Use of organic cations for selective electrochemical co 2 conversion to methanol

Abstract

Disclosed is an electrode comprising a catalyst and an ionic liquid, wherein the catalyst comprises a support and a compound represented by structural formula (I). Also disclosed are methods of making the electrode, and methods of electrochemically reducing CO2, CO, or CO2 / CO mixture to methanol using the electrode.

Description

[0001] MTV-24925 USE OF ORGANIC CATIONS FOR SELECTIVE ELECTROCHEMICAL CO2CONVERSION TO METHANOL RELATED APPLICATION This application claims the benefit of priority to U.S. Provisional Patent Application No.: 63 / 638,511, filed April 25, 2024. BACKGROUND Various strategies have been proposed to mitigate the increasing concentration of CO2in the atmosphere, such as the separation, storage, and utilization of this gas.Among the available technologies, the electrochemical valorization of CO2appears to be an innovative technology, in which electrical energy is supplied to establish a potential between two electrodes, allowing CO2to be transformed into value-added chemicals under mild conditions. It provides a method to recycle CO2(in a carbon neutral cycle) and, at the same time, a way to chemically store the excess of renewable energy from intermittent sources, thus reducing dependence on fossil fuels. Among the useful products that can be obtained, methanol is particularly interesting as a platform chemical, and it has gained renewed and growing attention in the research community. Accomplishments to date in the electroreduction of CO2to methanol have been encouraging, although substantial advances are still needed for it to become a profitable technology able to shift society to renewable energy sources. SUMMARY OF THE INVENTION In some embodiments, the present disclosure relates to a system for performing a chemical or electrochemical reaction, comprising: a catalyst, wherein the catalyst mediates the chemical or electrochemical reaction; a proton donor / acceptor in contact with the catalyst; and a reaction chamber comprising the catalyst and the proton donor / acceptor, wherein the catalyst and the proton donor / acceptor cooperate to facilitate the chemical or electrochemical reaction. In some embodiments, the present disclosure relates to an electrode comprising a catalyst and an ionic liquid, wherein the catalyst comprises a support and a compound represented by structural formula (I): MTV-24925 wherein M is a transition metal; each R1, R2, R3, and R4is independently selected from the group consisting of H, halogen, CN, NO2, NR7R8, OR9, SR10, C(=O)R11, C(=O)OR12, OC(=O)R13, S(=O)R14, S(=O)2R15, NR16C(=O)R17, C(=O)NR18R19, C1-6alkyl, C3-12cycloalkyl, C6-12aryl, 4- to 10-membered heterocyclyl, and 5- to 12-membered heteroaryl, or one or more of the substituent pairs R1and R2, R2and R3, and R3and R4together with the carbon atoms to which they are attached form a C5-12carbocycle or 5- to 12-membered heterocycle; and each R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20is selected from the group consisting of H, C1-6alkyl, C3-12cycloalkyl, C6-12aryl, 4- to 10-membered heterocyclyl, and 5- to 12-membered heteroaryl. In some embodiments, the present disclosure relates to the method of making an electrode of the disclosure, comprising: a) providing a catalyst ink comprising the catalyst, the ionic liquid, and a first solvent; b) contacting an electrode substrate with the catalyst ink; thereby producing the electrode. In some embodiments, the present disclosure relates to the method of making an electrode of the disclosure, comprising: a) providing a catalyst ink comprising the catalyst and a first solvent; b) contacting an electrode substrate with the catalyst ink; thereby producing a coated electrode substrate; c) providing a solution comprising the ionic liquid and a second solvent; MTV-24925 d) contacting the coated electrode substrate with the solution, thereby producing the electrode. In some embodiments, the present disclosure relates to a method of producing methanol, comprising: a) contacting CO2, CO, or CO / CO2mixture with an electrode of the disclosure; and b) applying a voltage to the electrode. In some embodiments, the present disclosure relates to a method comprising a. providing a reaction mixture comprising carbon dioxide (CO2), an ionic liquid, and an organic cation with low pKa; b. contacting the reaction mixture with a catalyst; and c. applying a voltage to the reaction mixture in contact with the catalyst, wherein the method converts CO2to methanol. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing methanol selectivity as a function of applied potential (vs. reversible hydrogen electrode, RHE) for a CO2reduction reaction. FIG. 2 is a graph showing methanol production rate as a function of applied potential (vs. reversible hydrogen electrode, RHE) for a CO2reduction reaction. FIG. 3 shows graphs demonstrating Faradaic efficiency towards methanol (a) and methanol partial current density (b) for the pristine CoPc / CNT catalyst (gray) and the tested ionic liquids (displayed at the top). iMeOHat –0.9 VRHE(c) and –0.85 VRHE(d) as a function of the pKaof the ILs. FIG. 4 is a graph showing hydrogen partial current density for the different tested ionic liquids. FIG. 5 shows square wave voltammogram of the pristine (gray) and ionic liquid modified CoPc / CNT (a) and zoom-in on the reduction peak of the background-subtracted square wave voltammogram (b). MTV-24925 FIG. 6 shows Tafel plots for the ionic liquid modified CoPc / CNT, displaying all the measured valued (from different electrodes) independently. Comparable Tafel slopes were measured, indicating that the reaction pathway does not change upon changing the ionic liquid. FIG. 7 shows graphs demonstrating comparison in MeOH partial current densities for the [DiMIM][TFSI]-modified catalyst measured in 0.1 M KHCO3 / H2O (filled symbol) and 0.1 M KDHCO3 / D2O (empty symbol) (a) and1H NMR spectrum showing the presence of non- deuterated MeOH in the experiment performed in 0.1 M KDHCO3 / D2O (b). FIG. 8 is a plot showing Comparison of MeOH Faradaic efficiency for the [DEMA][OTf]-modified CoPc / CNT catalyst measured in the presence of different alkali cations (Li+, K+and Cs+). Measurements were performed in 0.1 M LiHCO3, KHCO3and CsHCO3, respectively, with a catalyst loading of 0.2 mg cm-2. FIG. 9 is a graph showing potentiostatic current density of [EMIM][BF4]-modified CoPc / CNT displaying a rapid deactivation with increasing [EMIM][BF4] amount (0.2, 2, 4 and 8 μL). FIG. 10 is a graph showing potentiostatic current density of the bulkier [HeMIM][BF4]- modified CoPc / CNT displaying a rapid deactivation of the catalyst becoming faster with a more negative applied potential. FIG. 11 is a graph showing Faradaic efficiency towards methanol for the pristine CoPc / CNT catalyst (gray) and the imidazole-modified one (light-blue). The imidazole molecule is displayed in the inset. FIG. 12 is a graph showing total current density and MeOH Faradaic efficiency for the [DEMA][OTf]-modified CoPc / CNT during continuous 9 hours measurement. FIG. 13 shows graphs demonstrating total and partial current density for the pristine CoPc / CNT (a) and the [DiMIM][TFSI]-modified CoPc / CNT (c) during continuous 12 hours measurement, and CV at the beginning (solid) and end (dashed) of test for CoPc / CNT (b) and [DiMIM][TFSI]-modified CoPc / CNT (d). FIG. 14 shows graphs demonstrating iMeOHof CoPc / CNT at –0.9 VRHEand –0.85 VRHEas a function of the residual H2O peak obtained from1H NMR for IL / CD3OD mixtures at different concentrations. MTV-24925 DETAILED DESCRIPTION OF THE INVENTION The electrochemical CO2reduction reaction (CO2RR) has benefitted from employing ionic liquids (ILs) as tailored electrolytes. ILs offer a versatile platform for CO2RR due to the higher CO2solubility compared to aqueous electrolytes, their ability to stabilize reaction intermediates (hence lowering the energy barrier) and their ability to alter reaction selectivity. For instance, it has been shown that the overpotential needed for conversion of CO2to CO could be significantly reduced in the presence of 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]). Since then, many studies have employed ILs to reduce the activation energy for the CO2RR and understand the underlying mechanism behind their beneficial effect. Additionally, ILs can alter the proton transfer or proton-coupled electron transfer (PT and PCET, respectively) kinetics and stabilize reaction intermediates for reactions beyond CO2RR. Cobalt phthalocyanine (CoPc) has recently drawn attention due to its capability to electrochemically reduce CO2and CO to methanol. CoPc, its derivatives, and other phthalocyanine metal complexes are described, for example, in WO2025 / 034958, which is incorporated herein by reference in its entirety. Because of its well-defined structure, it provides a model platform to understand the reaction mechanism and rationally improve catalytic activity. It has recently been determined that the protonation of adsorbed CHO as the rate determining step (RDS) for CO2-to-methanol conversion and that the hydration shell of more acidic alkali cations can enhance CO2-to-methanon kinetics via faster PCET. Since the RDS for the electrochemical