ENHANCED WATER ELECTROLYSIS WITH PROTIC CO-CATALYSTS

Abstract

Catalyst systems employing inexpensive and readily-available protic co-catalysts to increase a proton reduction rate in a hydrogen evolution reaction (HER) are described herein. The protic co-catalysts function to increase the rate without being consumed in the process of water splitting to hydrogen and oxygen. They may simultaneously serve to stabilize the pH of the water and be the electrolyte to carry the current for the electrolytic splitting of water. The protic co-catalysts also decrease the overpotential energy requirement for the process of water splitting. These protic co-catalysts can be used with both heterogeneous and homogenous catalysts, as well as assist photocatalysis and other processes for the reduction of protons.

Claims

1. A method of increasing a hydrogen (H.sub.2) generation rate of an electrolysis process in which protons from an aqueous medium are reduced to H.sub.2, the method comprising adding a protic co-catalyst to the aqueous medium, wherein the protic co-catalyst is in a protonated state, wherein the protic co-catalyst increases the rate of H.sub.2 generation without being consumed during the electrolysis process.

2. The method of claim 1, wherein the protic co-catalyst is a pH stabilizer.

3. The method of claim 1, wherein the protic co-catalyst acts as an electrolyte that carries a current for the electrolysis process.

4. (canceled)

5. The method of claim 1, wherein the electrolysis process comprises photocatalysis, a non-liquid process, a solid state process, water splitting, or ion exchange.

6. The method of claim 1, wherein the protic co-catalyst decreases an energy requirement of the electrolysis process.

7. The method of claim 1, wherein a pH of the proton source and a pK.sub.a of the co-catalyst are selected such that the co-catalyst is in a majority protic state.

8. The method of claim 1, wherein the protic co-catalyst comprises maleate, bicine, sodium phosphate, sodium dihydrogen phosphate, sodium carbonate, di-sodium hydrogenphosphate, glycine, glycylglycine, imidazole, citrate, triethanolamine, tricine, boric acid, ammonium acetate, magnesium acetate, potassium acetate, sodium acetate, N-(2-acetamido)-2-aminoethanesulfonic acid (ACES), N-(2-acetamido)iminodiacetic acid (ADA), taurine (AES), 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol (AMPD), N-(1,1-dimethyl-2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO), N,N-bis(2-hydroxethyl)-2-aminoethanesulfonic acid (BES), 4-(cyclohexylamino)-1-butane-sulfonic acid (CABS), N-cyclohexyl-3-aminopropanesulfonic acid (CAPS), 3-(cyclohexyl-amino)-2-hydroxy-1-propanesulfonic acid (CAPSO), N-cyclohexyl-2-aminoethane-sulfonic acid (CHES), N,N-bis(2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (DIPSO), N-(2-hydroxyethyl)piperazine-N-(4-butanesulfonic acid) (HEPBS), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (HEPPS), 4-(2-hydroxyethyl)-piperazine-1-(2-Hydroxy)-propane-sulfonic acid (HEPPSO), 4-morpholineethanesulfonate (MES), 4-(N-morpholino)butane-sulfonic acid (MOBS), 3-morpholinopropane-1-sulfonic acid (MOPS), 3-morpholino-2-hydroxy-propanesulfonic acid (MOPSO), 1,4-piperazineethanesulfonate (PIPES), piperazine-N,N-bis(2-hydroxypropanesulfonic acid) (POPSO), N-tris(hydroxymethyl)-methyl-4-aminobutanesulfonic acid (TABS), N-[tris(hydroxymethyl)methyl]-3-amino-propane-sulfonic acid (TAPS), 2-hydroxy-3-[tris(hydroxymethyl)methylamino]-1-propanesulfonic acid (TAPSO), 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-ethanesulfonic acid (TES), tris-(hydroxymethyl)-aminomethane (Tris), Bis-Tris, or Bis-Tris-Propane.

9. The method of claim 1, wherein the protic co-catalyst comprises a polymer.

10. (canceled)

11. A method for improving a hydrogen (H.sub.2) generation rate of an electrolysis process, wherein H.sub.2 is generated by reducing protons in an aqueous medium, the method comprising: a. adding a catalyst to the aqueous medium; and b. adding a protic co-catalyst to the aqueous medium, wherein the protic co-catalyst is in a protonated state; wherein the catalyst reduces protons of the aqueous medium to generate H.sub.2, wherein the protic co-catalyst acts increases the rate of H.sub.2 generation without being consumed during the electrolysis process.

