WO2011120021A1 - Novel catalyst mixtures - Google Patents

Novel catalyst mixtures Download PDF

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Publication number
WO2011120021A1
WO2011120021A1 PCT/US2011/030098 US2011030098W WO2011120021A1 WO 2011120021 A1 WO2011120021 A1 WO 2011120021A1 US 2011030098 W US2011030098 W US 2011030098W WO 2011120021 A1 WO2011120021 A1 WO 2011120021A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
helper
reaction
active element
helper catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/US2011/030098
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English (en)
French (fr)
Inventor
Richard I. Masel
Brian Rosen
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Dioxide Materials Inc
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Dioxide Materials Inc
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Filing date
Publication date
Application filed by Dioxide Materials Inc filed Critical Dioxide Materials Inc
Priority to CN201180023851.2A priority Critical patent/CN102892929B/zh
Priority to JP2013501536A priority patent/JP2013525088A/ja
Priority to CA2794105A priority patent/CA2794105C/en
Priority to EP11713569.9A priority patent/EP2553147B1/en
Priority to KR1020127027866A priority patent/KR101721287B1/ko
Priority to AU2011230545A priority patent/AU2011230545C1/en
Priority to US13/174,365 priority patent/US9566574B2/en
Priority to JP2013518759A priority patent/JP6059140B2/ja
Priority to CN201180033161.5A priority patent/CN102971451B/zh
Priority to BR112013000261A priority patent/BR112013000261A2/pt
Priority to AU2011276362A priority patent/AU2011276362B2/en
Priority to PCT/US2011/042809 priority patent/WO2012006240A1/en
Priority to CA2802893A priority patent/CA2802893C/en
Priority to KR1020137002749A priority patent/KR101801659B1/ko
Publication of WO2011120021A1 publication Critical patent/WO2011120021A1/en
Priority to US13/445,887 priority patent/US9012345B2/en
Priority to US13/626,873 priority patent/US8956990B2/en
Anticipated expiration legal-status Critical
Priority to US14/591,902 priority patent/US9464359B2/en
Priority to US15/226,894 priority patent/US9957624B2/en
Priority to JP2016238639A priority patent/JP6449839B2/ja
Ceased legal-status Critical Current

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    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
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    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
    • B01J31/0288—Phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
    • B01J31/0289—Sulfur
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    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • G—PHYSICS
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    • G—PHYSICS
    • G01—MEASURING; TESTING
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    • G01N33/0004—Gaseous mixtures, e.g. polluted air
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    • B01J2231/60—Reduction reactions, e.g. hydrogenation
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the field of the invention is catalysis and catalysts.
  • the catalysts of this invention are applicable, for example, to the electrochemical conversion of carbon dioxide into useful products.
  • an electrochemical cell contains an anode (50), a cathode (51) and an electrolyte (53) as indicated in Figure 1. Catalysts are placed on the anode, and or cathode and or in the electrolyte to promote desired chemical reactions. During operation, reactants or a solution containing reactants is fed into the cell. Then a voltage is applied between the anode and the cathode, to promote an electrochemical reaction.
  • catalysts comprising one or more of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd have all shown activity for C0 2 conversion.
  • Reviews include Ma, et al. (Catalysis Today, 148, 221-231, 2009), Hori (Modern Aspects of Electrochemistry, 42, 89-189, 2008), Gattrell, et al. (Journal of Electroanalytical Chemistry, 594, 1-19, 2006), DuBois (Encyclopedia of Electrochemistry, 7a, 202-225, 2006) and references therein.
  • Catalyst Today Volume 48, pages 189-410 Nov 2009 provides the proceedings of the 10th international conference on C0 2 utilization. These pages are incorporated by reference.
  • the catalysts have been in the form of either bulk materials, supported particles, collections of particles, small metal ions or organometallics. Still, according to Bell (A. Bell. Ed, Basic Research Needs, Catalysis For Energy, US Department Of Energy Report PNNL17712, 2008) ("the Bell Report”), "The major obstacle preventing efficient conversion of carbon dioxide into energy-bearing products is the lack of catalyst" with sufficient activity at low overpotentials and high electron conversion efficiencies.
