure of 4°C to 75°C, and an aromatic hydrocarbon/Rh (0) ratio of 1179.
  • Figure 9 shows electron transmission microscopy and a size distribution histogram for isolated nanoparticles of Rh(O) prepared in BMLBF 4 ionic liquid and redispersed in isopropanol.
  • the method described below comprises the preparation of a supported catalyst using noble metal nanoparticles dispersed in an ionic liquid and incorporated in a matrix through a sol-gel process, in a single stage.
  • the supported catalyst obtained has noble metal nanoparticles having a mean size within the range from 3 nm to 6 nm and a noble metal nanoparticle concentration in the supported catalyst within the range from 0.10% to 0.15% (m/m) .
  • the particle size is preferably a particle diameter of substantially spherical particles, and where the particles are not substantially spherical it is preferably the diameter of notional particles of the same volume as that of the actual particles .
  • the method according to this invention comprises the stages of: a) providing noble metal nanoparticles having a mean particle size within the range from 3 nm to 6 nm, b) providing a mixture comprising an ionic liquid and a co-solvent, c) obtaining a dispersion by adding noble metal nanoparticles to the mixture obtained in b) , d) adding a solid matrix molecular precursor to the dispersion obtained in c) , e) adding a catalyst for the sol-gel process, f) recovering a supported catalyst comprising noble metal nanoparticles dispersed in ionic liquid and incorporated in a solid matrix.
  • Noble metal nanoparticles which are useful for the method according to this invention may be obtained by any of the methods available in the state of the art for noble metals selected from: iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, platinum and palladium. Preferably, rhodium.
  • the use of nanoparticles of noble metals in elemental form represents a great advantage ever preparing supported catalysts obtained from metal precursors. When metal precursors are incorporated into a solid matrix there is an additional stage of reducing the metal to its elemental form, and the possibility of interaction between the metal precursor and the solid phase affecting the final size of the particles obtained. This is avoided through directly using nanoparticles of noble metal in elemental form without the additional stage of reducing the metal.
  • the noble metal nanoparticles must be dispersed in ionic liquids with the addition of an alcohol, preferably ethanol, which acts as a co-solvent having the function of reducing the viscosity of the ionic liquid and thus assisting handling.
  • an alcohol preferably ethanol
  • the useful proportion for achieving this objective is 10% to 20% of ionic liquid in relation to the quantity of co- solvent.
  • the ionic liquids act in steric and electrostatic stabilisation of the noble metal nanoparticles mainly because of their high charge and polarisation.
  • the ionic liquids useful for the method are derivatives of the 1-3-dialkylimidazolium cation associated with poorly coordinating anions, preferably PF 6 " , BF 4 " , CF 3 SO 3 " , (CF 3 SO 2 ) 2 N " .
  • the choice of anion used is based on the characteristics desired for the ionic liquid, as a correct choice of anion will influence the physical and chemical properties of the liquid such as viscosity, solvating power, catalytic activity, hydrophobicity and melting point.
  • the useful salts derived from the 1-3-dialkylimidazolium cation have pre-organised structures which can be adapted to different species, because they have both hydrophobic and hydrophilic regions, and high polarisability .
  • This structural organisation acts as an "entropy signpost" for solid matrices on the nanoscale, such as those prepared by a sol-gel process .
  • the chemistry of a sol-gel process is based on the hydrolysis and condensation of molecular precursors.
  • the stage of hydrolysing a metal alkoxide takes place by reacting this with water, generating a hydroxy group (M-OH) .
  • This reaction is based on the nucleophilic addition of the water molecule to the metal atom.
  • the second stage in the sol-gel process comprises condensing the M-OH species, giving rise to the formation of -M-O-H- bonds, which after various condensation stages result in a MOn "network".
  • a catalyst which may be an acid or a base.
  • Useful acids for this invention may be any inorganic acids, preferably HF or HCl.
  • bases NH 4 OH is preferably used.
  • the excess ionic liquid can be separated off and recovered by any known methods such as solvent extraction or calcination.
  • solvents used for extraction acetone is preferably used. • Calcination is carried out at a temperature of 450 0 C.
  • the supported catalysts prepared in this way have noble metal nanoparticles having a particle size in the range from 3 nm to 6 run, as shown in Figure 7, with no change in relation to the mean particle size of the noble metal used for the said method, illustrated in Figure 9, which is an indication that there is no sintering, and therefore of the stabilisation provided by the ionic liquids .
