WO2025193253A2 - Génération de catalyseurs de type acide de brønsted par polarisation électrique - Google Patents

Génération de catalyseurs de type acide de brønsted par polarisation électrique

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Publication number
WO2025193253A2
WO2025193253A2 PCT/US2024/038035 US2024038035W WO2025193253A2 WO 2025193253 A2 WO2025193253 A2 WO 2025193253A2 US 2024038035 W US2024038035 W US 2024038035W WO 2025193253 A2 WO2025193253 A2 WO 2025193253A2
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Prior art keywords
catalyst
electrolyte
carbon
electrode
electrochemical potential
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WO2025193253A3 (fr
WO2025193253A9 (fr
Inventor
Yuriy ROMAN
Yogesh Surendranath
Karl Speas WESTENDORFF
Max Joshua HUELSEY
Thejas Satish WESLEY
Neil RAZSAN
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Massachusetts Institute of Technology
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Massachusetts Institute of Technology
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Publication of WO2025193253A3 publication Critical patent/WO2025193253A3/fr
Publication of WO2025193253A9 publication Critical patent/WO2025193253A9/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • 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
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated

Definitions

  • BAC Bronsted acid catalysis
  • BAC is one of the largest and most commercially applied branches of catalysis.
  • BAC is employed for a wide variety of organic transformations, including but not limited to esterification reactions, Friedel Crafts acylation reactions, and Friedel Crafts alkylation reactions. The lattermost of these is widely applied in industry, as commodity chemicals such as ethylbenzene and cumene are produced via alkylation reactions and are typically catalyzed by Bronsted acid catalysts.
  • the disclosure provides a method of modulating the surface acidity of a catalyst, wherein the method comprises: i. providing a catalyst comprising an electrode having an acidic surface; ii. contacting the electrode with an electrolyte solution; and iii. applying an electrochemical potential to the electrode.
  • the disclosure provides a method of modulating the surface acidity of a catalyst, wherein the method comprises providing a catalyst having an acidic surface and contacting the catalyst with an electrolyte solution and a redox buffer.
  • the disclosure provides a method of modulating the rate of a chemical reaction on at least one reaction substrate on a conductive 3-D manifold, the method comprising: a. providing a reactor comprising: i. a working electrode chamber comprising a working electrode, a reference electrode, an electrolyte, and a conductive catalyst having an acidic surface dispersed in the electrolyte; ii. a counter electrode chamber comprising a counter electrode, the electrolyte; and iii. a separation membrane located between the working electrode and counter electrode chambers; b. contacting the working electrode, counter electrode, and catalyst with an electrolyte; c. introducing at least one reaction substrate into the working electrode chamber; and; d. applying an electrochemical potential to the working electrode.
  • the disclosure provides a method of catalyzing a chemical reaction in a reactor, wherein the method comprises: i. contacting a catalyst having an acidic surface with an electrolyte solution; ii. adding at least one reaction substrate to the catalyst and electrolyte solution; and iii. applying an electrochemical potential to the catalyst.
  • FIG. 1 depicts the design of a driven (wired) polarization experimental setup.
  • the catalyst being tested is the working electrode (WE)
  • the reference electrode (RE) is a leakless Ag/AgCl electrode
  • the counter electrode (CE) is a piece of carbon paper.
  • FIG. 2 is a graph showing the potential dependence of the lower-bound (l.b.) TOF for PTA/C electrodes polarized potentiostatically. All reactions were conducted at 40 °C in a solution of 0.1 M (B) 1 -methylcyclopentanol in MeCN with 0.1 M [TBA][PFe] as electrolyte and 0.1 M tri-tert-butylbenzene as internal standard.
  • FIG. 3 is a graph showing the conversion of representative reaction transients of the 1- methylcyclopentanol dehydration using 0.1 M [TBA][PF6] (red) and [TBA][TFSI] (blue) during the reaction, respectively.
  • FIG. 4 GC-MS chromatograms of products after 48hrs of reaction time at 70 °C.
  • Products include (A) 5-decene (E) and (B) cis-3 -decene.
  • FIG. 5 depicts a polarized slurry reactor experimental setup.
  • the working compartment consists of a reference electrode (RE), working electrode (WE), sensing electrode (SE), and a dispersed BAC.