CO2-to-methanol conversion is a PCET step, it was hypothesized that the organic cation of the ILs, interacting with the negatively charged electrode, can act as proton relays to facilitate proton transfer between the bulk electrolyte and the catalytic surface. By tuning the proton activity (or pKa) through different ILs, the role of local proton activity near the active sites in the kinetics of the CO2RR to maximize methanol formation can be explored. The CO2RR can be carried either in aqueous electrolytes or in organic ones, with the aqueous medium being preferred. Among organic electrolytes, ionic liquids (composed of an organic cation and an organic / inorganic anion) can be employed due to their advantages of reducing reaction overpotential, inhibiting the hydrogen evolution reaction, and improving product selectivity. Ionic liquids have also been employed as additive for both aqueous and organic electrolyte systems improving catalyst activity and selectivity. Although having been tested—mostly as electrolyte—for CO2 conversion, including CO2-to-methanol conversion, ionic MTV-24925 liquids (i.e. organic cations) have never been tested as additives to the CNT-supported CoPc catalyst for the electrochemical CO2-to-methanol conversion. The organic cations tested generally contain a nitrogen atom, but the process could be generally applicable to different types of organic cations. In some embodiments, the present disclosure relates to a method comprising selecting an IL from a library of ILs in an interfacial layer to tune the kinetics for electrochemical CO2-to- methanol conversion on a CoPc catalyst. In certain embodiments, the library of ILs comprises pyridinium trifluoromethansulfonate ([Py][OTf], pKa= 4.4), 1-ethylimidazolium bis(trifluoromethanesulfonyl)azanide, ([EIM][TFSI], pKa= 5.27), 1-methylimidazolium bis(trifluoromethanesulfonyl)azanide ([MIM][TFSI], pKa= 5.38), dimethylimidazolium bis(trifluoromethanesulfonyl)azanide ([DiMIM][TFSI], pKa= 6.31), diethylmethylammonium trifluoromethanesulfonate ([DEMA][OTf], pKa= 7.95), and 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4], pKa = 15.31). See Examples for pKacalculations. Methanol production was found to increase in the presence of the different ILs, with the rate of formation displaying a volcano trend with the pKaof the different ILs, pointing once more towards the importance of a tailored catalytic microenvironment at the electrified interface to enhance catalytic activity. In some embodiments, different organic cations (e.g. ionic liquids) can improve the catalytic outcome (activity, selectivity, and stability). The different organic cations (e.g. ionic liquids) can be added as a solution to the catalyst-coated-electrode or can be directly added in the reaction medium; organic cations (dissolved or not into a solvent) can also be added to the catalyst powder prior to ink preparation or in the ink itself. In some embodiments, organic cations with lower pKa have higher efficiency for the CO2-to-methanol conversion and require less overpotential, moreover they display higher stability. Similarly to what is observed for inorganic cations, more acidic organic cations enable facile proton transfer, which is a critical reaction step during electrochemical production of methanol, consequently improving the reaction rates. This cationic trend could be generally applicable to other types of catalysts that produce methanol from a CO2reduction reaction. Advantages and improvements When organic cations are used, CO2-to-methanol conversion rates are significantly enhanced, leading to a higher methanol selectivity at a certain applied potential. Moreover, when MTV-24925 employing organic cations with lower pKa, the required potential to start converting CO2to methanol is significantly reduced. For instance, at around –0.83 V vs. reversible hydrogen electrode (RHE), CoPc catalyst loaded on carbon nanotube (CoPc) shows 19.24% methanol selectivity for CO2conversion in 0.1 M KHCO3electrolyte (FIG. 1) and a methanol production rate of 21.07 µmol / h (FIG. 2). Meanwhile, it shows 38.3% methanol selectivity and 43.66 µmol / h methanol production rate in the presence of l-ethyl-3-methylimidazolium (EMIM) as organic cation, exhibiting a two-fold enhancement in product selectivity and production rate. Moreover, in the presence of the more acidic 1,2-dimethylimidazolium (DiMIM) cation, the catalyst shows 27.92% and 40.88% methanol selectivity for CO2conversion (corresponding to a methanol production rate of 27.66 µmol / h and 44.27 µmol / h, respectively) at –0.56 V vs. RHE and –0.69 V vs RHE, respectively, a potential window where the CoPc catalyst without the presence of organic cations does not show any methanol production at all (i.e., 0% selectivity and 0 µmol / h production rate). Comparing similar methanol selectivity (~19% for CoPc and CoPc + EMIM and ~28% for CoPc + DiMIM), ~100 mV less overpotential (that is, a lower energy input) is needed in the presence of EMIM and ~300 mV less overpotential is needed in the presence of DiMIM. This translates to ~10% and ~30% reduction in energy input at the cathode where the CO2-to- methanol conversion occurs, when EMIM or DiMIM cations are present, respectively. Commercial applications: Electrochemical CO2conversion is a highly promising technology in that it can utilize affordable renewable electricity and anthropogenic CO2captured from large-emission point sources or directly from the atmosphere to produce various value-added products such as methanol under ambient conditions (i.e., room temperature and ambient atmosphere). Furthermore, in this technology, water is conveniently used as a proton source for the CO2conversion reaction, in contrast to conventional Fischer-Tropsch process where gas-phase hydrogen (H2) is used to hydrogenate CO(g). Given large CO2emissions and high costs related to H2production / storage / transport, direct electrochemical CO2conversion can be an alternative carbon-neutral technology to conventional chemical manufacturing industry. Among the possible reaction products from the electrochemical CO2conversion, methanol is an industrially important and versatile chemical as it has wide industrial applications MTV-24925 (e.g., a liquid energy carrier, a chemical feedstock for further upgrading) with a high annual demand (>100 million metric tons per year). Since the methods disclosed herein significantly improve catalytic activity and selectivity for the CO2-to-methanol conversion and drastically reduce the overpotential needed for the reaction (i.e., energy input), they will be very attractive to companies that emit vast amounts of CO2annually and are interested in utilizing CO2captured from their industrial processes. These companies include methanol manufacturing companies that employ conventional fossil fuel- based technologies to produce methanol and are interested in decarbonizing their current methanol manufacturing process. They also include methanol- derivatives manufacturing companies that are interested in sourcing methanol from alternative green technologies. These companies also include energy-related startups who are investing in electrochemical CO2conversion technologies or are interested in utilizing clean energy technologies to replace conventional energy-intensive industrial processes. Results The catalyst comprising CoPc supported on carbon nanotubes (CoPc / CNT) was prepared following previous reports and tested in a typical H-cell for electrochemical CO2RR in a wide range of potentials. In order to probe the effect of ILs on catalytic activity, varying amounts of ILs / ethanol solutions were drop-casted onto the coated electrodes prior to the measurement. Gas and liquid products were analyzed using gas chromatography (GC) and proton nuclear magnetic resonance (1H NMR) spectroscopy, respectively. FIG. 3a and FIG. 3b show the Faradaic efficiency towards methanol (FEMeOH) and the methanol partial current density (iMeOH), respectively, for the pristine CoPc / CNT and the CoPc / CNT electrodes modified with different ILs. The different ILs clearly enhance the methanol production rate, with the three best-performing ones ([MIM][TFSI], [DiMIM][TFSI] and [DEMA][OTf]) increasing the FEMeOHand the iMeOHby ~2 and ~3 times, respectively. Earlier work showed that the interaction between the organic cation of an IL and the negatively charged electrode could suppress the hydrogen evolution reaction (HER) during CO2RR. Interestingly, [MIM][TFSI], [DiMIM][TFSI] and [DEMA][OTf] also display the highest H2production rate (FIG. 4), indicating that the reason behind the increased methanol production is not a suppressed HER but possibly a faster PCET. MTV-24925 The competitive binding between CO2and CO in the CO2-CO-MeOH cascade reaction has been previously addressed, with the former being more favorable. The *CO binding strength could be increased when using SWCNT instead of MWCNT, corresponding to an increased methanol production, and the effect has been attributed to a different electron density at the Co site (i.e., a shift in the Co(I) / Co(II) redox peak). In order to understand whether the different ILs could have an impact on the Co electron density, square-wave voltammetry (SWV) experiments were conducted on the pristine and ILs-modified CoPc / CNT catalyst (FIG. 5). SWV provided a more accurate identification of the peak position, thanks to the better sensitivity to Faradaic processes. Clearly, no shift in the redox peak could be detected, indicating an unmodified electron density around the Co active site. This is in contrast with what has been observed for a FePc catalyst, where different ILs changed the Fe electron density and shifted the Fe(II) / Fe(III) redox peak. By integrating the Co(I) / Co(II) redox peak obtained from SWV, the number of active sites and turnover frequency (TOF) for the pristine and ILs-modified CoPc / CNT were calculated. Interestingly, the best performing IL ([DEMA][OTf]) shows a reduced number of electrochemical active sites compared to the pristine catalyst (0.7410-8vs. 1.310-8), indicating paraphs a blocked access to some active sites and thus a decreased catalyst utilization. Nevertheless, in the presence of [DEMA][OTf], there is an unexpected 5x increase of the TOF at -0.9 VRHE(from 0.4 to 2 s-1), further pointing towards a faster RDS in the presence of the ILs. Furthermore, Tafel analysis (FIG. 6) indicates the same reaction mechanism independently of the presence and nature of the ILs, with all the tested samples showing a Tafel slope of ~ 70-80 mV dec-1, similarly to our previous report.17As shown in FIG.3c and FIG. 3d, the iMeOHof CoPc / CNT at –0.9 VRHEand –0.85 VRHEwas found first to increase and then decrease, exhibiting a volcano trend, as a function of the pKaof the ILs. Similarly to what has been observed for the ORR kinetics on Pt / C and Au / C, the different pKas alter the kinetics of the PCET step to the adsorbed CHO intermediate and consequently tune the overall CO2RR kinetics, showing how ILs can work as proton donors near the active sites, catalyzing the rate-limiting PCET. ILs can serve as proton donors during CO2RR when employed as solvents, with the acidity of the organic cation having a great impact on the observed CO2RR activity, but the nature of the microenvironment at the electrified interface is much more complex in ILs / water mixtures. To confirm the involvement of the proton of the ILs in the RDS during MeOH MTV-24925 production, measurements of the [DiMIM][TFSI]-modified CoPc / CNT catalyst using 0.1 M KDCO3in D2O were performed. In this experiment, if the proton of the IL is transferred during the RDS, some non-deuterated methanol (CH3OH) should be observed besides the deuterated one (CD3OD). This is indeed the case, and both CH3OH and CD3OD were observed (FIG. 7). Furthermore, this experiment was used to evaluate the kinetic isotope effect (KIE). A KIE of ~ 3.5 was observed, which is not surprising since a H+is involved in the RDS. Interestingly, this KIE is lower compared to the pristine CoPc / CNT in 0.1 LiHCO3, possibly indicating a different proton donor (the IL) or a different H-bonding network. This picture is further confirmed when measuring the IL-modified CoPc / CNT in different electrolytes (LiHCO3, KHCO3and CsHCO3; FIG. 8). Changing the nature of the alkali cation does not affect the MeOH production, indicating that the hydration shell of the different cations is less important compared to the ILs and its hydration shell. The importance of the H-bonding network around the ILs is further confirmed by control experiments where a larger amount of the hydrophobic [EMIM][BF4] or bulkier IL such as [HeMIM][BF4] are employed (FIGs. 9 and 10, respectively). In both cases, a fast deactivation of the catalyst is observed, which is exacerbated when going to more negative potentials (i.e., faster reaction rate), possibly because of the absence of water molecules around the ILs to replenish the consumed H+. Moreover, when employing a neutral molecule such as imidazole, no beneficial effect on MeOH production is observed (FIG.11), indicating that positively charged species are essential in order to interact with the negatively charged electrode surface. After demonstrating how ILs with different pKacan alter the hydrogen-bond structures and solvation environments at the electrified interface, impacting the kinetics of the PCET- relevant step, the stability of the ILs-modified CoPc / CNT catalyst was explored. It has been recently shown that formaldehyde, an intermediate generated during the CO2RR, when present in its oxygen-down configuration can inhibit its further reduction, poisoning the cobalt active site and causing the deactivation of the catalyst. Similarly, the pristine CoPc / CNT shows a decay in activity during continuous 12 hours of electrolysis at –0.9 VRHE, with the HER becoming more predominant compared to the CO2RR, and the catalyst not displaying the Co(I) / Co(II) redox peaks at the end of the measurement (FIG.12). On the other hand, the [DiMIM][TFSI]-modified catalyst, even though still displaying a certain decay during continuous 12 hours of electrolysis at –0.9 VRHE, shows more stable performance, with the Co(I) / Co(II) redox peaks still present at the MTV-24925 end of the measurement, indicating that the catalyst is still electrochemically active (FIG 12). Similarly, the [DEMA][OTf]-modified catalyst is able to maintain a FEMeOH> 30% over 9 hours at –0.9 VRHE(FIG. 13), demonstrating that the higher methanol production stemming from the presence of the ILs is not accompanied by a stability tradeoff, but the ILs seem to even increase the stability of the CoPc / CNT catalyst. In order to be economically viable, electrochemical CO2-to-methanol conversion needs to be carried out at industrially relevant current densities (e.g., >100 mA / cm2). Due to the limited solubility of CO2into water-based electrolytes in H-cells, high current densities can be achieved only when using gas-phase CO2in flow-type cells. Recently, arecord-high CO2-to-methanol conversion has been demonstrated in a flow cell with tetraamine-substituted CoPc (CoPc-NH2) supported on carbon nanotubes (CNTs). CoPc-NH2 / CNT was chosen due to its better stability compared to CoPc / CNT and showed a FEMeOH≃ 50% and an iMeOH≃ 130 mA cm-2at a total current density of 300 mA cm-2, corresponding to an iMeOHmass activity of ~ 108 A g-1at a total current of 250 A g-1(1.2 mg cm-2catalyst loading). Here, the pristine and IL-modified CoPc- NH2 / CNT in a flow cell setup at a total current density of ~ 100 mA cm-2. The pristine CoPc- NH2 / CNT showed only a FEMeOH≃ 7% and an iMeOH≃ 7 mA cm-2. On the other hand, the [DiMIM][TFSI]-modified catalyst could reach an unexpected FEMeOH≃ 28% and an iMeOH≃ 45 mA cm-2at the same total current density. Considering the loading of 0.4 mg cm-2that was employed, this corresponds to an unexpectedly high mass activity of ~ 114 A g-1at a total current of 250 A g-1. As disclosed herein, the CO2RR activity of CoPc / CNT displays a volcano relationship with the pKaof ionic liquids, which serve as proton donor. Tuning the catalytic microenvironment by manipulating non-covalent interactions at the electrified interface could enhance catalytic performance by accelerating the rate-limiting PCET, drastically improving methanol production in the electrochemical CO2-to-methanol conversion. In some embodiments, the present disclosure relates to a system for performing a chemical or electrochemical reaction, comprising: a catalyst, wherein the catalyst mediates the chemical or electrochemical reaction; a proton donor / acceptor in contact with the catalyst; and a reaction chamber comprising the catalyst and the proton donor / acceptor, wherein the catalyst and the proton donor / acceptor cooperate to facilitate the chemical or electrochemical reaction. MTV-24925 In some embodiments, the proton donor / acceptor is selected from the group consisting of an ionic liquid, a salt containing an organic cation, a salt containing an organic anion, a mineral acid, an organic acid, an amphiprotic solvent, a buffer, an amine-containing molecule, a polymeric proton donor / acceptor, and a solid state proton donor / acceptor. In some embodiments, the proton donor / acceptor is phenol / phenoxide. Phenol's acidity is due to resonance stabilization of the phenoxide ion. In some embodiments, the proton donor / acceptor is ammonium ion / ammonia. Ammonium ion is commonly used as a weak acid in buffer systems. In some embodiments, the proton donor / acceptor is amine / conjugate acid of amine. Conjugate acids of amines often have pKa around 9–11. In some embodiments, the proton donor / acceptor is phosphoric acid derivative / phosphate. Phosphoric acid derivatives are important in biochemistry (e.g., DNA, ATP). In some embodiments, the proton donor / acceptor is a β-dicarbonyl compound / conjugate anion. β-Dicarbonyl compounds like acetoacetic acid have acidic hydrogens due to keto-enol tautomerism. In some embodiments, the proton donor is selected from the group consisting of phenol(C₆H₅OH) (pKa ~10.0), ammonium ion (NH₄⁺)(pKa ~9.25), anilinium ion (C₆H₅NH₃⁺)(pKa~4.6), imidazolium ion (pKa ~6.95), 2,4-pentanedione (acetylacetone) (pKa ~9.0–9.5), acetoacetic acid (pKa ~9.6–10.7), diethyl malonate (pKa ~10.6), hydrogen phosphate (H₂PO₄⁻) (pKa ~7.2 and ~12.3), and thiophenol (C₆H₅SH) (pKa ~6.5–7). In some embodiments, the present disclosure relates to an electrode comprising a catalyst and an ionic liquid, wherein the catalyst comprises a support and a compound represented by structural formula (I):