12. The method of claim 11, wherein the protic co-catalyst stabilizes a pH of the aqueous solution and acts as an electrolyte that carries a current for electrolysis.

13. The method of claim 11, wherein the protic co-catalyst decreases an energy requirement of the electrolysis process.

14. The method of claim 11, wherein the pH of the aqueous medium and a pK.sub.a of the co-catalyst are selected such that the co-catalyst is in a majority protic state.

15. The method of claim 11, wherein the protic co-catalyst comprises maleate, bicine, sodium phosphate, sodium dihydrogen phosphate, sodium carbonate, di-sodium hydrogenphosphate, glycine, glycylglycine, imidazole, citrate, triethanolamine, tricine, boric acid, ammonium acetate, magnesium acetate, potassium acetate, sodium acetate, N-(2-acetamido)-2-aminoethanesulfonic acid (ACES), N-(2-acetamido)iminodiacetic acid (ADA), taurine (AES), 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol (AMPD), N-(1,1-dimethyl-2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO), N,N-bis(2-hydroxethyl)-2-aminoethanesulfonic acid (BES), 4-(cyclohexylamino)-1-butane-sulfonic acid (CABS), N-cyclohexyl-3-aminopropanesulfonic acid (CAPS), 3-(cyclohexyl-amino)-2-hydroxy-1-propanesulfonic acid (CAPSO), N-cyclohexyl-2-aminoethane-sulfonic acid (CHES), N,N-bis(2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (DIPSO), N-(2-hydroxyethyl)piperazine-N-(4-butanesulfonic acid) (HEPBS), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (HEPPS), 4-(2-hydroxyethyl)-piperazine-1-(2-Hydroxy)-propane-sulfonic acid (HEPPSO), 4-morpholineethanesulfonate (MES), 4-(N-morpholino)butane-sulfonic acid (MOBS), 3-morpholinopropane-1-sulfonic acid (MOPS), 3-morpholino-2-hydroxy-propanesulfonic acid (MOPSO), 1,4-piperazineethanesulfonate (PIPES), piperazine-N,N-bis(2-hydroxypropanesulfonic acid) (POPSO), N-tris(hydroxymethyl)-methyl-4-aminobutanesulfonic acid (TABS), N-[tris(hydroxymethyl)methyl]-3-amino-propane-sulfonic acid (TAPS), 2-hydroxy-3-[tris(hydroxymethyl)methylamino]-1-propanesulfonic acid (TAPSO), 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-ethanesulfonic acid (TES), tris-(hydroxymethyl)-aminomethane (Tris), Bis-Tris, or Bis-Tris-Propane.

16. The method of claim 11, wherein the protic co-catalyst comprises a polymer.

17. (canceled)

18. The method of claim 11, wherein the catalyst is a homogenous or heterogeneous catalyst.

19. (canceled)

20. The method of claim 18, wherein the catalyst is comprised of a water-soluble metallopolymer, platinum, or alloys or oxides of iridium, nickel, nickel-iron, or nickel-oxide.

21. An electrolyzer system for generating hydrogen (H.sub.2) via an electrolysis reaction, said system comprising: a. an anode; b. a cathode comprising a catalyst; c. an external power supply operatively coupled to the anode and cathode; d. a protic co-catalyst; and e. an aqueous medium, wherein the anode, cathode, and protic co-catalyst are disposed in the aqueous medium; wherein the external power supply passes an electric current between the anode and cathode to effect water splitting in the aqueous medium, wherein the catalyst reduces protons to generate H.sub.2, wherein the protic co-catalyst increases a rate of H.sub.2 generation without being consumed during the electrolysis reaction.

22.-25. (canceled)