  • RE reference electrode
  • WE working electrode
  • SE sensing electrode
  • BAC dispersed BAC
  • FIG. 6 is a graph demonstrating the potential dependence of the rate of colloidal 5% PTA/C polarized through contact with the WE in the working compartment of the polarized slurry reactor. 100 mg of 5% PTA/C were dispersed in the working compartment in each of these experiments.
  • FIG. 7 is a graph demonstrating the potential dependence of the TOF of colloidal 5% PTA/C polarized by exposure to varying ratios of [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.
  • BACs Bronsted acid catalysts
  • Our methodology relies on the presence of a conductive interface which has acidic moieties and involves polarizing the conductive interface to make it positive relative to its point of zero free charge. This is an effect where protons bound to the interface, which are responsible for the catalytic activity of BACs, are made more labile as the interfacial electric field increases in strength, thereby making them more active for catalysis.
  • One aspect of the disclosure herein is a method of increasing the reaction rate of a Bronsted acid catalyst, the method comprising: a. providing an electrode comprising the Bronsted acid catalyst; b. contacting the electrode with an aqueous solution; and c. applying an electrical potential to the electrode; wherein the electrical potential increases the reaction rate of the Bronsted acid catalyst.
  • the electrode comprises a metal oxide with surface hydroxyl (-OH) groups.
  • the electrode comprises a metal oxide with surface acidic groups.
  • the electrical potential increases the acidity of the catalyst.
  • the electrical potential anodically polarizes the electrode.
  • the electrode comprises Ti/TiOH x .
  • the electrical potential is -140 mV.
  • the electrode comprises phosphotungstic acid on carbon (PTA/C).
  • the electrical potential is -330 mV.
  • One aspect of the disclosure herein is a Bronsted acid catalyst produced by the disclosed method.
  • the disclosed Bronsted acid catalyst catalyzes esterification reactions, Friedel Crafts acylation reactions, dehydration reactions, and/or Friedel Crafts alkylation reactions.
  • the disclosed Bronsted acid catalyst increases the rate of production of 1 -methylcyclopentene from 1 -methyl cyclopentanol in an aqueous solution by over 1,000-, 10,000-, or 100,000-fold.
  • the disclosed Bronsted acid catalyst increases the rate of an acylation reaction between anisole and acetic anhydride by over 100-, 1,000-, or 10,000-fold.
  • One aspect of the disclosure herein is a reactor comprising the disclosed Bronsted acid catalyst.
  • the disclosure provides a method of increasing the reaction rate of a Bronsted acid catalyst, the method comprising: a. providing an electrode comprising the Bronsted acid catalyst; b. contacting the electrode with an aqueous solution; and c. applying an electrical potential to the electrode; wherein the electrical potential increases the reaction rate of the Bronsted acid catalyst.
  • the electrode comprises a metal oxide with surface hydroxyl (- OH) groups.
  • the electrode comprises a metal oxide with surface acidic groups.
  • the electrical potential increases the acidity of the catalyst.
  • the electrical potential anodically polarizes the electrode.
  • the electrode comprises Ti/TiOH x .
  • the electrical potential is -140 mV.
  • the electrode comprises phosphotungstic acid on carbon (PTA/C).
  • the electrical potential is -330 mV.
  • the Bronsted acid catalyst catalyzes esterification reactions, Friedel Crafts acylation reactions, dehydration reactions, and/or Friedel Crafts alkylation reactions.
  • the Bronsted acid catalyst increases the rate of production of 1 -methylcyclopentene from 1 -methylcyclopentanol in an aqueous solution by over 1,000- , 10,000-, or 100,000-fold.
  • the Bronsted acid catalyst increases the rate of an acylation reaction between anisole and acetic anhydride by over 100-, 1,000-, or 10,000-fold.
  • the disclosure provides a Bronsted acid catalyst produced by the method of any of the above embodiments.
  • the disclosure provides a reactor comprising the Bronsted acid catalyst described in any of the above embodiments.
  • the disclosure provides a method of modulating the surface acidity of a catalyst, wherein the method comprises: a. providing a catalyst comprising an electrode having an acidic surface; b. contacting the electrode with an electrolyte solution; and c. applying an electrochemical potential to the electrode.
  • the electrode comprises a metal, a metal oxide, a metal sulfide, a metal nitride, carbon, or silicon, or a combination of any of them.
