Generating bronsted acid catalysts by electrical polarization

Abstract

Disclosed are methods of modulating the surface acidity of a catalyst and methods of catalyzing chemical reactions with a modified catalyst. Also disclosed are methods and reactors for catalyzing chemical reactions with catalysts having modulated surface acidity.

Description

GENERATING BR0NSTED ACID CATALYSTS BY ELECTRICAL POLARIZATIONRELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 513,371, filed July 13, 2023.GOVERNMENT SUPPORT

[0002] This invention was made with government support under grant number FA9550-20-1- 0291 awarded by the Air Force Office of Scientific Research. The government has certain rights in this invention.BACKGROUND

[0003] 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.

[0004] Typically, these industrial reactions are sped up by increasing the temperature of the reactor, increasing the pressure of the reactor, or by altering the chemical composition of the reactor feed. These methods of increasing reaction rates are costly, as they require expensive reactor infrastructure and are often energy intensive. Considering growing chemical demands and the need for more energy-efficient processes, new strategies for promoting chemical reaction rates must be developed.SUMMARY

[0005] This Summary introduces a selection of concepts in simplified form that are described further below in the Detailed Description. This Summary neither identifies key or essential features, nor limits the scope, of the claimed subject matter.

[0006] In some embodiments, 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; andiii. applying an electrochemical potential to the electrode.

[0007] In some embodiments, 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.

[0008] In some embodiments, 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.

[0009] In some embodiments, 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.

[0010] The following Detailed Description references the accompanying drawings which form a part of this application, and which show, by way of illustration, specific example implementations. Other implementations may be made without departing from the scope of the disclosure.BRIEF DESCRIPTION OF THE DRAWINGSFIG. 1 depicts the design of a driven (wired) polarization experimental setup. In these systems, the catalyst being tested is the working electrode (WE), the reference electrode (RE) is a leakless Ag / AgCl electrode, and 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.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.DETAILED DESCRIPTION

[0011] Disclosed herein is a method to increase the activity of Bronsted acid catalysts (BACs) by as much as 100,000-fold at solid / liquid interfaces. In this methodology, we modify the strength of the naturally occurring electric field at the solid / liquid interface to effectively increase the acidity of the catalyst. Our methodology relies on the presence of a conductive interface which has acidic moieties and involves polarizing the conductiveinterface 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.

[0012] In a test BAC reaction where we dehydrate 1 -methylcyclopentanol to 1- methylcyclopentene and water with phosphotungstic acid on carbon (PTA / C), we are able to increase the activity of this already employed industrial catalyst by over 100,000-fold. This increase in activity occurs over a range of -330 mV of applied potential, suggesting this promotion strategy is as effective for thermochemical reactions as it is for Faradaic reactions. As a result, only small changes in potential are required to observe large changes in reactivity.

[0013] Our mechanistic studies suggest that by further anodically polarizing the catalyst, the interfacial electric field is strengthened, and this stabilizes a pre-rate determining intermediate in the reaction sequence. This stabilization lowers the apparent activation energy of the overall reaction, thereby increasing the rate of the reaction.

[0014] We note explicitly that this methodology is agnostic to the material, provided the material has a conductive interface and has chemical moi eties capable of BAC (hydroxyl moieties). We demonstrate the generality of this promotion methodology by increasing the reactivity of Ti / TiOHxfoils, which have hydroxyl moieties, by over 30 times only by changing the degree of polarization of the foil by 140 mV. We expect that other metal oxides with surface -OH groups should undergo a similar effect.

[0015] We further note that this methodology encompasses more than dehydration reaction chemistries, as we find that Bronsted acid catalyzed acylation reactions are even more sensitive to potential than the previously mentioned dehydration chemistry. We demonstrate this by increasing the rate of an acylation reaction between anisole and acetic anhydride by 10,000-fold over the span of 50 mV of applied potential.

[0016] We emphasize that, in the limit where parasitic currents are absent, this promotion strategy requires no additional energy input beyond what is required to polarize the catalytic interface. We note that, because thermochemical reactions transfer no charge in net, this promotion effect must destabilize other intermediates in the reaction sequence to conserve the total free energy of the system. These destabilized intermediates do not influence the promoted kinetics, however, because they occur after the rate determining step.

[0017] The disclosed method would increase the reactivity of many of the already industrially employed Bronsted acid catalyzed reactions. These reactions are a significant portion of the chemical products industry, as the markets of chemicals which are produced via BAC reactions - E.g., ethylbenzene and cumene - are -21 and 9.7 billion USD markets, respectively, as of 2020. There is a significant value in these markets, but the profitability and efficiency of these chemical production processes is limited by their harsh conditions. The disclosed methodology does not require the high temperatures and pressures that are typically employed in these reactions, thereby making our strategy for increasing BAC activity a more economical and efficient alternative than the industry standard.