26. The system of claim 21, wherein the protic co-catalyst comprises maleate, bicine, sodium phosphate, sodium dihydrogen phosphate, sodium carbonate, di-sodium hydrogenphosphate, glycine, glycylglycine, imidazole, citrate, triethanolamine, tricine, boric acid, ammonium acetate, magnesium acetate, potassium acetate, sodium acetate, N-(2-acetamido)-2-aminoethanesulfonic acid (ACES), N-(2-acetamido)iminodiacetic acid (ADA), taurine (AES), 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol (AMPD), N-(1,1-dimethyl-2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO), N,N-bis(2-hydroxethyl)-2-aminoethanesulfonic acid (BES), 4-(cyclohexylamino)-1-butane-sulfonic acid (CABS), N-cyclohexyl-3-aminopropanesulfonic acid (CAPS), 3-(cyclohexyl-amino)-2-hydroxy-1-propanesulfonic acid (CAPSO), N-cyclohexyl-2-aminoethane-sulfonic acid (CHES), N,N-bis(2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (DIPSO), N-(2-hydroxyethyl)piperazine-N-(4-butanesulfonic acid) (HEPBS), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (HEPPS), 4-(2-hydroxyethyl)-piperazine-1-(2-Hydroxy)-propane-sulfonic acid (HEPPSO), 4-morpholineethanesulfonate (MES), 4-(N-morpholino)butane-sulfonic acid (MOBS), 3-morpholinopropane-1-sulfonic acid (MOPS), 3-morpholino-2-hydroxy-propanesulfonic acid (MOPSO), 1,4-piperazineethanesulfonate (PIPES), piperazine-N,N-bis(2-hydroxypropanesulfonic acid) (POPSO), N-tris(hydroxymethyl)-methyl-4-aminobutanesulfonic acid (TABS), N-[tris(hydroxymethyl)methyl]-3-amino-propane-sulfonic acid (TAPS), 2-hydroxy-3-[tris(hydroxymethyl)methylamino]-1-propanesulfonic acid (TAPSO), 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-ethanesulfonic acid (TES), tris-(hydroxymethyl)-aminomethane (Tris), Bis-Tris, or Bis-Tris-Propane.

27. The system of claim 21, wherein the protic co-catalyst comprises a polymer.

28. (canceled)

29. The system of claim 21, wherein the catalyst is a homogenous or heterogeneous catalyst.

30.-33. (canceled)

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

[0013] The features and advantages of the present invention will become apparent from a consideration of the following detailed description presented in connection with the accompanying drawings in which:

[0014] FIG. 1A shows a reaction schematic of water-splitting electrolysis.

[0015] FIG. 1B shows a reaction schematic of water-splitting with a protic co-catalyst of the present invention.

[0016] FIG. 2 shows cyclic voltammograms (CV) that illustrate the effect of two protic co-catalysts, one derived from Tris and the other derived from phosphate, on the rate of electrocatalytic hydrogen production from water at pH 7 by a catalyst. The rate is dependent on both the concentration and nature of the co-catalyst. The bottom curve shows the negligible rate in the absence of catalysts.

[0017] FIG. 3 shows another CV that illustrates the effect of concentration of the protic co-catalyst derived from Tris on the rate of electrocatalytic hydrogen production from water at pH 7 by a heterogeneous catalyst, in this case a planar platinum surface. The lines become jagged due to the rapid production of hydrogen bubbles.

[0018] FIG. 4A-4C show CV comparisons of 1 M sodium phosphate and 1 M Tris solution conditions adjusted to pH 7 for Pt (FIG. 4A), PDMAEMA-g-[2Fe-2S] (FIG. 4B), and POEGMA-g-[2Fe-2S] (FIG. 4C). This CV data indicates the improvement of having a higher concentration of protic species in solution across different catalyst examples while maintain the same pH. The CV scans were done at a sweep rate of 0.1 V/s using a platinum disk electrode for FIG. 4A and glassy carbon disk electrode for FIGS. 4B and 4C. The catalyst concentration used in FIGS. 4B and 4C was 10 M based on [2Fe-2S] content using IR spectroscopy.

[0019] FIG. 5 shows a Tafel comparison of a homogeneous catalyst to Pt in 1 M Tris solution at pH 7 and a glassy carbon disk electrode in the same solution with added PDMAEMA-g-[2Fe-2S] (100 M [2Fe-2S] by IR, 1.9 mg/mL mass loading). Currents were measured by linear sweep voltammetry at a rate of 5 mV/s with 1600 rpm magnetic stirring. The dashed overlay lines show the segments for determination of the Tafel slopes.

[0020] FIG. 6 is a plot of charge vs. time resulting from a controlled potential electrolysis (CPE) experiment in a CV cell using 1.0 M Tris solution. The working electrode was a glassy carbon disk of 3 mm diameter. A counter electrode was present and produced copious amounts of O.sub.2. Using a 25 M solution of PDMAEMA-g-[2Fe-2S], over 1000 coulombs of charge were passed over 6 days at a holding voltage of 1.09 V vs SHE, yielding nearly 60,000 molecules of hydrogen per molecule of catalyst in this experiment. The limiting factor was the catalyst and not the co-catalyst.