  • the acidic surface comprises at least one acidic group selected from hydroxyl (-OH), carboxylic acid (-COOH), thiol (-SH), sulfonate (-SO3H), hydrogenate phosphonate (-PO3H ), dihydrogen phosphate (-PO3H2), oxonium (-O + (H)-), ammonium (-NH3 + ), amine (-NH2) groups, their deprotonated conjugate bases, and a combination of any of them.
  • acidic group selected from hydroxyl (-OH), carboxylic acid (-COOH), thiol (-SH), sulfonate (-SO3H), hydrogenate phosphonate (-PO3H ), dihydrogen phosphate (-PO3H2), oxonium (-O + (H)-), ammonium (-NH3 + ), amine (-NH2) groups, their deprotonated conjugate bases, and a combination of any of them.
  • the electrode comprises a metal selected from carbon, titanium, zirconium, tungsten, molybdenum, aluminum, indium, tin, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, platinum, iridium, silver, gold, lead, and bismuth, or a combination of any of them.
  • the electrode is selected from phosphotungstic acid on carbon (PTA/C), boron-doped diamond, carbon, phosphomolybdic acid on carbon (PMA/C), silicotungstic acid on carbon (STA/C), Ti/TiOH x , Zr/ZrO y H x , W/WO y H x , Mo/MoO y H x , Al/A10 y H x , In/InO y H x , Sn/SnO y H x , Fe/FeO y H x , Co/CoO y H x , Ni/NiO y H x , Cu/CuO y H x , Zn/ZnO y H x , Ru/RuO y H x , Rh/RhO y H x , Pd/PdO y H x , Pt/PtO y H x , I
  • the applied electrochemical potential is about -30 V to about +30 V vs. SHE. In some embodiments, the applied electrochemical potential is about -20 V to about +20 V vs. SHE. In some embodiments, the applied electrochemical potential is about -15 V to about +15 V vs. SHE. In some embodiments, the applied electrochemical potential is about -10 V to about +10 V vs. SHE. In some embodiments, the applied electrochemical potential is about -7.5 V to about +7.5 V vs. SHE. In some embodiments, the applied electrochemical potential is about -5 V to about +5 V vs. SHE. In some embodiments, the applied electrochemical potential is about -4 V to about +4 V vs.
  • the applied electrochemical potential is about -3 V to about +3 V vs. SHE. In some embodiments, the applied electrochemical potential is about -2 V to about +2 V vs. SHE. In some embodiments, the applied electrochemical potential is about -1 V to about +1 V vs. SHE. In some embodiments, the applied electrochemical potential is about -500 mV to about +500 mV vs. SHE. In some embodiments, the applied electrochemical potential is about -250 mV to about +250 mV vs. SHE. In some embodiments, the applied electrochemical potential is about -100 mV to about +100 mV vs. SHE.
  • the applied electrochemical potential is about -30 V to about +30 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -20 V to about +20 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -15 V to about +15 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -10 V to about +10 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -7.5 V to about +7.5 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -5 V to about +5 V vs. Ag/AgCl.
  • the applied electrochemical potential is about -4 V to about +4 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -3 V to about +3 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -2 V to about +2 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -1 V to about +1 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -500 mV to about +500 mV vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -250 mV to about +250 mV vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -100 mV to about +100 mV vs. Ag/AgCl.
  • a positive polarity is applied to the catalyst vs. SHE.
  • the negative polarity is applied to the catalyst vs. SHE.
  • a positive polarity is applied to the catalyst vs. Ag/AgCl.
  • the negative polarity is applied to the catalyst vs. Ag/AgCl.
  • the electrolyte is selected from a molten salt, a room temperature ionic liquid, an aqueous solution, a non-polar organic solvent, and a polar organic solvent.
  • the electrolyte comprises at least one anion selected from F’’ Cl; Br I; o 2 OH; SO4 2 ; C1O 4 ; NO 3 ; PFe; and bistriflimide (TFSI).
  • the electrolyte comprises at least one borate.
  • the at least one borate is selected from tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph) 4 ‘.
  • the electrolyte comprises at least one metal cation selected from Li, Na, K, Rb, Cs, Ca, Mg, Sr, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • the electrolyte comprises at least one organic cation.
  • the organic cation is an alkylammonium or imidazolium.
  • the electrolyte comprises acetonitrile.
  • the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]) or tetrabutylammonium bis(trifluoromethanesulfonyl)imide.
  • the catalyst is in the form of a colloidal suspension in contact with the electrode.