  • the overpotential is associated with lost energy of the process, and so one needs the overpotential to be as low as possible. Yet, according to The Bell Report "Electron conversion efficiencies of greater than 50 percent can be obtained, but at the expense of very high overpotentials". This limitation needs to be overcome before practical processes can be obtained.
  • the ⁇ 34 patent also considers the use of salt (NaCl) as a secondary "catalyst" for C0 2 reduction in the gas phase, but salt does not lower the overpotential for the reaction.
  • a second disadvantage of many of the catalysts is that they also have low electron conversion efficiency. Electron conversion efficiencies over 50% are needed for practical catalyst systems.
  • the invention provides a novel catalyst mixture that can overcome one or more of the limitations of low rates, high overpotentials and low electron conversion efficiencies (namely, selectivities) for catalytic reactions and high power for sensors.
  • the catalyst mixture includes at least one Catalytically Active Element, and at least one Helper Catalyst.
  • the rate and/or selectivity of a chemical reaction can be enhanced over the rate seen in the absence of the Helper Catalyst.
  • the overpotential for electrochemical conversion of carbon dioxide can be substantially reduced, and the current efficiency (namely, selectivity) for C02 conversion can be substantially increased.
  • the invention is not limited to catalysts for C02 conversion.
  • catalysts that include Catalytically Active Elements and Helper Catalysts might enhance the rate of a wide variety of chemical reactions.
  • Reaction types include: homogeneously catalyzed reactions, heterogeneously catalyzed reactions, chemical reactions in chemical plants, chemical reactions in power plants, chemical reactions in pollution control equipment and devices, chemical reactions in fuel cells, and chemical reactions in sensors.
  • the invention includes all of these examples.
  • the invention also includes processes using these catalysts.
  • Figure 1 is a diagram of a typical electrochemical cell.
  • Figure 2 is a schematic of how the potential of the system moves as it proceeds along the reaction coordinate in the absence of the ionic liquid if the system goes through a (C0 2 ) _ intermediate.
  • the reaction coordinate indicates the fraction of the reaction that has been completed.
  • a high potential for (C0 2 ) _ formation can create a high overpotential for the reaction.
  • Figure 3 illustrates how the potential could change when a Helper Catalyst is used.
  • the reaction could go through a C0 2 -EMIM complex rather than a (C0 2 ) _ , substantially lowering the overpotential for the reaction.
  • Figures 4a, 4b and 4c illustrate some of the cations that may be used to form a complex with (C0 2 ) _ .
  • Figures 5 a and 5b illustrate some of the anions that may help to stabilize the (C0 2 ) _ anion.
  • Figure 6 illustrates some of the neutral molecules that may be used to form a complex with (C0 2 ) _ .
  • Figure 7 shows a schematic of a cell used for the experiments in Examples 1 , 2, 3, 4, and 5.
  • Figure 8 represents a comparison of the cyclic voltammetry for a blank scan where the catalyst was synthesized as in Example 1 where (i) the EMIM-BF4 was sparged with argon, and (ii) a scan where the EMIM-BF4 was sparged with C0 2 . Notice the large negative peak associated with C0 2 complex formation.
  • Figure 9 represents a series of Broad Band Sum Frequency Generation (BB- SFG) spectra taken sequentially as the potential in the cell was scanned from +0.0 to -1.2 with respect to SHE.
  • BB- SFG Broad Band Sum Frequency Generation
  • Figure 10 shows a CO stripping experiment done by holding the potential at - 0.6 V for 10 or 30 minutes and them measuring the size of the CO stripping peak between 1.2 and 1.5 V with respect to RHE.
  • Figure 11 represents a comparison of the cyclic voltammetry for a blank scan where the catalyst was synthesized as in Example 3 where i) the water-choline iodide mixture was sparged with argon and ii) a scan where the water-choline iodide mixture was sparged with C0 2 .