DETAILED DESCRIPTION OF THE INVENTION

[0021] As known to one of ordinary skill in the art, electrolysis is a process of using electricity to split water into hydrogen and oxygen, as depicted schematically in FIG. 1A. In a non-limiting example of an aqueous electrochemical system, two electrodes are placed in an aqueous solution of ions. An oxidation reaction at the anode produces oxygen and protons from water, and a reduction reaction at the cathode produces hydrogen and hydroxide ions from water. For instance, a water electrolyzer may comprise an anode and a cathode connected via an external power source and immersed in a conducting electrolyte. The general process of electrolysis involves applying a current to the electrolyzer via the external power source, thereby causing the water to react at the anode to form oxygen and positively charged hydrogen ions (protons) and causing the water to react at the cathode to form molecular H.sub.2 and OH.sup.+. In some embodiments, electrons flow through external circuitry of the power source to the cathode, and the OH.sup.+ from the cathode is neutralized by the H.sup.+ from the anode to form water. In some embodiments, the system may include a membrane through which hydrogen ions selectively move to the cathode side, although this membrane is optional. As depicted schematically in FIG. 1B, a protic co-catalyst can increase the rate of the reaction by assisting the transfer of protons to the catalyst at the cathode, and avoiding the formation of hydroxide ions. The protic co-catalyst is represented in FIG. 1B as (co-catalyst-H.sup.+).

[0022] As used herein, the term co-catalyst is defined as a species that increases the rate of catalytic reduction of protons to molecular hydrogen without being consumed. For example, the co-catalysts described herein carry the protons for rapid reduction by a primary catalyst without the co-catalyst itself being consumed. In one embodiment, the protons are supplied from a corresponding oxidation side of a complete cell reaction for water splitting, where oxygen and protons are produced (the oxygen evolving reaction, OER). In some embodiments, the co-catalyst may be a buffer that stabilizes a pH. All aqueous electrochemical systems require some type of electrolyte solution in order to carry the current. The electrolyte composition may vary greatly depending on the process conditions and the type of electrolysis being conducted. In other embodiments, the co-catalyst may be also act as an electrolyte that carries the current.

[0023] As used herein, the term protic, when describing a compound such as the co-catalyst, refers to said compound having at least one H.sup.+ ion, or proton, that it can donate. In some embodiments, a protic compound may be monoprotic (capable of donating one proton), diprotic (capable of donating two protons), or polyprotic (capable of donating multiple protons).

[0024] As used herein, the protonated or protic form refers to when the co-catalyst has a proton to contribute to the HER reaction. Conversely, the deprotonated form is when this proton is dissociated from the molecule. The concentration of the protonated or protic form relative to the deprotonated form depends on the pH compared to the pK.sub.a. As a general rule, when the pH=pK.sub.a, the protonated and deprotonated forms are in equal concentration. When the pH<pK.sub.a, the solution is more acidic and excess protons will protonate the co-catalyst, therefore the concentration of the protonated form will be greater than the concentration of the deprotonated form. When the pH>pKa, the solution is more basic and the protons will dissociate from the co-catalyst, therefore the concentration of the deprotonated form will be greater than the protonated form.

[0025] In preferred embodiments, any level of protonation of the co-catalyst can help accelerate the rate of the reaction. In more preferred embodiments, the more protonated a co-catalyst, the better it is at accelerating the reaction rate. As an example, a preferred embodiment of the co-catalyst is in its majority protonated state; however, being majority protonated is not necessarily required in the present invention. For example, a phosphate buffer that is 42% protonated can still accelerate the rate of the reaction.

[0026] The present invention may be applied to any electrochemical system for the reduction of protons to hydrogen. In embodiments for standard alkaline electrolysis, for example, appropriately selected protic co-catalysts will operate in an alkaline environment.

[0027] Referring now to FIGS. 1A-6, embodiments of the present invention feature a method of increasing a hydrogen (H.sub.2) generation rate of an electrolysis process in which protons from an aqueous medium are reduced to H.sub.2. The method may comprise adding a protic co-catalyst to the aqueous medium, thereby increasing the rate of H.sub.2 generation without being consumed during the electrolysis process. Preferably, the protic co-catalyst is in a protonated state. In one embodiment, a pH of the aqueous medium and a pK.sub.a of the co-catalyst are selected such that the co-catalyst is in the protonated state. For example, the pH of the aqueous medium may be less than the pK.sub.a of the co-catalyst.