[0018] It should be understood that the subject matter defined in the appended claims is not necessarily limited to the specific implementations described above. The specific implementations described above are disclosed as examples only.

[0019] 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.

[0020] In one embodiment of the disclosed method, the electrode comprises a metal oxide with surface hydroxyl (-OH) groups.

[0021] In one embodiment of the disclosed method, the electrode comprises a metal oxide with surface acidic groups.

[0022] In one embodiment of the disclosed method, the electrical potential increases the acidity of the catalyst.

[0023] In one embodiment of the disclosed method, the electrical potential anodically polarizes the electrode.

[0024] In one embodiment of the disclosed method, the electrode comprises Ti / TiOHx. In one embodiment, the electrical potential is -140 mV.

[0025] In one embodiment of the disclosed method, the electrode comprises phosphotungstic acid on carbon (PTA / C). In one embodiment, the electrical potential is -330 mV.

[0026] One aspect of the disclosure herein is a Bronsted acid catalyst produced by the disclosed method.

[0027] In one embodiment, the disclosed Bronsted acid catalyst catalyzes esterification reactions, Friedel Crafts acylation reactions, dehydration reactions, and / or Friedel Crafts alkylation reactions.

[0028] In one embodiment, 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.

[0029] In one embodiment, 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.

[0030] One aspect of the disclosure herein is a reactor comprising the disclosed Bronsted acid catalyst.

[0031] In some embodiments, 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.

[0032] In some embodiments, the electrode comprises a metal oxide with surface hydroxyl (- OH) groups.

[0033] In some embodiments, the electrode comprises a metal oxide with surface acidic groups.

[0034] In some embodiments, the electrical potential increases the acidity of the catalyst.

[0035] In some embodiments, the electrical potential anodically polarizes the electrode.

[0036] In some embodiments, the electrode comprises Ti / TiOHx.

[0037] In some embodiments, the electrical potential is -140 mV.

[0038] In some embodiments, the electrode comprises phosphotungstic acid on carbon (PTA / C).

[0039] In some embodiments, the electrical potential is -330 mV.

[0040] In some embodiments, the Bronsted acid catalyst catalyzes esterification reactions, Friedel Crafts acylation reactions, dehydration reactions, and / or Friedel Crafts alkylation reactions.

[0041] In some embodiments, 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.

[0042] In some embodiments, 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.

[0043] In some embodiments, the disclosure provides a Bronsted acid catalyst produced by the method of any of the above embodiments.

[0044] In some embodiments, the disclosure provides a reactor comprising the Bronsted acid catalyst described in any of the above embodiments.

[0045] In some 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.

[0046] In some embodiments, the electrode comprises a metal, a metal oxide, a metal sulfide, a metal nitride, carbon, or silicon, or a combination of any of them.

[0047] In some embodiments, 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.

[0048] In some embodiments, 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.

[0049] In some embodiments, 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 / TiOHx, Zr / ZrOyHx, W / WOyHx, Mo / MoOyHx,Al / A10yHx, In / InOyHx, Sn / SnOyHx, Fe / FeOyHx, Co / CoOyHx, Ni / NiOyHx, Cu / CuOyHx, Zn / ZnOyHx, Ru / RuOyHx, Rh / RhOyHx, Pd / PdOyHx, Pt / PtOyHx, Ir / IrOyHx, Ag / AgOyHx, Au / AuOyHx, Pb / PbOyHx, Bi / BiOyHx, indium tin oxide (ITO), and fluorine-doped tin oxide (FTO), and a combination of any of them.

[0050] In some embodiments, 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. SHE. In some embodiments, 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.

[0051] In some embodiments, 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. In some embodiments, 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 isabout -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.

[0052] In some embodiments, a positive polarity is applied to the catalyst vs. SHE. In some embodiments, the negative polarity is applied to the catalyst vs. SHE.

[0053] In some embodiments, a positive polarity is applied to the catalyst vs. Ag / AgCl. In some embodiments, the negative polarity is applied to the catalyst vs. Ag / AgCl.

[0054] In some embodiments, 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.

[0055] In some embodiments, the electrolyte comprises at least one anion selected from F’’ Cl; Br I; o2OH; SO42; C1O4; NO3; PFe; and bistriflimide (TFSI).

[0056] In some embodiments, the electrolyte comprises at least one borate. In some embodiments, the at least one borate is selected from tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph)4‘.

[0057] In some embodiments, 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.

[0058] In some embodiments, the electrolyte comprises at least one organic cation. In some embodiments, the organic cation is an alkylammonium or imidazolium.

[0059] In some embodiments, the electrolyte comprises acetonitrile.

[0060] In certain preferred embodiments, the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]) or tetrabutylammonium bis(trifluoromethanesulfonyl)imide.

[0061] In some embodiments, the catalyst is in the form of a colloidal suspension in contact with the electrode.

[0062] In some embodiments, the electrolyte solution further comprises at least one redox buffer system.