  • Figure 12 shows a comparison of the cyclic voltammetry for a blank scan where the catalyst was synthesized as in Example 4 where i) the water-choline chloride mixture was sparged with argon and ii) a scan where the water-choline chloride mixture was sparged with C0 2 .
  • Figure 13 shows a comparison of the cyclic voltammetry for a blank scan where the catalyst was synthesized as in Example 5 where i) the water-choline chloride mixture was sparged with argon and ii) a scan where the water-choline chloride mixture was sparged with C0 2 .
  • Figure 14 shows a schematic of an example sensor before the Helper Catalyst was added.
  • Figure 15 shows a schematic of where EMIM BF4 is placed on the sensor.
  • Figure 16 represents the current measured when the voltage on the sensor was exposed to various gases; the applied voltage on the sensor was swept from 0 to 5 volts at 0.1 V/sec.
  • Figure 17 represents the resistance of the sensor, in nitrogen and in carbon dioxide. The resistance was determined by measuring the voltage needed to maintain a current of 1 microamp. Time is the time from when the current was applied.
  • any numerical value ranges recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least two units between any lower value and any higher value.
  • concentration of a component or value of a process variable such as, for example, size, angle size, pressure, time and the like, is, for example, from 1 to 90, specifically from 20 to 80, more specifically from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc., are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • electrochemical conversion of C02 refers to any electrochemical process where carbon dioxide, carbonate, or bicarbonate is converted into another chemical substance in any step of the process.
  • CV refers to a cyclic voltamogram or cyclic voltammetry.
  • the term "Overpotential” as used here refers to the potential (voltage) difference between a reaction's thermodynamically determined reduction or oxidation potential and the potential at which the event is experimentally observed.
  • Cathode Overpotential refers to the overpotential on the cathode of an electrochemical cell.
  • Anode Overpotential refers to the overpotential on the anode of an electrochemical cell.
  • Electrode Conversion Efficiency refers to selectivity of an electrochemical reaction. More precisely, it is defined as the fraction of the current that is supplied to the cell that goes to the production of a desired product.
  • Catalytically Active Element refers to any chemical element that can serve as a catalyst for the electrochemical conversion of C02.
  • Helper Catalyst refers to any organic molecule or mixture of organic molecules that does at least one of the following:
  • Active Element refers to any mixture that includes one or more Catalytically Active Element(s) and at least one Helper Catalyst
  • Ionic Liquid refers to salts or ionic compounds that form stable liquids at temperatures below 200°C.
  • Deep Eutectic Solvent refers to an ionic solvent that includes a mixture which forms a eutectic with a melting point lower than that of the individual components.
  • the invention relates generally to Active Element, Helper Catalyst Mixtures where the mixture does at least one of the following:
  • such mixtures can lower the overpotential for C0 2 conversion to a value less than the overpotentials seen when the same Catalytically Active Element is used without the Helper Catalyst.
  • catalysts including one or more of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd all show activity for C0 2 conversion.
  • Products include one or more of CO, OH “ , HCO , H 2 CO, (HC0 2 ) “ , H 2 0 2 , CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO , CH 3 COOH, C 2 H 6 , 0 2 , H 2 , (COOH) 2 , and (COO " ) 2 .
  • V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd are each examples of Catalytically Active Elements, but the invention is not limited to this list of chemical elements.
  • Possible products of the reaction include one or more of CO, OH “ , HCO “ , H 2 CO, (HC0 2 ) “ , H 2 C0 2 , CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO “ , CH 3 COOH, C 2 H 6 , 0 2 , H 2 , (COOH) 2 , and (COO " ) 2 , but the invention is not limited to this list of products.
  • Figures 2 and 3 illustrate one possible mechanism by which a Helper Catalyst can enhance the rate of C0 2 conversion.