  • the noble metal nanoparticles are homogeneously distributed throughout the solid matrix, mainly because of the stabilisation provided by the ionic liquid.
  • Catalysts produced according to the method of this invention may be used in hydrogenation reactions, as the ionic liquid present in the pores of the solid matrix has the property of satisfactorily dissolving unsaturated hydrocarbons, but not alkanes, making the selective reduction of dienes to simple olefins (hydrogenation) possible.
  • the catalytic activity of these catalysts is greater than that of isolated noble metal nanoparticles, as shown in Table 2, as well as making it possible to use small quantities of noble metal in the catalyst without losing its catalytic activity, as illustrated in Table 3.
  • This example illustrates the preparation and isolation of rhodium nanoparticles.
  • Rh nanoparticles were carried out in a modified Fischer-Porter ® reactor with an inlet for introducing the substrate and/or removing aliquots of the substrates for analysis by gas chromatography.
  • a typical preparation approximately 0.026 g (0.1 mmol) of RhCl 3 .3H 2 ⁇ was dissolved in 3 mL of methanol, followed by the addition of 1 mL of the ionic liquid
  • Rh(O) particles obtained according to the method described in Example 1 and shown in Figure 1, together with the Debye-Scherrer equation, enables us to calculate the size of the Rh(O) nanoparticles.
  • the calculated value was a mean diameter of 5.8 run.
  • This example illustrates the preparation of Rh(O) nanoparticles supported on a silica matrix by the sol- gel process via the acid route.
  • TEOS tetraethoxysiloxane
  • the mixture was initially homogenised by gentle magnetic stirring (10 minutes) , followed by the application of ultrasound (2 minutes) and was finally allowed to stand in a semi- sealed beaker at a temperature of 60 0 C (18 hours) .
  • the resulting material was washed with acetone several times, dried under vacuum and then used in a catalytic process. Extraction with acetone may be used to remove the liquid. Calcination 450 0 C for 6 hours can also be used to extract the ionic liquid.
  • Figure 2 shows the amorphous nature of the silica produced in this way (halo centred on 22°) and the presence of rhodium is confirmed by the diffraction planes for Rh(O) (plane (1 1 1) at 41°C and plane (2 0
  • Rh(O) particles on the silica matrix was found to be relatively homogeneous, as shown in Figure 5, by the chemical mapping of Rh(O) /SiO 2 synthesised with BMLBF 4 using the sol-gel method in acid medium.
  • This example illustrates the preparation of Rh(O) nanoparticles supported on a silica matrix by the sol- gel process using the basic route.
  • TEOS tetraethoxysiloxane
  • BMLBF 4 ionic liquid
  • Rh(O) nanoparticles 10 mg
  • 95 mL of ethanol was added to the solution and finally 20 mL of NH 4 OH.
  • the mixture was kept gently stirred for 3 hours at ambient temperature and subsequently allowed to stand for 18 hours .
  • the solid material obtained was filtered, then washed with acetone and dried in a vacuum atmosphere for 1 hour. Extraction with acetone may be used to remove the liquid. Calcination at 450 0 C for 6 hours can also be used to extract the ionic liquid.
  • This example relates to the use of supported catalysts prepared according to the method described in this invention in aromatic hydrocarbon hydrogenation reactions .
  • Aromatic hydrocarbon hydrogenation reactions in heterogeneous medium were carried out in a Fischer- Porter ® reactor modified with an inlet to add the substrate or ionic liquid and/or to remove samples for chromatographic analysis.
  • Rh/SiO 2 Rh(O) ⁇ 0.2%) were placed in the reactor followed by the addition of 12.5 mmol of substrate (decene, cyclohexene and benzene) in an aromatic hydrocarbon/Rh ratio of 695 (12.5 mmol/0.018 mmol).
  • substrate decene, cyclohexene and benzene
  • the hydrogen pressure was held constant at 4 atm and the temperature at 75°C.
  • Progress of the reaction was monitored through consumption of the hydrogen present in a container coupled to a pressure transducer connected to the computer.
  • the conversion of substrate to product was analysed by gas chromatography.
  • Table 2 shows data relating to the hydrogenation of decene and cyclohexene. Data relating to the catalytic activity of isolated Rh(O) nanoparticles have been included for comparison.
  • the reaction conditions used were as follows: temperature 75°C; P H2 (4 atm, constant pressure) ; conversion (100%) ; TOF - turnover frequency - defined here as mol of hydrogenated product per mol of Rh(O) catalyst per minute; c (1) Rh (0) /HF/BMI .BF 4 (100 mg, 0.11% of Rh(O)) 12.5 mmol of alkene; d (2) Rh(O) /NH 4 OH/BMI. BF 4 (100 mg, 0.14% of Rh(O)) 12.5 mmol of arene; Rh(O) nanoparticles (3 mg, 0.03 mmol),
  • Table 3 shows data relating to the hydrogenation of benzene using the supported catalyst obtained via the acid route. Data relating to the catalytic activity of isolated Rh(O) nanoparticles have been included for comparison.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