[0028] In some embodiments, the protic co-catalyst may be a pH stabilizer. In other embodiments, the protic co-catalyst can act as an electrolyte that carries a current for the electrolysis process. In still other embodiments, the protic co-catalyst can decrease an energy requirement of the electrolysis process and/or increase the current density.

[0029] According to another embodiment, the present invention features a method for improving a hydrogen (H.sub.2) generation rate of an electrolysis process where H.sub.2 is generated by reducing protons in an aqueous medium. In one embodiment, the method may comprise adding a catalyst to the aqueous medium and adding a protic co-catalyst to the aqueous medium. Preferably, the protic co-catalyst is in a protonated state. This may be achieved by selecting the pH of the aqueous medium and a pKa of the co-catalyst are selected such that the co-catalyst is in a protonated state. For instance, the pH of the aqueous medium may selected to be less than the pKa of the co-catalyst. In one preferred embodiment, the protic co-catalyst is in a majority protic state.

[0030] In some embodiments, the catalyst can reduce protons to generate H.sub.2. In preferred embodiments, the protic co-catalyst can increase the rate of H.sub.2 generation without being consumed during the electrolysis process. In other preferred embodiments, the protic co-catalyst can decrease an energy requirement of the electrolysis process and/or increase the current density. In yet other preferred embodiments, the protic co-catalyst can stabilize a pH of the aqueous solution and act as an electrolyte that carries a current for electrolysis.

[0031] In conjunction with any of the methods described above, the electrolysis process may comprise a non-liquid process, a solid state process, water splitting, ion exchange, or any process in which the delivery of protons is a mechanistic feature. The methods of the present invention may also be utilized in photocatalysis, which in some embodiments, does not necessarily need electrolysis. In one embodiment, the process may further utilize a catalyst to reduce the protons to generate H.sub.2.

[0032] In preferred embodiments, the aqueous medium may comprise water. Examples of the aqueous medium include, but are not limited to, an acid solution, an aqueous suspension, an aqueous solution, an aqueous emulsion, or membrane with water in said membrane. In some embodiments, the aqueous medium may be separated into multiple compartments by one or more membranes, or alternatively a gel. The membranes may be permeable membranes or gel membranes. In other embodiments, the aqueous medium may be a proton source from another molecule, material, or process.

[0033] According to another embodiment, the present invention may feature an electrolyzer system for generating hydrogen (H.sub.2) via an electrolysis reaction. In some embodiments, the system may comprise an anode, a cathode comprising a catalyst, an external power supply operatively coupled to the anode and cathode, a protic co-catalyst that is in a majority protonated state, and an aqueous medium. In one embodiment, the cathode may function as the catalyst. Alternatively, the cathode may comprise an electrode functioning with the catalyst.

[0034] In some embodiments, the anode and cathode may be in contact with or disposed in the aqueous medium. In other embodiments, the protic co-catalyst may be disposed in the aqueous medium. In further embodiments, the electrolyzer system may further include one or more membranes that separate the aqueous medium into multiple compartments.

[0035] In some embodiments, the external power supply may be configured to drive the electrolysis reaction by passing an electric current between the anode and cathode to effect water splitting of the aqueous medium. In one embodiment, at least a portion of the external power supply may be derived from an alternative energy source, such as solar or wind power. In one embodiment, at least a portion of the external power supply may be derived from the power grid.

[0036] In preferred embodiments, the catalyst can reduce protons from the water splitting of the aqueous medium, thus generating H.sub.2. In other preferred embodiments, the protic co-catalyst can increase a rate of H.sub.2 generation without being consumed during the electrolysis reaction. In some embodiments, the protic co-catalyst can stabilize a pH of the aqueous solution and act as an electrolyte that carries a current for electrolysis. In further embodiments, the protic co-catalyst may decrease an energy requirement of the electrolysis reaction and/or increase the current density.

[0037] In accordance with any of the methods and systems described herein, without wishing to limit the present invention to a particular theory or mechanism, the pH of the solution and pKa of the protic co-catalyst are chosen such that the concentration of the protic form of the co-catalyst is maximized. As a non-limiting example, the co-catalyst is more than 50% in the form to deliver protons (majority protic form). In some embodiments, the pH may be in a range from about 1 to 10. In one embodiment, the pH may be in a range from about 1 to 7. In another embodiment, the pH may be in a range from about 7 to 10. In other embodiments, the pKa of the co-catalyst may be in a range from about 2 to 12. In one embodiment, the pKa of the co-catalyst may be in a range from about 2 to 7. In another embodiment, the pKa of the co-catalyst may be in a range from about 7 to 12.