[0002] MTV-24925 wherein M is a transition metal; each R1, R2, R3, and R4is independently selected from the group consisting of H, halogen, CN, NO2, NR7R8, OR9, SR10, C(=O)R11, C(=O)OR12, OC(=O)R13, S(=O)R14, S(=O)2R15, NR16C(=O)R17, C(=O)NR18R19, C1-6alkyl, C3-12cycloalkyl, C6-12aryl, 4- to 10-membered heterocyclyl, and 5- to 12-membered heteroaryl, or one or more of the substituent pairs R1and R2, R2and R3, and R3and R4together with the carbon atoms to which they are attached form a C5-12carbocycle or 5- to 12-membered heterocycle; and each R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20is selected from the group consisting of H, C1-6alkyl, C3-12cycloalkyl, C6-12aryl, 4- to 10-membered heterocyclyl, and 5- to 12-membered heteroaryl. In some embodiments, M is selected from the group consisting of Co, Fe, Ni, Mn, Cu, Zn, Zr, Ag, Cr, Ti, V, Nb, Mo, W, Ru, Os, Pd, Pt, Au, Al, Si, Ge, Sn, Pb, Bi, La, Nd, Lu, Y, Hf, Rh, Ir, and Ce. In some embodiments M is Co. In some embodiments, each R1, R2, R3, and R4is independently selected from the group consisting of H, F, Cl, NO2, CN, NH2, CH3, t-Bu, C(=O)H, and C(=O)OH. In some embodiments, each R1, R2, R3, and R4is H. In some embodiments, M is Co; and each R1, R2, R3, and R4is H. In some embodiments, each R1, R3, and R4is H; and each R2is NH2. In some embodiments, M is Co; each R1, R3, and R4is H; and each R2is NH2. MTV-24925 In some embodiments, the support comprises an allotrope of carbon, an oxide, a transition-metal nitride, a transition-metal carbide, a transition-metal sulfide, a metal–organic framework, a covalent organic framework, a metal, or a polymer. In some embodiments, the support comprises carbon black, graphene, or carbon nanotubes. In some embodiments, the support comprises single-walled carbon nanotubes or multi- walled carbon nanotubes. In some embodiments, the support is multi-walled carbon nanotubes. In some embodiments, the ionic liquid comprises a nitrogen-comprising cation. In some embodiments, the nitrogen containing cation is selected from the group consisting of diethylmethylammonium (DEMA), dimethylimidazolium (DiMIM), 1- ethylimidazolium (EIM), pyridinium (Py), 1-methylimidazolium (MIM), 1-ethyl-3- methylimidazolium (EMIM), 1-butyl-3-methylimidazolium (BMIM), 1-butyl-3- ethylimidazolium, triethylammonium, ethyldimethylammonium, dipropylmethylammonium, tetrabutylammonium, trioctylmethylammonium, N-butylpyridinium, 1-butyl-4- methylpyridinium, 1-butyl-1-methylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, 1-butyl-1- methylpiperidinium, 1-methyl-1-propylpiperidinium, and 1-ethyl-1-methylmorpholinium.In some embodiments, In some embodiments, the nitrogen containing cation is selected from the group consisting of DEMA, DiMIM, EIM, Py, MIM, and EMIM. In some embodiments, the nitrogen containing cation is selected from the group consisting of DEMA, DiMIM, and MIM. In some embodiments, the nitrogen containing cation is DEMA. In some embodiments, the pKa of the ionic liquid is about 1 to about 30. In some embodiments, the pKa of the ionic liquid is about 4 to about 10. In some embodiments, the pKa of the ionic liquid is about 5 to about 9. In some embodiments, the pKa of the ionic liquid is about 7 and to 8. In some embodiments, the ionic liquid comprises an anion selected from the group consisting of trifluoromethanesulfonate (OTf), bis(trifluoromethanesulfonyl)azanide (TFSI), tetrafluoroborate (BF4), hexafluorophosphate (PF6), trifluoroacetate, tris(pentafluoroethyl)trifluorophosphate, dicyanamide, thiocyanate, acetate, nitrate, chloride, MTV-24925 bromide, iodide, hydrogen sulfate, formate, methanesulfonate, p-toluenesulfonate, and bis(fluorosulfonyl)imide. In some embodiments, the ionic liquid comprises an anion selected from the group consisting of OTf, TFSI, and BF4. In some embodiments, the ionic liquid is selected from the group consisting of [DEMA][OTf], [DiMIM][TFSI], [EIM][TFSI], [Py][OTf], [MIM][TFSI], and [EMIM][BF4]. In some embodiments, the ionic liquid is [DEMA][OTf]. In some embodiments, the present disclosure relates to the method of making an electrode of the disclosure, comprising: a) providing a catalyst ink comprising the catalyst, the ionic liquid, and a first solvent; b) contacting an electrode substrate with the catalyst ink; thereby producing the electrode. In some embodiments, the present disclosure relates to the method of making an electrode of the disclosure, comprising: a) providing a catalyst ink comprising the catalyst and a first solvent; b) contacting an electrode substrate with the catalyst ink; thereby producing a coated electrode substrate; c) providing a solution comprising the ionic liquid and a second solvent; d) contacting the coated electrode substrate with the solution, thereby producing the electrode. In some embodiments, the first solvent comprises an alcohol. In some embodiments, the first solvent comprises ethanol. In some embodiments, the catalyst ink further comprises polyfluorosulfonic acid, e.g., Nafion. In some embodiments, the second solvent comprises an alcohol. In some embodiments, the second solvent is ethanol. In some embodiments, contacting the electrode substrate with the catalyst ink comprises drop casting the catalyst ink on the electrode substrate. In some embodiments, contacting the coated electrode substrate with the solution comprises drop casting the solution on the coated electrode substrate. In some embodiments, the present disclosure relates to a method of producing methanol, comprising: MTV-24925 a) contacting CO2, CO, or CO / CO2mixture with an electrode of the disclosure; and b) applying a voltage to the electrode. In some embodiments, contacting CO2, CO, or CO / CO2mixture with an electrode comprises contacting gaseous CO2, gaseous CO, or gaseous CO / CO2mixture with the electrode. In some embodiments, contacting CO2, CO, or CO / CO2mixture with an electrode comprises contacting an aqueous solution comprising CO2, an aqueous solution comprising CO, or an aqueous solution comprising CO and CO2with the electrode. In some embodiments, the aqueous solution comprising CO2, the aqueous solution comprising CO, or the aqueous solution comprising CO and CO2comprises an electrolyte. In some embodiments, the electrolyte is selected from the group consisting of LiHCO3, NaHCO3, KHCO3, CsHCO3, Be(HCO3)2, Mg(HCO3)2, Ca(HCO3)2, and Ba(HCO3)2. In some embodiments, the electrolyte is KHCO3. In some embodiments, the method has methanol Faradaic efficiency of about 10% to about 100% at a total current density of about 10 mA cm-2to about 1000 mA cm-2. In some embodiments, the method has methanol Faradaic efficiency of about 10% to about 50% at a total current density of about 100 mA cm-2. In some embodiments, the method has methanol Faradaic efficiency of about 20% to about 40% at a total current density of about 100 mA cm-2. In some embodiments, the method has methanol Faradaic efficiency of about 30% at a total current density of about 100 mA cm-2. In some embodiments, the method has methanol Faradaic efficiency of about 10% to about 50% after about 1 to about 100 hours of applying voltage of about –0.9V vs. reversible hydrogen electrode (VRHE) to the cathode or about 2V to 4V full cell voltage. In some embodiments, the method has methanol Faradaic efficiency of about 20% to about 40% after about 9 hours of applying voltage of about –0.9 VRHE. In some embodiments, the method has turnover frequency (TOF) of about 1 s-1to about 5 s-1at the voltage of about –0.9 VRHE. In some embodiments, the method has TOF of about 2 s-1at the voltage of about –0.9 VRHE. One aspect of the disclosure herein is a method, comprising: MTV-24925 a. providing a reaction mixture comprising carbon dioxide (CO2), an ionic liquid, and an organic cation with low pKa; b. contacting the reaction mixture with a catalyst; and c. applying a voltage to the reaction mixture in contact with the catalyst; d. wherein the method converts CO2to methanol. In one embodiment of the disclosed method, the catalyst comprises a cobalt phthalocyanine (CoPc) catalyst. In one embodiment of the disclosed method, the catalyst comprises a carbon nanotube-supported CoPc catalyst. In one embodiment of the disclosed method, the voltage is applied through a reversible hydrogen electrode (RHE). In one embodiment of the disclosed method, the ionic liquid comprises 0.1 M KHCO3electrolyte. In one embodiment of the disclosed method, the organic cation comprises diethylmethylamine (DEMA). In one embodiment of the disclosed method, the organic cation comprises l-ethyl-3- methylimidazolium (EMIM). In one embodiment of the disclosed method, the organic cation comprises 1,2- dimethylimidazolium (DiMIM) cation. In one embodiment of the disclosed method, the applied voltage is around-0.83 V vs. RHE. In one embodiment of the disclosed method, the applied voltage is around - 0.69 V vs. RHE. In one embodiment of the disclosed method, the applied voltage is around - 0.56 V vs. RHE. Definitions Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings that are commonly understood by those of ordinary skill in the art. Generally, nomenclature used in connection with, and techniques of chemistry described herein, are those well known and commonly used in the art. MTV-24925 The methods and techniques of the present disclosure are generally performed, unless otherwise indicated, according to conventional methods well known in the art and as described in various general and more specific references that are cited and discussed throughout this specification. See, e.g. “Principles of Neural Science”, McGraw-Hill Medical, New York, N.Y. (2000). Chemistry terms used herein, unless otherwise defined herein, are used according to conventional usage in the art, as exemplified by “The McGraw-Hill Dictionary of Chemical Terms”, Parker S., Ed., McGraw-Hill, San Francisco, C.A. (1985). All of the above, and any other