  • Chandrasekaran, et al. Surface Science, 185, 495-514, 1987
  • the high overpotentials for C0 2 conversion occur because the first step in the electroreduction of C0 2 is the formation of a (C0 2 ) _ intermediate. It takes energy to form the intermediate as illustrated in Figure 2. This results in a high overpotential for the reaction.
  • FIG 3 illustrates what might happen if a solution containing l-ethyl-3- methylimidazolium (EMIM + ) cations is added to the mixture.
  • EMIM + might be able to form a complex with the (C0 2 ) _ intermediate.
  • the reaction could proceed via the EMIM + -(C0 2 ) _ complex instead of going through a bare (C0 2 ) _ intermediate as illustrated in Figure 3.
  • the overpotential for C0 2 conversion could be substantially reduced. Therefore any substance that includes EMIM + cations could act as a Helper Catalyst for C0 2 conversion.
  • Catalytically Active Element that can catalyze reactions of (C0 2 ) _ in order to get high rates of C0 2 conversion.
  • Catalysts including at least one of the following Catalytically Active Elements have been previously reported to be active for electrochemical conversion of C0 2 :
  • salts that show ionic properties. Specific examples include compounds including one or more of acetocho lines, alanines, aminoacetonitriles, methylammoniums, arginines, aspartic acids, threonines, chloroformamidiniums, thiouroniums, quinoliniums, pyrrolidinols, serinols, benzamidines, sulfamates, acetates, carbamates, triflates, and cyanides. These salts may act as helper catalysts. These examples are meant for illustrative purposes only, and are not meant to limit the scope of the invention.
  • the substance to form a complex with the (C0 2 ) _ so that the complex is stable (that is, has a negative free energy of formation) at potentials less negative than -I V with respect to the standard hydrogen electrode (SHE.)
  • the complex should not be so stable that the free energy of the reaction between the complex and the Catalytically Active Element is more positive than about 3 kcal/mol
  • BMIM-Br l-butyl-3-methylimidazolium bromide
  • Solutions that include one or more of the cations in Figure 4, the anions in Figure 5, and/or the neutral species in Figure 6, where Rl, R2 and R3 (and R4-R17) include H, OH or any ligand containing at least on carbon atom, are believed to form complexes with C0 2 or (C0 2 ) _ .
  • Specific examples include: imidazoliums (also called imidazoniums), pyridiniums, pyrrolidiniums, phosphoniums, ammoniums, sulfoniums, prolinates, and methioninates. All of these examples might be able to be used as Helper Catalysts for C0 2 conversion, and are specifically included in the invention. These examples are meant for illustrative purposes only, and are not meant to limit the scope of the invention.
  • Electrode electrochemical cell Fill a standard 3 electrode electrochemical cell with the electrolyte commonly used for reaction R.
  • Common electrolytes include such as 0.1 M sulfuric acid or 0.1 M KOH in water can also be used.
  • V2 the difference between the onset potential of the peak associated with reaction and RHE
  • the substance S is a helper catalyst for the reaction.
  • the Helper Catalyst could be in any one of the following forms: (i) a solvent for the reaction; (ii) an electrolyte; (iii) an additive to any component of the system; or (iv) something that is bound to at least one of the catalysts in a system.
  • a solvent for the reaction e.g
  • Helper Catalyst Those trained in the state of the art should recognize that one might only need a tiny amount of the Helper Catalyst to have a significant effect. Catalytic reactions often occur on distinct active sites. The active site concentration can be very low, so in principle a small amount of Helper Catalyst can have a significant effect on the rate. One can obtain an estimate of how little of the helper catalyst would be needed to change the reaction from Pease, et al, JACS 47, 1235 (1925) study of the effect of carbon monoxide (CO) on the rate of ethylene hydrogenation on copper. This paper is incorporated into this disclosure by reference.
  • CO carbon monoxide
  • Example 1 The upper limit is illustrated in Example 1 below, where the Active Element, Helper Catalyst Mixture could have approximately 99.999% by weight of Helper Catalyst, and the Helper Catalyst could be at least an order of magnitude more concentrated.