[0063] In some embodiments, the at least one redox buffer system comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.

[0064] In some embodiments, 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.

[0065] In some embodiments, the method is performed in a batch reactor.

[0066] In some embodiments, the method is performed in a flow reactor.

[0067] In some 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.

[0068] In some embodiments, the method comprises providing a catalyst having an acidic surface and contacting the catalyst with an electrolyte solution and a redox buffer.

[0069] In some embodiments, 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.

[0070] In some embodiments, 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.

[0071] In some embodiments, 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 / TiOHx, Zr / ZrOyHx, W7W0yHx, Mo / MoOyHx, Al / A10yHx, In / InOyHx, Sn / SnOyHx, Fe / FeOyHx, Co / CoOyHx, Ni / NiOyHx, Cu / CuOyHx, Zn / ZnOyHx, Ru / RuOyHx, Rh / RhOyHx, Pd / PdOyHx, Pt / PtOyHx, Ir / IrOyHx, Ag / AgOyHx, Au / AuOyHx, Pb / PbOyHx, Bi / BiOyHx, indium tin oxide (ITO), and fluorine-doped tin oxide (FTO), and a combination of any of them.

[0072] In some embodiments, 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. SHE. In some embodiments, 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.

[0073] In some embodiments, 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. In some embodiments, 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.

[0074] In some embodiments, a positive polarity is applied to the catalyst vs. SHE. In some embodiments, the negative polarity is applied to the catalyst vs. SHE.

[0075] In some embodiments, a positive polarity is applied to the catalyst vs. Ag / AgCl. In some embodiments, the negative polarity is applied to the catalyst vs. Ag / AgCl.

[0076] In some embodiments, 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.

[0077] In some embodiments, the electrolyte comprises at least one anion selected from F; Cl; Br I; o2OH; SO42; C1O4; NO3; PFe; and bistriflimide (TFSI).

[0078] In some embodiments, the electrolyte comprises at least one borate.

[0079] In some embodiments, at least one borate is selected from tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph)4‘.

[0080] In some embodiments, 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.

[0081] In some embodiments, the electrolyte comprises at least one organic cation. In some embodiments, the at least one organic cation is alkylammonium or imidazolium.

[0082] In some embodiments, the electrolyte comprises acetonitrile.

[0083] In certain preferred embodiments, the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]) or tetrabutylammonium bis(trifluoromethanesulfonyl)imide.

[0084] In certain preferred embodiments, the redox buffer system comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.

[0085] In some embodiments, the method is performed in a batch reactor.

[0086] In some embodiments, the method is performed in a flow reactor.

[0087] In some embodiments, 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.

[0088] In some 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.

[0089] In some embodiments, 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.

[0090] In some embodiments, the working electrode comprises a metal, metal oxide, metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.

[0091] In some embodiments, 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.

[0092] In some embodiments, the counter electrode chamber further comprises a conductive material having an acidic surface dispersed in the electrolyte.

[0093] In some embodiments, 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.

[0094] In some embodiments, the electrolyte comprises at least one anion selected from F; Cl; Br I; o2OH; SO42; C1O4; NO3; PFe; and bistriflimide (TFSI).

[0095] In some embodiments, the electrolyte comprises at least one borate.

[0096] In some embodiments, the borate is selected from tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph)4‘

[0097] In some embodiments, 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.

[0098] In some embodiments, the electrolyte comprises at least one organic cation. In some embodiments, the at least one organic cation is an alkylammonium or imidazolium.

[0099] In certain preferred embodiments, the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]), tetrabutylammonium bis(trifluoromethanesulfonyl)imide, or acetonitrile.

[0100] In some embodiments, 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. SHE. In some embodiments, 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.

[0101] In some embodiments, 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. In some embodiments, 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 isabout -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.

[0102] In some embodiments, a positive polarity is applied to the catalyst vs. SHE. In some embodiments, the negative polarity is applied to the catalyst vs. SHE.

[0103] In some embodiments, a positive polarity is applied to the catalyst vs. Ag / AgCl. In some embodiments, the negative polarity is applied to the catalyst vs. Ag / AgCl.

[0104] In some embodiments, the electrolyte solution further comprises at least one redox buffer. In certain preferred embodiments, the redox buffer comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.

[0105] In some embodiments, 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.

[0106] In some embodiments, the working electrode and / or conductive catalyst comprises a metal oxide metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.

[0107] In some embodiments, 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.

[0108] In some embodiments, 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 / TiOHx, Zr / ZrOyHx, W / WOyHx, Mo / MoOyHx, Al / A10yHx, In / InOyHx, Sn / SnOyHx, Fe / FeOyHx, Co / CoOyHx, Ni / NiOyHx, Cu / CuOyHx, Zn / ZnOyHx, Ru / RuOyHx, Rh / RhOyHx, Pd / PdOyHx, Pt / PtOyHx, Ir / IrOyHx, Ag / AgOyHx, Au / AuOyHx, Pb / PbOyHx, Bi / BiOyHx, indium tin oxide (ITO), and fluorine-doped tin oxide (FTO), and a combination of any of them.