L'invention porte sur la préparation d'un catalyseur supporté comprenant des nanoparticules de métal noble incorporées dans une matrice solide par un procédé sol-gel dans un milieu liquide ionique.
PCT/GB2009/000821 2008-04-02 2009-03-27 Procédé de préparation d'un catalyseur supporté à l'aide de nanoparticules de métal noble et catalyseur ainsi obtenu Ceased WO2009122149A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI0800971-6 2008-04-02
BRPI0800971-6A BRPI0800971A2 (pt) 2008-04-02 2008-04-02 método para preparo de catalisador suportado utilizando nanopartìculas de metais nobres e catalisador assim obtido

Publications (1)

Publication Number Publication Date
WO2009122149A1 true WO2009122149A1 (fr) 2009-10-08

Family

ID=40601180

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2009/000821 Ceased WO2009122149A1 (fr) 2008-04-02 2009-03-27 Procédé de préparation d'un catalyseur supporté à l'aide de nanoparticules de métal noble et catalyseur ainsi obtenu

Country Status (3)

Country Link
AR (1) AR071138A1 (fr)
BR (1) BRPI0800971A2 (fr)
WO (1) WO2009122149A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011096898A1 (fr) * 2010-02-05 2011-08-11 Nanyang Technological University Procédé de modification des propriétés électriques de nanotubes de carbone à l'aide de nanoparticules
JP2013013864A (ja) * 2011-07-05 2013-01-24 Toyota Motor Corp 金属クラスター担持触媒の製造方法
WO2013158272A1 (fr) * 2012-04-17 2013-10-24 Momentive Performance Materials Inc. Catalyseur à haute activité destiné à des réactions d'hydrosilylation et procédés de réalisation associés
CN113522349A (zh) * 2021-07-28 2021-10-22 青岛科技大学 一种氮掺杂碳包覆分子筛负载钌催化剂及制备方法和应用
CN116673072A (zh) * 2023-05-12 2023-09-01 东华大学 一种三氮唑基聚合物胶体复合催化剂及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2901715A1 (fr) * 2006-06-01 2007-12-07 Centre Nat Rech Scient Nouveaux nanomateriaux hybrides, leur preparation et leur utilisation en tant que filtres pour capteurs de gaz

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2901715A1 (fr) * 2006-06-01 2007-12-07 Centre Nat Rech Scient Nouveaux nanomateriaux hybrides, leur preparation et leur utilisation en tant que filtres pour capteurs de gaz