  • the electrolyte solution further comprises at least one redox buffer system.
  • the at least one redox buffer system comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.
  • the disclosure provides a method of catalyzing a chemical reaction with a catalyst, wherein the surface acidity of the catalyst is modulated according to the above embodiments.
  • the method is performed in a batch reactor.
  • the method is performed in a flow reactor.
  • the chemical reaction is an esterification, a Friedel Crafts acylation, a dehydration, an etherification, a Friedel Crafts alkylation, a hydrocarbon cracking reaction, an olefin isomerization, a hydrogenation, an oxidation with at least one intermediate proton transfer step, or a reduction with at least one intermediate proton transfer step.
  • the method comprises providing a catalyst having an acidic surface and contacting the catalyst with an electrolyte solution and a redox buffer.
  • the catalyst comprises at least one acidic surface group selected from hydroxyl (-OH), carboxylic acid (-COOH), thiol (-SH), sulfonate (-SO3H), hydrogenate phosphonate (-PO3H ), dihydrogen phosphate (-PO3H2), oxonium (-O + (H)-), ammonium (-NH3 + ), amine (-NH2) groups, their deprotonated conjugate bases, and a combination of any of them.
  • acidic surface group selected from hydroxyl (-OH), carboxylic acid (-COOH), thiol (-SH), sulfonate (-SO3H), hydrogenate phosphonate (-PO3H ), dihydrogen phosphate (-PO3H2), oxonium (-O + (H)-), ammonium (-NH3 + ), amine (-NH2) groups, their deprotonated conjugate bases, and a combination of any of them.
  • the catalyst comprises a metal selected from carbon, titanium, zirconium, tungsten, molybdenum, aluminum, indium, tin, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, platinum, iridium, silver, gold, lead, and bismuth, and a combination of any of them.
  • the catalyst is selected from phosphotungstic acid on carbon (PTA/C), boron-doped diamond, carbon, phosphomolybdic acid on carbon (PMA/C), silicotungstic acid on carbon (STA/C), Ti/TiOH x , Zr/ZrO y H x , W7W0 y H x , Mo/MoO y H x , Al/A10 y H x , In/InO y H x , Sn/SnO y H x , Fe/FeO y H x , Co/CoO y H x , Ni/NiO y H x , Cu/CuO y H x , Zn/ZnO y H x , Ru/RuO y H x , Rh/RhO y H x , Pd/PdO y H x , Pt/PtO y H x ,
  • the applied electrochemical potential is about -30 V to about +30 V vs. SHE. In some embodiments, the applied electrochemical potential is about -20 V to about +20 V vs. SHE. In some embodiments, the applied electrochemical potential is about -15 V to about +15 V vs. SHE. In some embodiments, the applied electrochemical potential is about -10 V to about +10 V vs. SHE. In some embodiments, the applied electrochemical potential is about -7.5 V to about +7.5 V vs. SHE. In some embodiments, the applied electrochemical potential is about -5 V to about +5 V vs. SHE. In some embodiments, the applied electrochemical potential is about -4 V to about +4 V vs.
  • the applied electrochemical potential is about -3 V to about +3 V vs. SHE. In some embodiments, the applied electrochemical potential is about -2 V to about +2 V vs. SHE. In some embodiments, the applied electrochemical potential is about -1 V to about +1 V vs. SHE. In some embodiments, the applied electrochemical potential is about -500 mV to about +500 mV vs. SHE. In some embodiments, the applied electrochemical potential is about -250 mV to about +250 mV vs. SHE. In some embodiments, the applied electrochemical potential is about -100 mV to about +100 mV vs. SHE.
  • the applied electrochemical potential is about -30 V to about +30 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -20 V to about +20 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -15 V to about +15 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -10 V to about +10 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -7.5 V to about +7.5 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -5 V to about +5 V vs. Ag/AgCl.
  • the applied electrochemical potential is about -4 V to about +4 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -3 V to about +3 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -2 V to about +2 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -1 V to about +1 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -500 mV to about +500 mV vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -250 mV to about +250 mV vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -100 mV to about +100 mV vs. Ag/AgCl.
  • a positive polarity is applied to the catalyst vs. SHE.
  • the negative polarity is applied to the catalyst vs. SHE.
  • a positive polarity is applied to the catalyst vs. Ag/AgCl.