[0109] In some 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.

[0110] In some embodiments, the reference electrode comprises Ag / AgCl.

[0111] In some embodiments, 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.

[0112] In some embodiments, 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.

[0113] In some embodiments, the catalyst comprises a metal, metal oxide, metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.

[0114] In some embodiments, 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.

[0115] In some embodiments, 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.

[0116] In some embodiments, 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 / TiOHx, Zr / ZrOyHx, W / WOyHx, Mo / MoOyHx, Al / A10yHx, In / InOyHx, Sn / SnOyHx, Fe / FeOyHx, Co / CoOyHx, Ni / NiOyHx, Cu / CuOyHx, Zn / ZnOyHx, Ru / RuOyHx, Rh / RhOyHx, Pd / PdOyHx, Pt / PtOyHx, Ir / IrOyHx,Ag / AgOyHx, Au / AuOyHx, Pb / PbOyHx, Bi / BiOyHx, indium tin oxide (ITO), and fluorinedoped tin oxide (FTO), and a combination of any of them.

[0117] In some embodiments, the electrochemical potential is applied via the insertion of a conductive electrode into the electrolyte solution.

[0118] In some embodiments, the conductive electrode comprises a metal, metal oxide, metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.

[0119] In some embodiments, 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.

[0120] In some embodiments, the electrochemical potential is applied via the addition of a redox buffer into the electrolyte solution.

[0121] In some embodiments, 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.

[0122] In certain preferred embodiments, the redox buffer comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.

[0123] In some embodiments, 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. SHE. In some embodiments, 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.

[0124] In some embodiments, 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. In some embodiments, 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.

[0125] In some embodiments, a positive polarity is applied to the catalyst vs. SHE. In some embodiments, the negative polarity is applied to the catalyst vs. SHE.

[0126] In some embodiments, a positive polarity is applied to the catalyst vs. Ag / AgCl. In some embodiments, the negative polarity is applied to the catalyst vs. Ag / AgCl.

[0127] In some embodiments, the method is performed in a batch reactor.

[0128] In some embodiments, the method is performed in a flow reactor.

[0129] In some embodiments, the catalyst is in the form of a colloidal suspension in contact with the conductive electrode.

[0130] In some embodiments, 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.

[0131] In some embodiments, the electrolyte comprises at least one anion selected from F’, Cl’, Br , I’, O2', OH’, SO42’, C1O4’, NOs’, PFe’, and bistrifhmide (TFSI).

[0132] In some embodiments, the electrolyte comprises at least one borate. In some embodiments, the at least one borate is selected from tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and BfPhfy.

[0133] In some embodiments, 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.

[0134] In some embodiments, the electrolyte comprises at least one organic cation. In some embodiments, the organic cation is an alkylammonium or imidazolium.

[0135] In some embodiments, the electrolyte comprises acetonitrile.

[0136] In certain preferred embodiments, the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]), tetrabutylammonium bis(trifluoromethanesulfonyl)imide, or acetonitrile.

[0137] In some embodiments, the catalyst is purchased from a commercial source. In some embodiments, the catalyst is pre-treated or otherwise activated prior to use.EXAMPLESExample 1: Polarizing a 2D Electrode to increase its Bronsted Acidity1.1 Phosphotungstic Acid (PTA) / Carbon Electrode Synthesis

[0138] 2 cm x 1 cm rectangles of carbon paper were cut with a clean ceramic knife absent of any metal contamination. From these rectangles, one 1 cm x 0.5 cm quadrant was cut, yielding a “flag” shape for further use.

[0139] To deposit PTA onto the carbon electrode, a fresh solution of 10 mg PTA in 10 mL of MeCN was prepared. A carbon flag was placed on a hotplate set to 80°C, and 0.2 mL of the PTA / MeCN solution was dropped onto the square portion of the flag. After drying completely, the electrode was placed in an oven at 100°C for 1 hour to ensure PTA clusters were chemically bound to the surface.1.2 Wired Dehydration Reaction Procedure

[0140] Before a typical driven polarized dehydration reaction with PTA as a catalyst, PTA / C working electrodes (WEs) were stirred in fresh acetonitrile for 5 min and dried. A standard undivided three-electrode setup was then constructed (FIG. 1) in a 20 mL scintillation vial containing electrolyte solution 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 workingelectrode by initiating a chronoamperometry experiment. The temperature of the reaction was controlled via a thermocouple attached to an aluminum jacket around the vial.