  • the range of Helper Catalyst concentrations for the invention here may be 0.0000062% to 99.9999% by weight.
  • Figure 3 only considered the electrochemical conversion of C0 2 , but the method is general.
  • energy is needed to create a key intermediate in a reaction sequence. Examples include: homogeneously catalyzed reactions, heterogeneously catalyzed reactions, chemical reactions in chemical plants, chemical reactions in power plants, chemical reactions in pollution control equipment and devices, chemical reactions in safety equipment, chemical reactions in fuel cells, and chemical reactions in sensors.
  • Theoretically if one could find a Helper Catalyst that forms a complex with a key intermediate, the rate of the reaction should increase. All of these examples are within the scope of the invention.
  • Specific examples of specific processes that may benefit with Helper Catalysts include the electrochemical process to produce products including one or more of Cl 2 , Br 2 , 1 2 , NaOH, KOH, NaCIO, NaC10 3 , KC10 3 , CF 3 COOH.
  • the Helper Catalyst could enhance the rate of a reaction even if it does not form a complex with a key intermediate.
  • Examples of possible mechanisms of action include the Helper Catalyst (i) lowering the energy to form a key intermediate by any means, (ii) donating or accepting electrons or atoms or ligands, (iii) weakening bonds or otherwise making them easier to break, (iv) stabilizing excited states, (v) stabilizing transition states, (vi) holding the reactants in close proximity or in the right configuration to react, or (vii) blocking side reactions.
  • Each of these mechanisms is described on pages 707 to 742 of Masel, Chemical Kinetics and Catalysis, Wiley, NY (2001). All of these modes of action are within the scope of the invention.
  • the invention is not limited to just the catalyst. Instead it includes any process or device that uses an Active Element, Helper Catalyst Mixture as a catalyst. Fuel cells are sensors are specifically included in the invention.
  • Helper Catalyst Mixture including platinum and 1- ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) to lower the overpotential for electrochemical conversion of C0 2 and raise the selectivity (current efficiency) of the reaction.
  • the reference electrode (103) was fitted with a Vycor® frit to prevent any of the reference electrode solution from contaminating the ionic liquid in the capillary.
  • the reference electrode was calibrated against the ferrocene Fc/Fc+ redox couple.
  • a conversion factor of +535 was used to convert our potential axis to reference the Standard Hydrogen Electrode (SHE).
  • SHE Standard Hydrogen Electrode
  • a 25x25mm platinum gauze (size 52) (113) was connected to the anode while a 0.33 cm2 polycrystalline gold plug (115) was connected to the cathode.
  • a catalyst ink comprising a Catalytically Active Element, platinum was first prepared as follows: First 0.056 grams of Johnson-Matthey Hispec 1000 platinum black purchased from Alfa-Aesar was mixed with 1 gram of Millipore water and sonicated for 10 minutes to produce a solution containing a 5.6mg/ml suspension of platinum black in Millipore water. A 25 ⁇ drop of the ink was placed on the gold plug (115) and allowed to dry under a heat lamp for 20 min, and subsequently allowed to dry in air for an additional hour. This yielded a catalyst with 0.00014 grams of Catalytically Active Element, platinum, on a gold plug. The gold plug was mounted into the three neck flask (101).
  • EMIM-BF4 EMD Chemicals, Inc., San Diego, CA, USA
  • concentration of water in the ionic liquid after this procedure was found to be ca. 90mM by conducting a Karl-Fischer titration. (That is, the ionic liquid contained 99.9999% of Helper Catalyst.) 13 grams of the EMIM-BF4 was added to the vessel, creating an Active Element, Helper Catalyst Mixture that contained about 99.999% of the Helper Catalyst.
  • the geometry was such that the gold plug formed a meniscus with the EMIM-BF4 Next ultra- high-purity (UHP) argon was fed through the sparging tube (104) and glass frit (112) for 2 hours at 200 seem to further remove any moisture picked up by contact with the air.