  • the negative polarity is applied to the catalyst vs. Ag/AgCl.
  • the electrolyte is selected from a molten salt, a room temperature ionic liquid, an aqueous solution, a non-polar organic solvent, and a polar organic solvent.
  • the electrolyte comprises at least one anion selected from F; Cl; Br I; o 2 OH; SO4 2 ; C1O 4 ; NO 3 ; PFe; and bistriflimide (TFSI).
  • the electrolyte comprises at least one borate.
  • At least one borate is selected from tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph) 4 ‘.
  • the electrolyte comprises at least one metal cation selected from Li, Na, K, Rb, Cs, Ca, Mg, Sr, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • the electrolyte comprises at least one organic cation.
  • the at least one organic cation is alkylammonium or imidazolium.
  • the electrolyte comprises acetonitrile.
  • the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]) or tetrabutylammonium bis(trifluoromethanesulfonyl)imide.
  • the redox buffer system comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.
  • the method is performed in a batch reactor.
  • the method is performed in a flow reactor.
  • the disclosure provides a method of catalyzing a chemical reaction with a catalyst, wherein the surface acidity of the catalyst is modulated according to the above embodiments.
  • the chemical reaction is an esterification, a Friedel Crafts acylation, a dehydration, an etherification, a Friedel Crafts alkylation, a hydrocarbon cracking reaction, an olefin isomerization, a hydrogenation, an oxidation with at least one intermediate proton transfer step, or a reduction with at least one intermediate proton transfer step.
  • the disclosure provides a method of modulating the rate of a chemical reaction on at least one reaction substrate on a conductive 3-D manifold, the method comprising: a. providing a reactor comprising: i. a working electrode chamber comprising a working electrode, a reference electrode, an electrolyte, and a conductive catalyst having an acidic surface dispersed in the electrolyte; ii. a counter electrode chamber comprising a counter electrode, the electrolyte; and iii. a separation membrane located between the working electrode and counter electrode chambers; b. contacting the working electrode, counter electrode, and catalyst with an electrolyte; c. introducing at least one reaction substrate into the working electrode chamber; and d. applying an electrochemical potential to the working electrode.
  • the working electrode comprises a metal, metal oxide, metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.
  • the counter electrode comprises a metal selected from carbon, titanium, zirconium, tungsten, molybdenum, aluminum, indium, tin, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, platinum, iridium, silver, gold, lead, and bismuth, and a combination of any of them.
  • the counter electrode chamber further comprises a conductive material having an acidic surface dispersed in the electrolyte.
  • the electrolyte is selected from a molten salt, a room temperature ionic liquid, an aqueous solution, a non-polar organic solvent, and a polar organic solvent.
  • the electrolyte comprises at least one anion selected from F; Cl; Br I; o 2 OH; SO4 2 ; C1O 4 ; NO 3 ; PFe; and bistriflimide (TFSI).
  • the electrolyte comprises at least one borate.
  • the borate is selected from tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph) 4 ‘
  • the electrolyte comprises at least one metal cation selected from Li, Na, K, Rb, Cs, Ca, Mg, Sr, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • the electrolyte comprises at least one organic cation.
  • the at least one organic cation is an alkylammonium or imidazolium.
  • the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]), tetrabutylammonium bis(trifluoromethanesulfonyl)imide, or acetonitrile.
  • the applied electrochemical potential is about -30 V to about +30 V vs. SHE. In some embodiments, the applied electrochemical potential is about -20 V to about +20 V vs. SHE. In some embodiments, the applied electrochemical potential is about -15 V to about +15 V vs. SHE. In some embodiments, the applied electrochemical potential is about -10 V to about +10 V vs. SHE. In some embodiments, the applied electrochemical potential is about -7.5 V to about +7.5 V vs. SHE. In some embodiments, the applied electrochemical potential is about -5 V to about +5 V vs. SHE. In some embodiments, the applied electrochemical potential is about -4 V to about +4 V vs.
  • the applied electrochemical potential is about -3 V to about +3 V vs. SHE. In some embodiments, the applied electrochemical potential is about -2 V to about +2 V vs. SHE. In some embodiments, the applied electrochemical potential is about -1 V to about +1 V vs. SHE. In some embodiments, the applied electrochemical potential is about -500 mV to about +500 mV vs. SHE. In some embodiments, the applied electrochemical potential is about -250 mV to about +250 mV vs. SHE. In some embodiments, the applied electrochemical potential is about -100 mV to about +100 mV vs. SHE.