publications, patents and published patent applications referred to in this application are specifically incorporated by reference herein. In case of conflict, the present specification, including its specific definitions, will control. As used herein, the terms “optional” or “optionally” mean that the subsequently described event or circumstance may occur or may not occur, and that the description includes instances where the event or circumstance occurs as well as instances in which it does not. For example, “optionally substituted alkyl” refers to the alkyl may be substituted as well as where the alkyl is not substituted. It is understood that substituents and substitution patterns on the compounds of the present invention can be selected by one of ordinary skilled person in the art to result chemically stable compounds which can be readily synthesized by techniques known in the art, as well as those methods set forth below, from readily available starting materials. If a substituent is itself substituted with more than one group, it is understood that these multiple groups may be on the same carbon or on different carbons, so long as a stable structure results. As used herein, the term “optionally substituted” refers to the replacement of one to six hydrogen radicals in a given structure with the radical of a specified substituent including, but not limited to: hydroxyl, hydroxyalkyl, alkoxy, halogen, alkyl, nitro, silyl, acyl, acyloxy, aryl, cycloalkyl, heterocyclyl, amino, aminoalkyl, cyano, haloalkyl, haloalkoxy, -OCO-CH2-O-alkyl, - OP(O)(O-alkyl)2or –CH2-OP(O)(O-alkyl)2. Preferably, “optionally substituted” refers to the replacement of one to four hydrogen radicals in a given structure with the substituents mentioned above. More preferably, one to three hydrogen radicals are replaced by the substituents as mentioned above. It is understood that the substituent can be further substituted. MTV-24925 The term “acyl” is art-recognized and refers to a group represented by the general formula hydrocarbylC(O)-, preferably alkylC(O)-. The term “acylamino” is art-recognized and refers to an amino group substituted with an acyl group and may be represented, for example, by the formula hydrocarbylC(O)NH-. The term “acyloxy” is art-recognized and refers to a group represented by the general formula hydrocarbylC(O)O-, preferably alkylC(O)O-. The term “alkoxy” refers to an alkyl group having an oxygen attached thereto. Representative alkoxy groups include methoxy, ethoxy, propoxy, tert-butoxy and the like. The term “alkoxyalkyl” refers to an alkyl group substituted with an alkoxy group and may be represented by the general formula alkyl-O-alkyl. The term “alkyl” refers to saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups. In preferred embodiments, a straight chain or branched chain alkyl has 30 or fewer carbon atoms in its backbone (e.g., C1-30for straight chains, C3-30for branched chains), and more preferably 20 or fewer. Moreover, the term “alkyl” as used throughout the specification, examples, and claims is intended to include both unsubstituted and substituted alkyl groups, the latter of which refers to alkyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone, including haloalkyl groups such as trifluoromethyl and 2,2,2-trifluoroethyl, etc. The term “alkylamino”, as used herein, refers to an amino group substituted with at least one alkyl group. The term “alkylthio”, as used herein, refers to a thiol group substituted with an alkyl group and may be represented by the general formula alkylS-. The term “amido”, as used herein, refers to a group , wherein R9and R10each independently represent a hydrogen or hydrocarbyl group, or R9and R10taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure. MTV-24925 The terms “amine” and “amino” are art-recognized and refer to both unsubstituted and substituted amines and salts thereof, e.g., a moiety that can be represented by , wherein R9, R10, and R10’ each independently represent a hydrogen or a hydrocarbyl group, or R9and R10taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure. The term “aminoalkyl”, as used herein, refers to an alkyl group substituted with an amino group. The term “aralkyl”, as used herein, refers to an alkyl group substituted with an aryl group. The term “aryl” as used herein include substituted or unsubstituted single-ring aromatic groups in which each atom of the ring is carbon. Preferably the ring is a 5- to 7-membered ring, more preferably a 6-membered ring. The term “aryl” also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is aromatic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and / or heterocyclyls. Aryl groups include benzene, naphthalene, phenanthrene, phenol, aniline, and the like. The term “carbamate” is art-recognized and refers to a group , wherein R9and R10independently represent hydrogen or a hydrocarbyl group. The term “carbocyclylalkyl”, as used herein, refers to an alkyl group substituted with a carbocycle group. The term “carbocycle” includes 5-7 membered monocyclic and 8-12 membered bicyclic rings. Each ring of a bicyclic carbocycle may be selected from saturated, unsaturated and aromatic rings. Carbocycle includes bicyclic molecules in which one, two or three or more atoms are shared between the two rings. The term “fused carbocycle” refers to a bicyclic carbocycle in which each of the rings shares two adjacent atoms with the other ring. Each ring of a fused carbocycle may be selected from saturated, unsaturated and aromatic rings. In an exemplary embodiment, an aromatic ring, e.g., phenyl, may be fused to a saturated or unsaturated ring, e.g., cyclohexane, cyclopentane, MTV-24925 or cyclohexene. Any combination of saturated, unsaturated and aromatic bicyclic rings, as valence permits, is included in the definition of carbocyclic. Exemplary “carbocycles” include cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, 1,5-cyclooctadiene, 1,2,3,4- tetrahydronaphthalene, bicyclo[4.2.0]oct-3-ene, naphthalene and adamantane. Exemplary fused carbocycles include decalin, naphthalene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]octane, 4,5,6,7-tetrahydro-1H-indene and bicyclo[4.1.0]hept-3-ene. “Carbocycles” may be substituted at any one or more positions capable of bearing a hydrogen atom. The term “carbocyclylalkyl”, as used herein, refers to an alkyl group substituted with a carbocycle group. The term “carbonate” is art-recognized and refers to a group -OCO2-. The term “carboxy”, as used herein, refers to a group represented by the formula -CO2H. The term “cycloalkyl” includes substituted or unsubstituted non-aromatic single ring structures, preferably 4- to 8-membered rings, more preferably 4- to 6-membered rings. The term “cycloalkyl” also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is cycloalkyl and the substituent (e.g., R100) is attached to the cycloalkyl ring, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and / or heterocyclyls. Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, denzodioxane, tetrahydroquinoline, and the like. The term “ester”, as used herein, refers to a group -C(O)OR9wherein R9represents a hydrocarbyl group. The term “ether”, as used herein, refers to a hydrocarbyl group linked through an oxygen to another hydrocarbyl group. Accordingly, an ether substituent of a hydrocarbyl group may be hydrocarbyl-O-. Ethers may be either symmetrical or unsymmetrical. Examples of ethers include, but are not limited to, heterocycle-O-heterocycle and aryl-O-heterocycle. Ethers include “alkoxyalkyl” groups, which may be represented by the general formula alkyl-O-alkyl. The terms “halo” and “halogen” as used herein means halogen and includes chloro, fluoro, bromo, and iodo. The terms “hetaralkyl” and “heteroaralkyl”, as used herein, refers to an alkyl group substituted with a hetaryl group. MTV-24925 The terms “heteroaryl” and “hetaryl” include substituted or unsubstituted aromatic single ring structures, preferably 5- to 7-membered rings, more preferably 5- to 6-membered rings, whose ring structures include at least one heteroatom, preferably one to four heteroatoms, more preferably one or two heteroatoms. The terms “heteroaryl” and “hetaryl” also include polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is heteroaromatic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and / or heterocyclyls. Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine, and the like. The term “heteroatom” as used herein means an atom of any element other than carbon or hydrogen. Preferred heteroatoms are nitrogen, oxygen, and sulfur. The term “heterocyclylalkyl”, as used herein, refers to an alkyl group substituted with a heterocycle group. The terms “heterocyclyl”, “heterocycle”, and “heterocyclic” refer to substituted or unsubstituted non-aromatic ring structures, preferably 3- to 10-membered rings, more preferably 3- to 7-membered rings, whose ring structures include at least one heteroatom, preferably one to four heteroatoms, more preferably one or two heteroatoms. The terms “heterocyclyl” and “heterocyclic” also include polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is heterocyclic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and / or heterocyclyls. Heterocyclyl groups include, for example, piperidine, piperazine, pyrrolidine, morpholine, lactones, lactams, and the like. The term “hydrocarbyl”, as used herein, refers to a group that is bonded through a carbon atom that does not have a =O or =S substituent, and typically has at least one carbon-hydrogen bond and a primarily carbon backbone, but may optionally include heteroatoms. Thus, groups like methyl, ethoxyethyl, 2-pyridyl, and even trifluoromethyl are considered to be hydrocarbyl for the purposes of this application, but substituents such as acetyl (which has a =O substituent on the linking carbon) and ethoxy (which is linked through oxygen, not