[0141] For a model Bronsted acid catalyzed reaction involving the dehydration of 1- methylcy cl opentanol, with a substrate solution consisting of 10 mL of MeCN (7.86 g) containing 0.1 M 1 -methylcyclopentanol (0.100 g, 1 mmol), 0.1 M [TBA][PFe] (0.393 g, 1 mmol), and 0.1 M 1,3,5-tri-tert-butylbenzene (TTB) (0.240 g, 1 mmol), dehydration experiments polarized from 1390 mV to 1530 mV vs. the DmFc / DmFc+couple show an increase in catalyst activity by nearly 100-fold (FIG. 2).Example 2: Polarizing a 2D Electrode to increase its Bronsted Acidity with a Different Electrolyte2.1 Phosphotungstic Acid (PTA) / Carbon Electrode Synthesis

[0142] 2 cm x 1 cm rectangles of carbon paper were cut with a clean ceramic knife absent of any metal contamination. From these rectangles, one 1 cm x 0.5 cm quadrant was cut, yielding a “flag” shape for further use.

[0143] To deposit PTA onto the carbon electrode, a fresh solution of 10 mg PTA in 10 mL of MeCN was prepared. A carbon flag was placed on a hotplate set to 80°C, and 0.2 mL of the PTA / MeCN solution was dropped onto the square portion of the flag. After drying completely, the electrode was placed in an oven at 100°C for 1 hour to ensure PTA clusters were chemically bound to the surface.2.2 Wired Dehydration Reaction Procedure

[0144] Before a typical driven polarized dehydration reaction with PTA as a catalyst, PTA / C working electrodes (WEs) were stirred in fresh acetonitrile for 5 min and dried. A standard undivided three-electrode setup was then constructed (FIG. 1) in a 20 mL scintillation vial containing electrolyte solution 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.

[0145] For a model Bronsted acid catalyzed reaction involving the dehydration of 1- methylcy cl opentanol, with a substrate solution consisting of 10 mL of MeCN (7.86 g) containing 0.1 M 1 -methylcyclopentanol (0.100 g, 1 mmol), 0.1 M tetrabutyl ammonium bis(trifluoromethanesulfonyl)imide ([TBA][TFSI]) (0.522 g, 1 mmol), and 0.1 M TTB(0.240 g, 1 mmol), dehydration experiments polarized at 1530 mV vs. the DmFc / DmFc+ couple show an similar reaction rate to those using [TBA][PFe] as an electrolyte (within -36%, FIG. 3).Example 3: Polarizing a 2D Electrode to increase its Bronsted Acidity and Isomerize 1- Decene3.1 Phosphotungstic Acid (PTA) / Carbon Electrode Synthesis

[0146] 2 cm x 1 cm rectangles of carbon paper were cut with a clean ceramic knife absent of any metal contamination. From these rectangles, one 1 cm x 0.5 cm quadrant was cut, yielding a “flag” shape for further use.

[0147] To deposit PTA onto the carbon electrode, a fresh solution of 10 mg PTA in 10 mL of MeCN was prepared. A carbon flag was placed on a hotplate set to 80°C, and 0.2 mL of the PTA / MeCN solution was dropped onto the square portion of the flag. After drying completely, the electrode was placed in an oven at 100°C for 1 hour to ensure PTA clusters were chemically bound to the surface.3.2 Wired Isomerization Reaction Procedure

[0148] 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.

[0149] For a model alkene isomerization reaction involving the isomerization of 1- decene, with a substrate solution consisting of 10 mL of 1 -decene containing 0.1 M tetradodecylammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, dehydration experiments polarized at 5000 mV vs. the Ag / AgCl couple at 70°C show 1 -decene isomerization products via GC-MS patterns (FIG. 4). Experiments in the same setup without any applied polarization did not display any isomerization products.Example 4: Use of a Polarized Slurry Reactor to increase the Bronsted Acidity of aDispersed Conductive Catalyst4.1 Polarized Slurry Reactor Experimental Design

[0150] 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).

[0151] After the potential of the WE is set to the desired electrochemical potential and the electrochemical potential of the SE measures the same value as the WE, substrate is introduced into the working compartment.

[0152] For a model Bronsted acid catalyzed reaction involving the dehydration of 1- methylcy cl opentanol, with a substrate solution consisting of 20 mL of MeCN containing 0.0025 M 1 -methylcyclopentanol and 0.5 M [TBA][PFe] throughout the slurry reactor, dehydration experiments polarized from 1200 mV to 1290 mV vs. the Ag / AgCl couple show an increase in catalyst activity by nearly 10-fold (FIG. 6). 100 mg of 5% PTA / C were dispersed in the working compartment in each of these experiments.Example 5: Use of Chemical Additive (Redox Buffer) to increase the Bronsted Acidity of a Dispersed Conductive Catalyst5.1 Redox Buffer Syntheses5.1.1 [Fe(phen)3][PFe]2 (Ferroin) Synthesis

[0153] 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 oncewith 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.5.1.2 [Fe (phen) 3] [PF 6] 3 (Ferriin) Synthesis