[0038] In some embodiments, the concentration of the co-catalyst may range from about 0.01 M to about 1 M. In one embodiment, the concentration of the co-catalyst may range from about 0.01 M to about 0.5 M. In another embodiment, the concentration of the co-catalyst may range from about 0.5 M to about 1 M. In some other embodiments, the concentration of the co-catalyst may range up to saturation, defined herein as the maximum of co-catalyst solubility.

[0039] Without wishing to limit the present invention to a particular theory or mechanism, the use of the protic co-catalyst may reduce the amount of the primary catalyst. In some embodiments, for a homogeneous catalyst, the catalyst concentration may range from about 0.1 M to about 10 M. In another embodiment, the concentration of the catalyst may range from about 10 M to about 100 M. In other embodiments, the concentration of the catalyst may range from about 100 M to about 500 M. In yet other embodiments, the concentration of the catalyst may range from about 500 M to about 1,000 M.

[0040] Examples of molecules that function as protic co-catalysts at an appropriate pH for each molecule and that may be used in accordance with any embodiment of the present invention include, but are not limited to, maleate, bicine, sodium phosphate, sodium dihydrogen phosphate, sodium carbonate, di-sodium hydrogenphosphate, glycine, glycylglycine, imidazole, citrate, triethanolamine, tricine, boric acid, ammonium acetate, magnesium acetate, potassium acetate, sodium acetate, N-(2-acetamido)-2-am inoethanesulfonic acid (ACES), N-(2-acetamido)iminodiacetic acid (ADA), taurine (AES), 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol (AMPD), N-(1,1-dimethyl-2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO), N, N-bis(2-hydroxethyl)-2-aminoethanesulfonic acid (BES), 4-(cyclohexylamino)-1-butane-sulfonic acid (CABS), N-cyclohexyl-3-aminopropanesulfonic acid (CAPS), 3-(cyclohexyl-amino)-2-hydroxy-1-propanesulfonic acid (CAPSO), N-cyclohexyl-2-aminoethane-sulfonic acid (CHES), N,N-bis(2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (DIPSO), N-(2-hydroxyethyl)piperazine-N-(4-butanesulfonic acid) (HEPBS), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), 4-(2-hydroxyethyl)piperazine-1-propanesulfonic acid (HEPPS), 4-(2-hydroxyethyl)-piperazine-1-(2-Hydroxy)-propane-sulfonic acid (HEPPSO), 4-morpholineethanesulfonate (MES), 4-(N-morpholino)butane-sulfonic acid (MOBS), 3-morpholinopropane-1-sulfonic acid (MOPS), 3-morpholino-2-hydroxy-propanesulfonic acid (MOPSO), 1,4-piperazineethanesulfonate (PIPES), piperazine-N,N-bis(2-hydroxypropanesulfonic acid) (POPSO), N-tris(hydroxymethyl)-methyl-4-aminobutanesulfonic acid (TABS), N-[tris(hydroxymethyl)methyl]-3-amino-propane-sulfonic acid (TAPS), 2-hydroxy-3-[tris(hydroxymethyl)methylamino]-1-propanesulfonic acid (TAPSO), 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-ethanesulfonic acid (TES), tris-(hydroxymethyl)-aminomethane (Tris), Bis-Tris, and Bis-Tris-Propane.

[0041] In some embodiments, examples of other co-catalysts may include polymers such as, for example, poly((N,N-dimethylaminoethyl) methacrylate) (PDMAEMA) or poly((oligoethylene glycol) methacrylate) (POEGMA) from a methylacrylate macromonomer with oligomeric ethylene glycol pendant groups as side chain. Additional embodiments of the co-catalysts may include protic polymers and macromolecular species that include, but are not limited to, other styrenic and methacrylic polymers, dendrimers, hydrogels, polypeptides, proteins, polysaccharides, cyclodextrines, micelles, amphiphilic polymers, and fibers. In some other embodiments, the co-catalyst may also carry protic donor groups to accelerate H.sub.2 formation.

[0042] Consistent with the methods and systems described herein, the catalyst may be a homogenous catalyst. In some embodiments, the catalyst is a water-soluble metallopolymer. In one embodiment, the water-soluble metallopolymer may comprise a hydrogen evolution reaction (HER) electrocatalytic complex. The HER electrocatalytic complex may be a diiron-disulfide complex [2Fe-2S].