carbon) are not. Hydrocarbyl groups include, but are not limited to aryl, heteroaryl, carbocycle, heterocycle, alkyl, alkenyl, alkynyl, and combinations thereof. MTV-24925 The term “hydroxyalkyl”, as used herein, refers to an alkyl group substituted with a hydroxy group. The term “lower” when used in conjunction with a chemical moiety, such as, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant to include groups where there are ten or fewer atoms in the substituent, preferably six or fewer. A “lower alkyl”, for example, refers to an alkyl group that contains ten or fewer carbon atoms, preferably six or fewer. In certain embodiments, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy substituents defined herein are respectively lower acyl, lower acyloxy, lower alkyl, lower alkenyl, lower alkynyl, or lower alkoxy, whether they appear alone or in combination with other substituents, such as in the recitations hydroxyalkyl and aralkyl (in which case, for example, the atoms within the aryl group are not counted when counting the carbon atoms in the alkyl substituent). The terms “polycyclyl”, “polycycle”, and “polycyclic” refer to two or more rings (e.g., cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and / or heterocyclyls) in which two or more atoms are common to two adjoining rings, e.g., the rings are “fused rings”. Each of the rings of the polycycle can be substituted or unsubstituted. In certain embodiments, each ring of the polycycle contains from 3 to 10 atoms in the ring, preferably from 5 to 7. The term “sulfate” is art-recognized and refers to the group –OSO3H, or a pharmaceutically acceptable salt thereof. The term “sulfonamido” is art-recognized and refers to the group represented by the general formulae , wherein R9and R10independently represents hydrogen or hydrocarbyl. The term “sulfoxide” is art-recognized and refers to the group–S(O)-. The term “sulfonate” is art-recognized and refers to the group SO3H, or a pharmaceutically acceptable salt thereof. The term “sulfone” is art-recognized and refers to the group –S(O)2-. The term “substituted” refers to moieties having substituents replacing a hydrogen on one or more carbons of the backbone. It will be understood that “substitution” or “substituted with” includes the implicit proviso that such substitution is in accordance with permitted valence of the MTV-24925 substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this invention, the heteroatoms such as nitrogen may have hydrogen substituents and / or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. Substituents can include any substituents described herein, for example, a halogen, a hydroxyl, a carbonyl (such as a carboxyl, an alkoxycarbonyl, a formyl, or an acyl), a thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), an alkoxyl, a phosphoryl, a phosphate, a phosphonate, a phosphinate, an amino, an amido, an amidine, an imine, a cyano, a nitro, an azido, a sulfhydryl, an alkylthio, a sulfate, a sulfonate, a sulfamoyl, a sulfonamido, a sulfonyl, a heterocyclyl, an aralkyl, or an aromatic or heteroaromatic moiety. It will be understood by those skilled in the art that the moieties substituted on the hydrocarbon chain can themselves be substituted, if appropriate. The term “thioalkyl”, as used herein, refers to an alkyl group substituted with a thiol group. The term “thioester”, as used herein, refers to a group -C(O)SR9or –SC(O)R9wherein R9represents a hydrocarbyl. The term “thioether”, as used herein, is equivalent to an ether, wherein the oxygen is replaced with a sulfur. The term “urea” is art-recognized and may be represented by the general formula ,wherein R9and R10independently represent hydrogen or a hydrocarbyl. EXAMPLES The invention now being generally described, it will be more readily understood by reference to the following examples which are included merely for purposes of illustration of MTV-24925 certain aspects and embodiments of the present invention and are not intended to limit the invention. Ionic liquids Diethylmethylammonium trifluoromethanesulfonate ([DEMA][OTf]), dimethylimidazolium bis(trifluoromethanesulfonyl)azanide ([DiMIM][TFSI]), 1- ethylimidazolium bis(trifluoromethanesulfonyl)azanide ([EIM][TFSI]), pyridinium trifluoromethansulfonate ([Py][OTf]), 1-methylimidazolium bis(trifluoromethanesulfonyl)azanide ([MIM][TFSI]), and 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) were purchased from Iolitec and used as-received without further modifications. Computed pKavalues were obtained similarly to previous reports. To confirm the trend obtained from the calculations, an experiment was performed to evaluate the dependency of the H-bonding network strength from the proton activity (or pKa) of the different ILs. Different IL / CD3OD mixtures were prepared and1H NMR was performed to measure the shift of the residual H2O peak, which was found to shift differently depending on the acidity of the different ILs. Deuterated methanol (CD3OD) was employed instead of D2O due to the limited solubility of ILs in water and experiments were performed at different ILs concentrations. As shown in FIG. 14, for all the different ILs concentrations, the iMeOHof CoPc / CNT at -0.9 VRHEand –0.85 VRHEwas found first to increase and then decrease, exhibiting a volcano trend, as a function of the residual H2O peak (or different H-bonding network strength, i.e. the pKaof the ILs). Product quantification Gas products were analyzed by using an on-line gas chromatograph (GC, SRI Instruments, 8610C) with a thermal conductivity detector and a flame ionization detector. Gas samples were injected into the GC every 20 minutes and averaged values over 1 hour of measurements are reported. Liquid products were analyzed by proton nuclear magnetic resonance (1H NMR, Bruker Avance Neo 500) with water suppression. Dimethylsulfoxide (DMSO) with a known concentration was typically used as an internal standard. Faradaic efficiency (FE) of a product MTV-24925 was calculated by dividing the amount of charge consumed to produce each product by the total charge passed during CO2RR. Example 1. Catalyst preparation Cobalt phthalocyanine supported on carbon nanotubes (CoPc / CNT) was prepared following previous literature reports with some modifications. As-received multi-walled CNTs (>98% carbon basis, Sigma-Aldrich) were calcined at 500 °C for 1 hour under ambient atmosphere. The calcined CNTs were then sonicated for 30 minutes in 5 wt.% HCl solution and stirred overnight. The obtained purified CNTs were washed multiple times with deionized water until neutral pH was reached. 1.5 mg of CoPc (Thermo Fisher Scientific) was dispersed in 10 ml of dimethylformamide (DMF, HPLC grade, ≥99.9%, Sigma-Aldrich), while 30 mg of purified CNTs were dispersed in 20 ml of DMF. Both solutions were sonicated for 30 minutes and afterwards mixed. The resulting mixture was sonicated for another 30 minutes, stirred for 24 hours and centrifuged. The precipitate was washed several times with DMF and ethanol and dried overnight. Example 2. Electrode Preparation Catalyst ink was prepared dispersing 8 mg of CoPc / CNT in 2 ml of absolute ethanol and 24 µL of Nafion solution (5 wt.%, Sigma-Aldrich). The ink was sonicated for at least 2 hours in order to obtain a good dispersion. Electrodes were prepared by drop casting 100 µL of catalyst ink onto a carbon paper (Sigracet 29AA, Fuel Cell Store) with 1 cm2geometric active area, obtaining a catalyst loading of 0.4 mg cm-2. Ionic liquids (ILs) dispersions were prepared by mixing a certain amount of IL into a certain volume of absolute ethanol followed by sonication and ILs-modified electrodes were obtained by drop casting a certain amount of ILs dispersion onto the catalyst-coated electrode. For example, in order to prepare an electrode coated with 4 µL of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4), 40 µL of EMIM-BF4were added to 560 µL of absolute ethanol and sonicated for few minutes. 60 µL of the obtained EMIM-BF4solution were then drop casted onto the CoPc / CNT coated electrode. MTV-24925 Example 3. Electrochemical testing Electrochemical measurements were conducted in a commercially available H-cell (Dek Research) where two compartments were separated by an anion exchange membrane (Selemion, DSVN, Bellex International Corp.). Platinum foil was used as a counter electrode and an Ag / AgCl 3M KCl was used as reference electrode. 0.1 M KHCO3electrolyte for CO2RR was prepared by purging 0.05 M K2CO3(prepared by dissolving the carbonate salt, 99.997%, Thermo Fisher Scientific, in deionized water, 18.2 MΩ·cm, Milli-Q Direct Water Purification System) with CO2gas (Airgas, Research Grade) overnight and pH was measured (~6.8). Prior to each measurement, the electrolyte was saturated with CO2, and the gas flow was kept at 20 sccm (standard cubic centimeters per minute) with continuous stirring during CO2RR. Potentiostatic experiments were performed typically for 65 minutes, and cathode potentials were converted to the reversible hydrogen electrode (RHE) scale using the following equation: ERHE= EAg / AgCl 3 M KCl+ 0.210 + 0.0591 × pH. Solution resistance was measured at the end of each testing and the iR drop was manually compensated. INCORPORATION BY REFERENCE All publications and patents mentioned herein are hereby incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of conflict, the present application, including any definitions herein, will control. EQUIVALENTS While specific embodiments of the subject invention have been discussed, the above specification is illustrative and not restrictive. Many variations of the invention will become apparent to those skilled in the art upon review of this specification and the claims below. The full scope of the invention should be determined by reference to the claims, along with their full scope of equivalents, and the specification, along with such variations.