  • the applied electrochemical potential is about -30 V to about +30 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -20 V to about +20 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -15 V to about +15 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -10 V to about +10 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -7.5 V to about +7.5 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -5 V to about +5 V vs. Ag/AgCl.
  • the applied electrochemical potential is about -4 V to about +4 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -3 V to about +3 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -2 V to about +2 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -1 V to about +1 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -500 mV to about +500 mV vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -250 mV to about +250 mV vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -100 mV to about +100 mV vs. Ag/AgCl.
  • a positive polarity is applied to the catalyst vs. SHE.
  • the negative polarity is applied to the catalyst vs. SHE.
  • a positive polarity is applied to the catalyst vs. Ag/AgCl.
  • the negative polarity is applied to the catalyst vs. Ag/AgCl.
  • the electrolyte solution further comprises at least one redox buffer.
  • the redox buffer comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.
  • the acidic surface comprises at least one acidic group selected from hydroxyl (-OH), carboxylic acid (-COOH), thiol (-SH), sulfonate (-SO3H), hydrogenate phosphonate (-PO3H ), dihydrogen phosphate (-PO3H2), oxonium (-O + (H)-), ammonium (-NH3 + ), amine (-NH2) groups, their deprotonated conjugate bases, or a combination of any of them.
  • acidic group selected from hydroxyl (-OH), carboxylic acid (-COOH), thiol (-SH), sulfonate (-SO3H), hydrogenate phosphonate (-PO3H ), dihydrogen phosphate (-PO3H2), oxonium (-O + (H)-), ammonium (-NH3 + ), amine (-NH2) groups, their deprotonated conjugate bases, or a combination of any of them.
  • the working electrode and/or conductive catalyst comprises a metal oxide metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.
  • the working electrode or conductive catalyst comprises carbon, titanium, zirconium, tungsten, molybdenum, aluminum, indium, tin, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, platinum, iridium, silver, gold, lead, or bismuth, or a combination of any of them.
  • the working electrode and/or the conductive catalyst is selected from phosphotungstic acid on carbon (PTA/C), boron-doped diamond, carbon, phosphomolybdic acid on carbon (PMA/C), silicotungstic acid on carbon (STA/C), Ti/TiOH x , Zr/ZrO y H x , W/WO y H x , Mo/MoO y H x , Al/A10 y H x , In/InO y H x , Sn/SnO y H x , Fe/FeO y H x , Co/CoO y H x , Ni/NiO y H x , Cu/CuO y H x , Zn/ZnO y H x , Ru/RuO y H x , Rh/RhO y H x , Pd/PdO y H x , Pt/PtO
  • the chemical reaction is an esterification, a Friedel Crafts acylation, a dehydration, an etherification, a Friedel Crafts alkylation, a hydrocarbon cracking reaction, an olefin isomerization, a hydrogenation, an oxidation with at least one intermediate proton transfer step, or a reduction with at least one intermediate proton transfer step.
  • the reference electrode comprises Ag/AgCl.
  • the disclosure provides a method of catalyzing a chemical reaction in a reactor, wherein the method comprises: a. contacting a catalyst having an acidic surface with an electrolyte solution; b. adding at least one reaction substrate to the catalyst and electrolyte solution; and c. applying an electrochemical potential to the catalyst.
  • the reaction is an esterification, a Friedel Crafts acylation, a dehydration, an etherification, a Friedel Crafts alkylation, a hydrocarbon cracking reaction, an olefin isomerization, a hydrogenation, an oxidation with at least one intermediate proton transfer step, or a reduction with at least one intermediate proton transfer step.
  • the catalyst comprises a metal, metal oxide, metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.
  • the catalyst comprises carbon, titanium, zirconium, tungsten, molybdenum, aluminum, indium, tin, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, platinum, iridium, silver, gold, lead, or bismuth, or a combination of any of them.
  • the acidic surface comprises at least one acidic group selected from hydroxyl (-OH), carboxylic acid (-COOH), thiol (-SH), sulfonate (-SO3H), hydrogenate phosphonate (-PO3H ), dihydrogen phosphate (-PO3H2), oxonium (-O + (H)-), ammonium (-NH3 + ), amine (-NH2) groups, their deprotonated conjugate bases, or a combination of any of them.