[0043] In another embodiment, the water-soluble metallopolymer may comprise the HER electrocatalytic complex and a polymer coupled to the HER electrocatalytic complex. In some embodiments, the polymer may be derived from functional unsaturated vinyl monomers bearing non-polar and water-soluble side chain groups. Non-limiting examples of the vinyl monomers include styrenic monomers or methacrylate monomers. For instance, the polymer may be poly((N,N-dimethylaminoethyl) methacrylate) (PDMAEMA) or poly((oligoethylene glycol) methacrylate) (POEGMA) from a methylacrylate macromonomer with oligomeric ethylene glycol pendant groups as side chain. Additional examples of metallopolymeric electrocatalysts are described in PCT/US2017/065632, the specification of which is incorporated herein in its entirety by reference.

[0044] In other embodiments, the catalyst may be a heterogeneous catalyst. In one embodiment, the catalyst may be comprised of platinum. In other embodiments, the heterogeneous catalyst may be comprised of for example, but not limited to, alloys and oxides of iridium, nickel, nickel-iron, and nickel-oxide. Consistent with previous embodiments, the cathode may be further comprised of a carbon material. Examples of the carbon material include, but are not limited to, graphite, glassy carbon, or the like.

[0045] In some embodiments, the polymers may be co-catalysts by themselves and can work separately with another catalyst. In alternative embodiments, a catalyst may be incorporated into the polymer to make an all-in-one macromolecule which has both a catalyst portion and the polymer is the co-catalyst portion. For example, the macromolecule may be a metallopolymer (or other similar structures) that comprises a catalyst (from the metallo part) combined with a co-catalyst (the polymer part). The polymer part may further impart additional functionalities, such as increased solubility, to the macromolecule.

[0046] In preferred embodiments, the present invention may be applied to any technology that produces hydrogen with water as the source of the hydrogen atoms. The hydrogen molecules may be used in a variety of applications, such as internal combustion engines, fuel cells, batteries, and hydrogenation of raw materials. The present invention may also be used in electrocatalytic hydrogen reduction of chemical feedstocks. Other applications may include, but are not limited to, any splitting of molecules using an anode and cathode in an aqueous solution.

EXAMPLES

[0047] The following are non-limiting examples of the present invention. It is to be understood that said examples are provided for the purpose of demonstrating the present invention in practice, and is in no way intended to limit the invention. Equivalents or substitutes are within the scope of the invention. In particular, the present invention may be practiced with heterogeneous catalysts or homogeneous catalysts.

[0048] In one embodiment, the PDMAEMA-g-[2Fe-2S] metallopolymer (Scheme 1) was catalytically active for H.sub.2 generation at low potentials, and modest metallopolymer loadings (1.6 mg/mL in sodium phosphate adjusted to pH 7.0). In another embodiment, the current densities generated by the PDMAEMA-g-[2Fe-2S] metallopolymer were comparable to that of a Pt electrode for H.sub.2 generation in a Tris solution (FIG. 5).

##STR00001##

[0049] In another embodiment, the POEGMA-g-[2Fe-2S] metallopolymer (Scheme 2) was catalytically active for H.sub.2 generation at low potentials, and modest metallopolymer loadings with addition of the protic co-catalyst derived from Tris at pH 7. This metallopolymer had barely perceptible activity at the same potentials without the addition of Tris (FIG. 4C).

##STR00002##

[0050] Effects of Protic Co-Catalyst on Catalysis.

[0051] FIG. 2 shows cyclic voltammograms comparing HER current of a glassy carbon (GC) electrode in pH 7.0 aqueous Tris (1.0 M) without catalyst (bottom curve) and with a PDMAEMA-g-[2Fe-2S] metallopolymer catalyst in the same solution and in 1.0 M or 0.1 M sodium phosphate. Polymer mass loading was 0.19 mg/mL.

[0052] One of the key advantages of the present invention is that a plethora of inexpensive molecules for aqueous media can be adjusted to protic co-catalysts with adjustment of pH. Furthermore, modulation of co-catalyst identity and concentration can provide a facile method to improve catalytic performance without the need to increase catalyst loading. As a non-limiting example, as shown in FIG. 2, electrochemical simulations indicated current density was being limited by the concentration of the conjugate acid (i.e. NaH.sub.2PO.sub.4 in sodium phosphate) consistent with the observation of greatly increased current densities at increased co-catalyst concentration. To further increase the concentration of the protic co-catalyst, tris(hydroxymethyl)aminomethane (Tris) was used as it has a higher solubility and higher proportion of protic species at pH 7. This change in protic co-catalyst significantly increased current density without changing the reduction potential required to initiate catalysis. Such high current densities allowed for the catalyst concentrations to be lowered. It was surprisingly discovered that catalysts loadings as low as 100 nM [2Fe-2S] (0.0002% w/w) gave appreciable, and reproducible catalytic currents. The ability to increase catalytic activity by modulating an inexpensive protic co-catalyst highlights the utility of this invention.