Claims

MTV-24925 CLAIMS We claim:

1. A system for performing a chemical or electrochemical reaction, comprising: a catalyst, wherein the catalyst mediates the chemical or electrochemical reaction; a proton donor / acceptor in contact with the catalyst; and a reaction chamber comprising the catalyst and the proton donor / acceptor, wherein the catalyst and the proton donor / acceptor cooperate to facilitate the chemical or electrochemical reaction.

2. The system of claim 1, wherein the proton donor / acceptor is selected from the group consisting of an ionic liquid, a salt containing an organic cation, a salt containing an organic anion, a mineral acid, an organic acid, an amphiprotic solvent, a buffer, an amine-containing molecule, a polymeric proton donor / acceptor, and a solid state proton donor / acceptor.

3. An electrode comprising a catalyst and an ionic liquid, wherein the catalyst comprises a support and a compound represented by structural formula (I):wherein M is a transition metal; each R1, R2, R3, and R4is independently selected from the group consisting of H, halogen, CN, NO2, NR7R8, OR9, SR10, C(=O)R11, C(=O)OR12, OC(=O)R13, S(=O)R14, S(=O)2R15,MTV-24925 NR16C(=O)R17, C(=O)NR18R19, C1-6alkyl, C3-12cycloalkyl, C6-12aryl, 4- to 10-membered heterocyclyl, and 5- to 12-membered heteroaryl, or one or more of the substituent pairs R1and R2, R2and R3, and R3and R4together with the carbon atoms to which they are attached form a C5-12carbocycle or 5- to 12-membered heterocycle; and each R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, and R20is selected from the group consisting of H, C1-6alkyl, C3-12cycloalkyl, C6-12aryl, 4- to 10-membered heterocyclyl, and 5- to 12-membered heteroaryl.

4. The electrode of claim 3, wherein M is selected from the group consisting of Co, Fe, Ni, Mn, Cu, Zn, Zr, Ag, Cr, Ti, V, Nb, Mo, W, Ru, Os, Pd, Pt, Au, Al, Si, Ge, Sn, Pb, Bi, La, Nd, Lu, Y, Hf, Rh, Ir, and Ce.

5. The electrode of claim 4, wherein M is Co.

6. The electrode of any one of claims 3-5, wherein each R1, R2, R3, and R4is independently selected from the group consisting of H, F, Cl, NO2, CN, NH2, CH3, t-Bu, C(O)H, and C(O)OH.

7. The electrode of claim 6, wherein each R1, R2, R3, and R4is H.

8. The electrode of claim 7, wherein M is Co; and each R1, R2, R3, and R4is H.

9. The electrode of claim 6, wherein each R1, R3, and R4is H; and each R2is NH2.

10. The electrode of claim 9, wherein M is Co; each R1, R3, and R4is H; and each R2is NH2.

11. The electrode of any one of claims 3-10, wherein the support comprises an allotrope of carbon, an oxide, a transition-metal nitride, a transition-metal carbide, a transition-metal sulfide, a metal–organic framework, a covalent organic framework, a metal, or a polymer.MTV-24925 12. The electrode of any one of claims 1-10, wherein the support comprises carbon black, graphene, or carbon nanotubes.

13. The electrode of claim 12, wherein the support comprises single-walled carbon nanotubes or multi-walled carbon nanotubes.