[0154] 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. The solid was washed with water until the filtrate’s pH was 7. The solid was then washed with 40 mL Et2O to remove residual water. The resulting dark-blue powder was vacuum-dried overnight to yield 1.19 g (1.1 mmol, 98% yield) as a dark blue colored powder.5.2 5% PTA / C Powder Synthesis

[0155] To a 50 mL Falcon tube, 50 mg of PTA, 30 mL of acetonitrile, and 1 g of Vulcan Carbon were added. The mixture was shaken, then stirred at 1150 rpm for 15 min. Afterwards, the mixture was sonicated for 5 min, then centrifuged to isolate the solids. The resulting pellet was then dried in an oven at 90°C for 6 hrs. The 5% PTA / C powder pellet was then broken into a fine powder with a spatula, after which it was unmodified before further use.5.3 Wireless Reaction Procedure

[0156] In a prototypical wirelessly polarized dehydration reaction, electrolyte and substrate solution were stirred at 1400 rpm in a 20 mL scintillation vial at 40°C. The temperature of the reaction was controlled via a thermocouple attached to an aluminum jacket around the vial. To this solution, the Ferroin / Ferriin redox buffer was added to the reaction solution and stirred for 1 min prior to reaction. Subsequently, PTA / C was added to the reaction mixture to initiate the reaction.

[0157] For a model Bronsted acid catalyzed reaction involving the dehydration of 1- methylcy cl opentanol, with a substrate solution consisting of 10 mL of MeCN (7.86 g) containing 1 M 1 -methylcyclopentanol (1.00 g, 10 mmol), 0.1 M [TBA][PFe] (0.393 g, 1 mmol), and 0.1 M TTB (0.240 g, 1 mmol), dehydration experiments polarized from 1390mV to 1530 mV vs. the DmFc / DmFc+couple show an increase in catalyst activity by nearly 10-fold (FIG. 7).INCORPORATION BY REFERENCE

[0158] All patents and published patent applications mentioned in the description above are incorporated by reference herein in their entirety.EQUIVALENTS

[0159] Having described the present invention in some detail by way of illustration and example for purposes of clarity of understanding, it will be obvious to one of ordinary skill in the art that the same can be performed by modifying or changing the invention within a wide and equivalent range of conditions, formulations and other parameters without affecting the scope of the invention or any specific embodiment thereof, and that such modifications or changes are intended to be encompassed within the scope of the appended claims.

Claims

CLAIMSWhat is claimed is:

1. 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.

2. The method of claim 1, wherein the electrode comprises a metal, a metal oxide, a metal sulfide, a metal nitride, carbon, or silicon, or a combination of any of them.

3. The method according to any one of claims 1 and 2, wherein in 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.

4. The method according to any one of claims 1-3, wherein 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.

5. The method according to any one of claims 1-4, wherein 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 / TiOHx, Zr / ZrOyHx, W / WOyHx, Mo / MoOyHx, Al / A10yHx, In / InOyHx, Sn / SnOyHx, Fe / FeOyHx, Co / CoOyHx, Ni / NiOyHx, Cu / CuOyHx, Zn / ZnOyHx, Ru / RuOyHx, Rh / RhOyHx, Pd / PdOyHx, Pt / PtOyHx, Ir / IrOyHx, Ag / AgOyHx, Au / AuOyHxPb / PbOyHx, Bi / BiOyHx, indium tin oxide (ITO), and fluorine-doped tin oxide (FTO), and a combination of any of them.

6. The method according to any one of claims 1-5, wherein the applied electrochemical potential is about -30 V to about +30 V vs. SHE.

7. The method according to any one of claims 1-6, wherein the applied electrochemical potential is about -3 V to about +3 V vs. SHE.

8. The method according to any one of claims 1-7, wherein a positive polarity is applied to the catalyst vs. SHE.

9. The method according to any one of claims 1-7, wherein a negative polarity is applied to the catalyst vs. SHE.

10. The method according to any one of claims 1-9, wherein 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.

11. The method according to any one of claims 1-10, wherein the electrolyte comprises at least one anion selected from F; Cl’, Br , I’, Ch’, OH’, SO42’, ClOF, NOs’, PFe’, and bistriflimide (TFSI).

12. The method according to any one of claims 1-11, wherein the electrolyte comprises at least one borate.

13. The method according to claim 12, wherein the at least one borate is selected from tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph)4’.

14. The method according to any one of claims 1-13, wherein 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.

15. The method according to any one of claims 1-14, wherein the electrolyte comprises at least one organic cation.

16. The method according to claim 15, wherein the organic cation is an alkylammonium or imidazolium.

17. The method according to any one of claims 1-10, wherein the electrolyte comprises acetonitrile.

18. The method according to any one of claims 1-10, wherein the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]) or tetrabutylammonium bis(trifluoromethanesulfonyl)imide.

19. The method according to any one of claims 1-18, wherein the catalyst is in the form of a colloidal suspension in contact with the electrode.