  • acidic group selected from hydroxyl (-OH), carboxylic acid (-COOH), thiol (-SH), sulfonate (-SO3H), hydrogenate phosphonate (-PO3H ), dihydrogen phosphate (-PO3H2), oxonium (-O + (H)-), ammonium (-NH3 + ), amine (-NH2) groups, their deprotonated conjugate bases, or a combination of any of them.
  • the catalyst is selected from phosphotungstic acid on carbon (PTA/C), boron-doped diamond, carbon, phosphomolybdic acid on carbon (PMA/C), silicotungstic acid on carbon (STA/C), Ti/TiOH x , Zr/ZrO y H x , W/WO y H x , Mo/MoO y H x , Al/A10 y H x , In/InO y H x , Sn/SnO y H x , Fe/FeO y H x , Co/CoO y H x , Ni/NiO y H x , Cu/CuO y H x , Zn/ZnO y H x , Ru/RuO y H x , Rh/RhO y H x , Pd/PdO y H x , Pt/PtO y H x , I
  • the electrochemical potential is applied via the insertion of a conductive electrode into the electrolyte solution.
  • the conductive electrode comprises a metal, metal oxide, metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.
  • the conductive electrode comprises carbon, titanium, zirconium, tungsten, molybdenum, aluminum, indium, tin, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, platinum, iridium, silver, gold, lead, or bismuth, or a combination of any of them.
  • the electrochemical potential is applied via the addition of a redox buffer into the electrolyte solution.
  • the electrochemical potential is applied via a combination of the insertion of a conductive electrode and addition of a redox buffer into the electrolyte solution.
  • the redox buffer comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.
  • the applied electrochemical potential is about -30 V to about +30 V vs. SHE. In some embodiments, the applied electrochemical potential is about -20 V to about +20 V vs. SHE. In some embodiments, the applied electrochemical potential is about -15 V to about +15 V vs. SHE. In some embodiments, the applied electrochemical potential is about -10 V to about +10 V vs. SHE. In some embodiments, the applied electrochemical potential is about -7.5 V to about +7.5 V vs. SHE. In some embodiments, the applied electrochemical potential is about -5 V to about +5 V vs. SHE. In some embodiments, the applied electrochemical potential is about -4 V to about +4 V vs.
  • the applied electrochemical potential is about -3 V to about +3 V vs. SHE. In some embodiments, the applied electrochemical potential is about -2 V to about +2 V vs. SHE. In some embodiments, the applied electrochemical potential is about -1 V to about +1 V vs. SHE. In some embodiments, the applied electrochemical potential is about -500 mV to about +500 mV vs. SHE. In some embodiments, the applied electrochemical potential is about -250 mV to about +250 mV vs. SHE. In some embodiments, the applied electrochemical potential is about -100 mV to about +100 mV vs. SHE.
  • the applied electrochemical potential is about -30 V to about +30 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -20 V to about +20 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -15 V to about +15 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -10 V to about +10 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -7.5 V to about +7.5 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -5 V to about +5 V vs. Ag/AgCl.
  • the applied electrochemical potential is about -4 V to about +4 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -3 V to about +3 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -2 V to about +2 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -1 V to about +1 V vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -500 mV to about +500 mV vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -250 mV to about +250 mV vs. Ag/AgCl. In some embodiments, the applied electrochemical potential is about -100 mV to about +100 mV vs. Ag/AgCl.
  • a positive polarity is applied to the catalyst vs. SHE.
  • the negative polarity is applied to the catalyst vs. SHE.
  • a positive polarity is applied to the catalyst vs. Ag/AgCl.
  • the negative polarity is applied to the catalyst vs. Ag/AgCl.
  • the method is performed in a batch reactor.
  • the method is performed in a flow reactor.
  • the catalyst is in the form of a colloidal suspension in contact with the conductive electrode.
  • the electrolyte is selected from a molten salt, a room temperature ionic liquid, an aqueous solution, a non-polar organic solvent, and a polar organic solvent.
  • the electrolyte comprises at least one anion selected from F’, Cl’, Br , I’, O2', OH’, SO4 2 ’, C1O4’, NOs’, PFe’, and bistrifhmide (TFSI).
  • the electrolyte comprises at least one borate.
  • the at least one borate is selected from tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and BfPhfy.