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FENG SHI, QINGHUA ZHANG, DONGMEI LI, YOUQUAN DENG: "Silica-Gel-Confined Ionic Liquids: A new attempt for the development of supported nanoliquid catalysis", CHEMISTRY - A EUROPEAN JOURNAL, vol. 11, 4 July 2005 (2005-07-04), pages 5279 - 5288, XP002532459, Retrieved from the Internet <URL:DOI: 10.1002/chem.200500107> *
FONSECA G S ET AL: "The use of imidazolium ionic liquids for the formation and stabilization of Ir DEG and Rh DEG nanoparticles: efficient catalysts for the hydrogenation of arenes", CHEMISTRY - A EUROPEAN JOURNAL, WILEY - V C H VERLAG GMBH & CO. KGAA, WEINHEIM, DE, vol. 9, 1 January 2003 (2003-01-01), pages 3263 - 3269, XP002462143, ISSN: 0947-6539 *
MARCOS A. GELESKY, SANDRA S.X. CHIARO, FLAVIO A. PAVAN, JOAO H.Z.DOS SANTOS, JAIRTON DUPONT: "SUPPORTED IONIC LIQUID PHASE RHODIUM NANOPARTICLE HYDROGENATION CATALYSTS", THE ROYAL SOCIETY OF CHEMISTRY, vol. 2007, 9 August 2007 (2007-08-09), pages 5549 - 5553, XP002532364, Retrieved from the Internet <URL:http://www.rsc.org/Publishing/Journals/DT/article.asp?doi=b708111a> *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011096898A1 (fr) * 2010-02-05 2011-08-11 Nanyang Technological University Procédé de modification des propriétés électriques de nanotubes de carbone à l'aide de nanoparticules
US10077189B2 (en) 2010-02-05 2018-09-18 Nanyang Technological University Method of modifying electrical properties of carbon nanotubes using nanoparticles
JP2013013864A (ja) * 2011-07-05 2013-01-24 Toyota Motor Corp 金属クラスター担持触媒の製造方法
WO2013158272A1 (fr) * 2012-04-17 2013-10-24 Momentive Performance Materials Inc. Catalyseur à haute activité destiné à des réactions d'hydrosilylation et procédés de réalisation associés
CN104245132A (zh) * 2012-04-17 2014-12-24 莫门蒂夫性能材料股份有限公司 用于氢化硅烷化反应的高活性催化剂和其制备方法
US9993812B2 (en) 2012-04-17 2018-06-12 Momentive Pereformance Materials Inc. High activity catalyst for hydrosilylation reactions and methods of making the same
CN113522349A (zh) * 2021-07-28 2021-10-22 青岛科技大学 一种氮掺杂碳包覆分子筛负载钌催化剂及制备方法和应用
CN116673072A (zh) * 2023-05-12 2023-09-01 东华大学 一种三氮唑基聚合物胶体复合催化剂及其制备方法和应用

Also Published As

Publication number Publication date
BRPI0800971A2 (pt) 2009-11-17
AR071138A1 (es) 2010-05-26

Similar Documents

Publication Publication Date Title
Axet et al. Catalysis with colloidal ruthenium nanoparticles
Biradar et al. Silica–dendrimer core–shell microspheres with encapsulated ultrasmall palladium nanoparticles: efficient and easily recyclable heterogeneous nanocatalysts
RU2491988C2 (ru) Способ получения водной суспензии коллоида благородного металла
US6197720B1 (en) Palladium clusters and their use as catalysts
Chen et al. Selective hydrogenation of 5-hydroxymethylfurfural via zeolite encapsulation to avoid further hydrodehydroxylation
Bianchini et al. Immobilization of Optically Active Rhodium‐Diphosphine Complexes on Porous Silica via Hydrogen Bonding
CN103619479B (zh) 包含金属纳米颗粒的无机/聚合物的杂化催化材料
CA2499782A1 (fr) Catalyseur a base de silicate et capteur de silicate fonctionnalises par un procede sol-gel
EP2148740A1 (fr) Catalyseurs à base de palladium
CN116020513A (zh) 一种钯原子级分散催化剂、制备方法及其应用
CN110935481A (zh) 一种用于芳香醚键选择性氢解催化剂及制备和应用
CN114849694A (zh) 一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用
Pérez Alonso et al. Nickel nanoparticles immobilized on pristine halloysite: an outstanding catalyst for hydrogenation processes
JP2005509515A (ja) 金属塗布ナノ粒子の凝集体を構成する不均質触媒
KR100852309B1 (ko) 담지금속촉매의 제조방법
CN108654698B (zh) 一种手性纳米金光催化剂的制备方法及其应用
Dhiman et al. Silica‐supported nanoparticles as heterogeneous catalysts
CN109046442B (zh) 多级孔分子筛负载铂铁双金属催化剂及其制备和应用
Liu et al. Bridging the Gap between Bioreduction and Ullmann Homocoupling for Continuous-Flow Chemoenzymatic Cascades
CN116747909B (zh) 铱-铼双金属络合固载型催化剂及其制备方法和应用
US12162001B2 (en) Magnetic-nanoparticle-supported catalyst and method of making
CN104125860A (zh) 在各种溶剂中具有高活性的无机/高分子杂化催化材料
CN112169840A (zh) 三齿配体修饰的硅胶固载含铂硅氢加成催化剂及其制备方法
Noël et al. Asymmetric hydrogenation of ethyl pyruvate over aqueous dispersed Pt nanoparticles stabilized by a cinchonidine-functionalized β-cyclodextrin
CN117101673A (zh) 一种Ni-Re双金属基催化剂及其制备方法和应用

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: 09728168

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 02-02-2011).

122 Ep: pct application non-entry in european phase

Ref document number: 09728168

Country of ref document: EP

Kind code of ref document: A1