20. The method according to any one of claims 1-19, wherein the electrolyte solution further comprises at least one redox buffer system.

21. The method according to claim 20, wherein the at least one redox buffer system comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.

22. A method of catalyzing a chemical reaction with a catalyst, wherein the surface acidity of the catalyst is modulated according to the method of any one of claims 1-21.

23. The method according to any one of claims 1-22, wherein the method is performed in a batch reactor.

24. The method according to any one of claims 1-22, wherein the method is performed in a flow reactor.

25. The method of any one of claims 22-24, wherein 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.

26. 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.

27. The method according to claim 26, wherein 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.

28. The method of either claim 26 or 27, wherein 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.

29. The method according to any one of claims 26-28, wherein 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 / TiOHx, Zr / ZrOyHx, W / WOyHx, Mo / MoOyHx, Al / A10yHx, In / InOyHx, Sn / SnOyHx, Fe / FeOyHx, Co / CoOyHx, Ni / NiOyHx, Cu / CuOyHx, Zn / ZnOyHx, Ru / RuOyHx, Rh / RhOyHx, Pd / PdOyHx, Pt / PtOyHx, Ir / IrOyHx, Ag / AgOyHx, Au / AuOyHxPb / PbOyHx, Bi / BiOyHx, indium tin oxide (ITO), and fluorine-doped tin oxide (FTO), and a combination of any of them.

30. The method according to any one of claims 26-29, wherein the applied electrochemical potential is about -30 V to about +30 V vs. SHE.

31. The method according to any one of claims 26-30, wherein the applied electrochemical potential is about -3 V to about +3 V vs. SHE.

32. The method according to any one of claims 26-31, wherein a positive polarity is applied to the catalyst vs. SHE.

33. The method according to any one of claims 26-31, wherein a negative polarity is applied to the catalyst vs. SHE.

34. The method according to any one of claims 26-33, wherein 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.

35. The method according to any one of claims 26-34, wherein the electrolyte comprises at least one anion selected from F’, Cl’, Br , I’, Ch’, OH’, SO42’, CIOT, NOs’, PFe’, and bistriflimide (TFSI).

36. The method according to any one of claims 26-35, wherein the electrolyte comprises at least one borate.

37. The method according to claim 36, wherein the at least one borate is selected from tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph)4’.

38. The method according to any one of claims 26-37, wherein 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.

39. The method according to any one of claims 26-38, wherein the electrolyte comprises at least one organic cation.

40. The method according to claim 39, wherein the at least one organic cation is alkylammonium or imidazolium.

41. The method according to any one of claims 26-34, wherein the electrolyte comprises acetonitrile.

42. The method according to any one of claims 26-34, wherein the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]) or tetrabutylammonium bis(trifluoromethanesulfonyl)imide.

43. The method according to any one of claims 26-42, wherein the redox buffer system comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.

44. The method according to any one of claims 26-43, wherein the method is performed in a batch reactor.

45. The method according to any one of claims 26-43, wherein the method is performed in a flow reactor.

46. A method of catalyzing a chemical reaction with a catalyst, wherein the surface acidity of the catalyst is modulated according to the method of any one of claims 26-45.

47. The method of claim 46, wherein 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.

48. 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: i. providing a reactor comprising: a) 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; b) a counter electrode chamber comprising a counter electrode, the electrolyte; and c) a separation membrane located between the working electrode and counter electrode chambers; ii. contacting the working electrode, counter electrode, and catalyst with an electrolyte; iii. introducing at least one reaction substrate into the working electrode chamber; and iv. applying an electrochemical potential to the working electrode.

49. The method of claim 48, wherein the working electrode comprises a metal, metal oxide, metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.

50. The method of claim 48 or 49, wherein 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.

51. The method of any one of claims 48-50, wherein the counter electrode chamber further comprises a conductive material having an acidic surface dispersed in the electrolyte.

52. The method according to any one of claims 48-51, wherein 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.

53. The method according to any one of claims 48-52, wherein the electrolyte comprises at least one anion selected from F’, Cl’, Br , I’, Ch’, OH’, SO42’, CIOT, NOs’, PFe’, and bistriflimide (TFSI).

54. The method according to any one of claims 48-53, wherein the electrolyte comprises at least one borate.

55. The method according to claim 54, wherein the at least one borate is selected from tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph)4’.

56. The method according to any one of claims 48-55, wherein 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.

57. The method according to any one of claims 48-56, wherein the electrolyte comprises at least one organic cation.

58. The method according to claim 57, wherein the at least one organic cation is an alkylammonium or imidazolium.

59. The method of any one of claims 48-52, wherein the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PF6]), tetrabutylammonium bis(trifluoromethanesulfonyl)imide, or acetonitrile.

60. The method according to any one of claims 48-59, wherein the applied electrochemical potential is about -30 V to about +30 V vs. SHE.

61. The method according to any one of claims 48-60, wherein the applied electrochemical potential is about -3 V to about +3 V vs. SHE.