  • the electrolyte comprises at least one metal cation selected from Li, Na, K, Rb, Cs, Ca, Mg, Sr, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • the electrolyte comprises at least one organic cation.
  • the organic cation is an alkylammonium or imidazolium.
  • the electrolyte comprises acetonitrile.
  • the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]), tetrabutylammonium bis(trifluoromethanesulfonyl)imide, or acetonitrile.
  • the catalyst is purchased from a commercial source. In some embodiments, the catalyst is pre-treated or otherwise activated prior to use.
  • Example 1 Polarizing a 2D Electrode to increase its Bronsted Acidity
  • Example 2 Polarizing a 2D Electrode to increase its Bronsted Acidity with a Different Electrolyte
  • Example 3 Polarizing a 2D Electrode to increase its Bronsted Acidity and Isomerize 1- Decene
  • FIG. 1 A standard undivided three-electrode setup was then constructed (FIG. 1) in a 20 mL scintillation vial containing electrolyte and substrate.
  • the working and counter electrodes (CEs) were suspended with Ti wire, and the reference electrode (RE) was a commercial Ag/AgCl leakless electrode.
  • the desired potential was applied to the working electrode by initiating a chronoamperometry experiment.
  • the temperature of the reaction was controlled via a thermocouple attached to an aluminum jacket around the vial.
  • Example 4 Use of a Polarized Slurry Reactor to increase the Bronsted Acidity of a
  • a typical polarized slurry reactor consists of a working electrode chamber, a counter electrode chamber, and a separation membrane.
  • the separation membrane is located between the working electrode and counter electrode chambers.
  • the working electrode chamber contains a working electrode comprised of a conductive material including metals, metal oxides, metal sulfides, metal nitrides, carbon, silicon or a combination thereof, an electrolyte solution, and a conductive material comprising surface Bronsted acid sites dispersed in the electrolyte solution.
  • the working electrode chamber contains a reference electrode which the working electrode is polarized relative to.
  • the counter electrode chamber contains a counter electrode and an electrolyte solution with or without a dispersed conductive material (FIG. 5).
  • Example 5 Use of Chemical Additive (Redox Buffer) to increase the Bronsted Acidity of a Dispersed Conductive Catalyst
  • Ferroin was synthesized according to a previously reported procedure, reproduced here. Iron sulfate heptahydrate (1.25 g, 4.4 mmol) was added to 20 mL of deionized water in a 50 mL Falcon tube, after which 1,10-phenanthroline (2.43 g, 13 mmol) was added to the solution. The solution immediately turned bright red and was vortexed for 3 min or until the solids were completely dissolved. After this, ammonium hexafluorophosphate (1.47 g, 9 mmol) was added to the solution. The resulting thick red suspension was stirred for 5 min, after which the precipitate was collected on a 40 mL fine frit.
  • the isolated solid was washed with deionized water (3* 40 mL), and then once with 40 mL Et2O to remove residual water.
  • the resulting red powder was vacuum-dried overnight to yield 3.25 g (3.6 mmol, 80% yield) as a red colored powder.
  • Ferriin was synthesized according to a previously reported procedure, reproduced here. Starting with [Fe(phen)3][PFe]2 (1 g, 1.1 mmol), the red powder was taken up in 11 mL of 1 M H2SO4 in a 50 mL Falcon tube. Cerium ammonium nitrate (0.59 g, 1.1 mmol) was then added to the red solution, after which the solution immediately turned a deep blue. The solution was vortexed for 2 min, after which ammonium hexafluorophosphate (0.47 g, 2.9 mmol) was added to the solution. A dark blue precipitate formed, which was isolated by filtration of the solution through a 40 mL fine frit.

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Abstract

Sont divulgués des procédés de modulation de l'acidité de surface d'un catalyseur et des procédés de catalyse de réactions chimiques avec un catalyseur modifié. Sont également divulgués des procédés et des réacteurs pour catalyser des réactions chimiques avec des catalyseurs ayant une acidité de surface modulée.
PCT/US2024/038035 2023-07-13 2024-07-15 Génération de catalyseurs de type acide de brønsted par polarisation électrique Pending WO2025193253A2 (fr)

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KR100927718B1 (ko) * 2007-11-27 2009-11-18 삼성에스디아이 주식회사 다공성 탄소 구조체, 이의 제조 방법, 및 이를 포함하는 연료 전지용 전극 촉매, 전극, 및 막-전극 어셈블리
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