[0053] Referring to FIG. 3, electrocatalytic CV experiments with a heterogenous planar platinum catalyst show a dependence on the concentration of the protic co-catalyst used. As with the case of homogenous HER, the current density can be significantly increased by increasing the concentration of the protic species without modification of the heterogeneous surface.

[0054] The CV comparisons between protic co-catalysts derived from 1 M sodium phosphate and 1 M Tris solution conditions in FIG. 4A-4C show increased rates of catalysis across several examples of catalysts. FIG. 4A uses Pt in a sodium phosphate aqueous system. In neutral conditions, sodium phosphate (pK.sub.a,2=7.21) has an approximate concentration of 0.40 M in the monobasic form (NaH.sub.2PO.sub.4), while Tris (pK.sub.a=8.06) exists in a concentration of 0.92 M in the protic form. The versatility to this approach is demonstrated in FIGS. 4B and 4C showing that metallopolymer systems, PDMAEMA-g-[2Fe-2S] and POEGMA-g-[2Fe-2S], also have increased rates by increasing the concentration of a protic co-catalyst. By increasing the concentration without changing the pH, the current density (related to the rate of catalysis) was increased to 104 mA cm.sup.2 (FIG. 4A), 22 mA cm.sup.2 (FIG. 4B), and 58 mA cm.sup.2 (FIG. 4C).

[0055] Linear sweep voltammetry was performed at a scan rate of 5 mV/s in a rapidly stirred solution of 1 M Tris using a planar Pt disk electrode, and in the same solution using a planar glassy carbon electrode and added PDMAEMA-g-[2Fe-2S] (0.1 mM [2Fe-2S] by IR). The experimentally determined Tafel plot is shown in FIG. 5, with the dashed line highlighting the 200 mV region used to determine the Tafel slope of each system. A Tafel slope of 124 mV/decade of current was obtained for Pt. The PDMAEMA system matches this performance almost exactly, with a Tafel slope of 122 mV/decade of current and an increased overpotential of only 0.23 V to match the current density of the Pt electrode. Extending the Tafel figure to 1 V overpotential shows that the platinum electrode and the glassy carbon electrode with 0.1 millimolar PDMAEMA catalyst converge to the same current density of about 100 mA/cm.sup.2. Furthermore, a Faradaic yield of 93% was determined by gas chromatography to confirm the currents were truly representative of HER catalysis. The same method gave a Faradaic yield of 96% for a Pt electrode, which confirms the system is operating at a Faradaic yield near unity.

[0056] Referring to FIG. 6, the CPE experiment was run at a voltage of 1.09 V vs. SHE, corresponding to an overpotential of 1.09-0.41=0.68 V at pH 7. The current density was 40 mA/cm.sup.2 or greater for 24 hours. Generation of bubbles (O.sub.2) at the counter electrode was observed in the cell during operation and in close proximity to the working electrode (which also had bubbles confirmed to be H.sub.2). The coulombs translate to generation of nearly 60,000 molecules of hydrogen per molecule of catalyst.

[0057] As used herein, the term about refers to plus or minus 10% of the referenced number.

[0058] Various modifications of the invention, in addition to those described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. Each reference cited in the present application is incorporated herein by reference in its entirety.

[0059] Although there has been shown and described the preferred embodiment of the present invention, it will be readily apparent to those skilled in the art that modifications may be made thereto which do not exceed the scope of the appended claims. Therefore, the scope of the invention is only to be limited by the following claims. Reference numbers recited in the claims are exemplary and for ease of review by the patent office only, and are not limiting in any way. In some embodiments, the figures presented in this patent application are drawn to scale, including the angles, ratios of dimensions, etc. In some embodiments, the figures are representative only and the claims are not limited by the dimensions of the figures. In some embodiments, descriptions of the inventions described herein using the phrase comprising includes embodiments that could be described as consisting of, and as such the written description requirement for claiming one or more embodiments of the present invention using the phrase consisting of is met.