14. The electrode of claim 13, wherein the support is multi-walled carbon nanotubes.

15. The electrode of any one of claims 1-14, wherein the ionic liquid comprises a nitrogen- containing cation.

16. The electrode of claim 15, wherein the nitrogen containing cation is selected from the group consisting of diethylmethylammonium (DEMA), dimethylimidazolium (DiMIM), 1- ethylimidazolium (EIM), pyridinium (Py), 1-methylimidazolium (MIM), 1-ethyl-3- methylimidazolium (EMIM), 1-butyl-3-methylimidazolium (BMIM), 1-butyl-3- ethylimidazolium, triethylammonium, ethyldimethylammonium, dipropylmethylammonium, tetrabutylammonium, trioctylmethylammonium, N-butylpyridinium, 1-butyl-4- methylpyridinium, 1-butyl-1-methylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, 1-butyl-1- methylpiperidinium, 1-methyl-1-propylpiperidinium, and 1-ethyl-1-methylmorpholinium.

17. The electrode of claim 16, wherein the nitrogen containing cation is selected from the group consisting of DEMA, DiMIM, EIM, Py, MIM, and EMIM.

18. The electrode of claim 17, wherein the nitrogen containing cation is selected from the group consisting of DEMA, DiMIM, and MIM.

19. The electrode of claim 18, wherein the nitrogen containing cation is DEMA.

20. The electrode of any one of claims 3-19, wherein the pKa of the ionic liquid is about 1 to about 30.

21. The electrode of claim 20, wherein the pKa of the ionic liquid is about 4 to about 10.MTV-24925 22. The electrode of claim 21, wherein the pKa of the ionic liquid is about 5 to about 9.

23. The electrode of claim 22, wherein the pKa of the ionic liquid is about 7 and to 8.

24. The electrode of any one of claims 3-23, wherein the ionic liquid comprises an anion selected from the group consisting of trifluoromethanesulfonate (OTf), bis(trifluoromethanesulfonyl)azanide (TFSI), tetrafluoroborate (BF4), hexafluorophosphate (PF6), trifluoroacetate, tris(pentafluoroethyl)trifluorophosphate, dicyanamide, thiocyanate, acetate, nitrate, chloride, bromide, iodide, hydrogen sulfate, formate, methanesulfonate, p- toluenesulfonate, and bis(fluorosulfonyl)imide.

25. The electrode of claim 24, wherein the ionic liquid comprises an anion selected from the group consisting of OTf, TFSI, and BF4.

26. The electrode of any one of claims 3-25, wherein the ionic liquid is selected from the group consisting of [DEMA][OTf], [DiMIM][TFSI], [EIM][TFSI], [Py][OTf], [MIM][TFSI], and [EMIM][BF4].

27. The electrode of claim 26, wherein the ionic liquid is selected from the group consisting of [DEMA][OTf], [DiMIM][TFSI], and [MIM][TFSI].

28. The electrode of claim 27, wherein the ionic liquid is [DEMA][OTf].

29. A method of making an electrode of any one of claims 3-28, comprising: a) providing a catalyst ink comprising the catalyst, the ionic liquid, and a first solvent; b) contacting an electrode substrate with the catalyst ink; thereby producing the electrode.

30. A method of making an electrode of any one of claims 3-28, comprising: a) providing a catalyst ink comprising the catalyst and a first solvent; b) contacting an electrode substrate with the catalyst ink; thereby producing a coated electrode substrate; c) providing a solution comprising the ionic liquid and a second solvent;MTV-24925 d) contacting the coated electrode substrate with the solution, thereby producing the electrode.

31. The method of claim 29 or 30, wherein the first solvent comprises an alcohol.

32. The method of claim 31, wherein the first solvent comprises ethanol.

33. The method of any one of claims 29-32, wherein the catalyst ink further comprises polyfluorosulfonic acid.

34. The method of any one of claims 30-33, wherein the second solvent comprises an alcohol.

35. The method of claim 34, wherein the second solvent is ethanol.

36. The method of any one of claims 29-35, wherein contacting the electrode substrate with the catalyst ink comprises drop casting the catalyst ink on the electrode substrate.

37. The method of any one of claims 30-36, wherein contacting the coated electrode substrate with the solution comprises drop casting the solution on the coated electrode substrate.

38. A method of producing methanol, comprising: a) contacting a CO2, CO, or CO / CO2mixture with an electrode of any one of claims 3-28; and b) applying a voltage to the electrode.

39. The method of claim 38, wherein contacting the CO2, CO, or CO / CO2mixture with an electrode comprises contacting a gaseous CO2, gaseous CO, or gaseous CO / CO2mixture with the electrode.MTV-24925 40. The method of claim 38, wherein contacting CO2, CO, or CO / CO2mixture with an electrode comprises contacting an aqueous solution comprising CO2, an aqueous solution comprising CO, or an aqueous solution comprising CO and CO2with the electrode.

41. The method of claim 40, wherein the aqueous solution comprising CO2, the aqueous solution comprising CO, or the aqueous solution comprising CO and CO2comprises an electrolyte.

42. The method of claim 41, wherein the electrolyte is selected from the group consisting of LiHCO3, NaHCO3, KHCO3, CsHCO3, Be(HCO3)2, Mg(HCO3)2, Ca(HCO3)2, and Ba(HCO3)2.

43. The method of claim 42, wherein the electrolyte is KHCO3.

44. The method of any one of claims 38-43, wherein the method has methanol Faradaic efficiency of about 10% to about 100% at a total current density of about 10 mA cm-2to about 1000 mA cm-2.

45. The method of claim 44, wherein the method has methanol Faradaic efficiency of about 10% to about 50% at a total current density of about 100 mA cm-2.

46. The method of claim 45, wherein the method has methanol Faradaic efficiency of about 20% to about 40% at a total current density of about 100 mA cm-2.

47. The method of claim 46, wherein the method has methanol Faradaic efficiency of about 30% at a total current density of about 100 mA cm-2.

48. The method of any one of claims 38-47, wherein the method has methanol Faradaic efficiency of about 10% to about 50% after about 1 to about 100 hours of applying voltage of about –0.9V vs. reversible hydrogen electrode (VRHE) to the cathode or about 2V to 4V full cell voltage.MTV-24925 49. The method of claim 48, wherein the method has methanol Faradaic efficiency of about 10% to about 50% after about 5 to about 10 hours of applying voltage of about –0.9V vs. reversible hydrogen electrode (VRHE).

50. The method of claim 49, wherein the method has methanol Faradaic efficiency of about 20% to about 40% after about 9 hours of applying voltage of about –0.9 VRHE.

51. The method of any one of claims 38-50, wherein the method has turnover frequency (TOF) of about 1 s-1to about 5 s-1at the voltage of about –0.9 VRHE.

52. The method of claim 51, wherein the method has TOF of about 2 s-1at the voltage of about –0.9 VRHE.

53. A method, comprising a. providing a reaction mixture comprising carbon dioxide (CO2), an ionic liquid, and an organic cation with low pKa; b. contacting the reaction mixture with a catalyst; and c. applying a voltage to the reaction mixture in contact with the catalyst, wherein the method converts CO2to methanol.

54. The method of claim 53, wherein the catalyst comprises a cobalt phthalocyanine (CoPc) catalyst.

55. The method of claim 54, wherein the catalyst comprises a carbon nanotube-supported CoPc catalyst.

56. The method of any one of claims 53-55, wherein the voltage is applied through a reversible hydrogen electrode (RHE).

57. The method of any one of claims 53-56, wherein the ionic liquid comprises 0.1 M KHCO3 electrolyte.MTV-24925 58. The method of any one of claims 53-57, wherein the organic cation comprises diethylmethylamine (DEMA).

59. The method of any one of claims 53-57, wherein the organic cation comprises l-ethyl- 3-methylimidazolium (EMIM).

60. The method of any one of claims 53-57, wherein the organic cation comprises 1,2- dimethylimidazolium (DiMIM) cation.

61. The method of claim 58, wherein the applied voltage is about –0.75 to –0.65 VRHE.

62. The method of claim 59, wherein the applied voltage is about –0.90 to –0.75 VRHE.

63. The method of claim 60, wherein the applied voltage is about –0.90 to –0.55 VRHE.

64. The method of any one of claims 53-60, wherein the applied voltage is less than about – 0.83 VRHE.

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