62. The method according to any one of claims 48-61, wherein a positive polarity is applied to the catalyst relative to the reference electrode.

63. The method according to any one of claims 48-61, wherein a negative polarity is applied to the catalyst relative to the reference electrode.

64. The method according to any one of claims 48-63, wherein the electrolyte solution further comprises at least one redox buffer.

65. The method of claim 64, wherein the redox buffer comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.

66. The method according to any one of claims 48-63, wherein in 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.

67. The method according to any one of claims 48-66, wherein the working electrode and / or conductive catalyst comprises a metal oxide metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.

68. The method according to any one of claims 48-67, wherein 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.

69. The method according to any one of claims 48-68, wherein 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 / TiOHx, Zr / ZrOyHx, W / WOyHx, Mo / MoOyHx, Al / A10yHx, In / InOyHx, Sn / SnOyHx, Fe / FeOyHx, Co / CoOyHx, Ni / NiOyHx, Cu / CuOyHx, Zn / ZnOyHx, Ru / RuOyHx, Rh / RhOyHx, Pd / PdOyHx, Pt / PtOyHx, Ir / IrOyHx, Ag / AgOyHx, Au / AuOyHxPb / PbOyHx, Bi / BiOyHx, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), and a combination of any of them.

70. The method according to any one of claims 48-69, wherein 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.

71. The method according to any one of claims 48-70, wherein the reference electrode comprises Ag / AgCl.

72. 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.

73. The method of claim 72, wherein 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.

74. The method of either claim 72 or 73, wherein the catalyst comprises a metal, metal oxide, metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.

75. The method according to any one of claims 72-74, wherein 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.

76. The method of any one of claims 72-75, wherein 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.

77. The method of any one of claims 72-76, wherein 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 / TiOHx, Zr / ZrOyHx, W / WOyHx, Mo / MoOyHx, Al / A10yHx, In / InOyHx, Sn / SnOyHx, Fe / FeOyHx, Co / CoOyHx, Ni / NiOyHx, Cu / CuOyHx, Zn / ZnOyHx, Ru / RuOyHx, Rh / RhOyHx, Pd / PdOyHx, Pt / PtOyHx, Ir / IrOyHx, Ag / AgOyHx, Au / AuOyHxPb / PbOyHx, Bi / BiOyHx, indium tin oxide (ITO), and fluorine-doped tin oxide (FTO), and a combination of any of them.

78. The method of any one of claims 72-77, wherein the electrochemical potential is applied via the insertion of a conductive electrode into the electrolyte solution.

79. The method of claim 78, wherein the conductive electrode comprises a metal, metal oxide, metal sulfide, metal nitride, carbon, silicon, or a combination of any of them.

80. The method of claim 79, wherein 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.

81. The method of any one of claims 72-77, wherein the electrochemical potential is applied via the addition of a redox buffer into the electrolyte solution.

82. The method of any one of claims 72-81, wherein 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.

83. The method of either claim 81 or 82, wherein the redox buffer comprises [Fe(phen)3][PFe]2 and [Fe(phen)3][PFe]3.

84. The method of any of claims 72-83, wherein the applied electrochemical potential is about -30 V to about +30 V vs. SHE.

85. The method of any of claims 72-84, wherein the applied electrochemical potential is about -3 V to about +3 V vs. SHE.

86. The method according to any one of claims 72-85, wherein a positive polarity is applied to the catalyst.

87. The method according to any one of claims 72-85, wherein a negative polarity is applied to the catalyst.

88. The method according to any one of claims 72-87, wherein the method is performed in a batch reactor.

89. The method according to any one of claims 72-87, wherein the method is performed in a flow reactor.

90. The method according to any one of claims 72-89, wherein the catalyst is in the form of a colloidal suspension in contact with the conductive electrode.

91. The method according to any one of claims 72-90, wherein 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.

92. The method according to any one of claims 72-91, wherein the electrolyte comprises at least one anion selected from F’, Cl’, Br’, I’, Ch’, OH’, SO42’, CIOT, NOs’, PFe’, and bistriflimide (TFSI).

93. The method according to any one of claims 72-91, wherein the electrolyte comprises at least one borate.

94. The method according to claim 93, wherein the at least one borate is selected from tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF), tetrakis(pentafluorophenyl)borate, and B(Ph)4’.

95. The method according to any one of claims 72-94, wherein 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.

96. The method according to any one of claims 72-95, wherein the electrolyte comprises at least one organic cation.

97. The method according to claim 96, wherein the organic cation is an alkylammonium or imidazolium.

98. The method according to any one of claims 72-91, wherein the electrolyte comprises acetonitrile.

99. The method according to any one of claims 72-91, wherein the electrolyte comprises tetrabutylammonium hexafluorphosphate ([TBA][PFe]), tetrabutylammonium bis(trifluoromethanesulfonyl)imide, or acetonitrile.

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