  • UHP ultra- high-purity
  • the cathode was connected to the working electrode connection in an SI 1287 Solartron electrical interface, the anode was connected to the counter electrode connection and the reference electrode was connected to the reference electrode connection on the Solartron. Then the potential on the cathode was swept from -1.5 V versus a standard hydrogen electrode (SHE) to IV vs. SHE, and then back to -1.5 volts versus SHE thirty times at a scan rate of 50m V/s. The current produced during the last scan is labeled as the "argon" scan in Figure 8.
  • SHE standard hydrogen electrode
  • BB-SFG broad-band sum frequency generation
  • Table 1 compares these results to results from the previous literature.
  • the table shows the actual cathode potential. More negative cathode potentials correspond to higher overpotentials. More precisely the overpotential is the difference between the thermodynamic potential for the reaction (about -0.2 V with respect to SHE) and the actual cathode potential. The values of the cathode overpotential are also given in the table. Notice that the addition of the Helper Catalyst has reduced the cathode overpotential (namely, lost work) on platinum by a factor of 4.5 and improved the selectivity to nearly 100%.
  • Table 2 indicates the cathode potential needed to convert C0 2 . Notice that all of the values are more negative than -0.9 V. By comparison, Figure 8 shows that C0 2 conversion starts at -0.2 V with respect to the reversible hydrogen electrode (RHE,) when the Active Element, Helper Catalyst Mixture is used as a catalyst. More negative cathode potentials correspond to higher overpotentials. This is further confirmation that Active Element, Helper Catalyst Mixtures are advantageous for C0 2 conversion.
  • RHE reversible hydrogen electrode
  • Figure 9 shows a series of BB-SFG spectra taken during the reaction. Notice the peak at 2350 cm-1. This peak corresponded to the formation of a stable complex between the Helper Catalyst and (C0 2 ) _ . It is significant that the peak starts at -0.1 V with respect to SHE. According to the Hori Review, (C0 2 ) _ is thermodynamically unstable unless the potential is more negative than -1.2 V with respect to SHE on platinum. Yet Figure 9 shows that the complex between EMIM-BF4 and (C0 2 ) ⁇ is stable at -0.1 V with respect to SHE.
  • (C0 2 ) ⁇ is the rate determining step in C0 2 conversion to CO, OH-, HCO-, H 2 CO, (HC0 2 )-, H 2 C0 2 , CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO , CH 3 COOH, C 2 H 6 , 0 2 , H 2 , (COOH) 2 , and (COO ⁇ ) 2 on V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd.
  • the (C0 2 ) ⁇ is thermodynamically unstable at low potentials, which leads to a high overpotential for the reaction as indicated in Figure 2.
  • the data in Figure 9 shows that one can form the EMIM- BF4-(C0 2 ) _ complex at low potentials.
  • reaction can follow a low energy pathway for C0 2 conversion to CO, OH " , HCO , H 2 CO, (HC0 2 ) ⁇ , H2 C0 2 , CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO , CH 3 COOH, C 2 H 6 , 0 2 , H 2 , (COOH) 2 , or (COO " ) 2 on V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd as indicated in Figure 3.
  • Helper Catalyst Mixture including palladium and choline iodide to C0 2 lower the overpotential for electrochemical conversion of C0 2 in water.
  • the cell contained 52 mg of palladium and 103 mg of helper catalyst, so the overall catalyst mixture contained 66% of helper catalyst.
  • Figure 11 shows a CV taken under these conditions.
  • the data in Table 2 indicates that one needs to use a voltage more negative that -1.2 V to convert C0 2 on palladium in the absence of the Helper Catalyst.
  • the Helper Catalyst has lowered the overpotential for C0 2 formation by about 0.5 V.
  • This example also demonstrates that the invention can be practiced with a second Active Element, palladium, and a second Helper Catalyst, choline iodide. Further, those trained in the state of the art will note that there is nothing special about the choice of palladium and choline iodide. Rather, this example shows that the results are general and not limited to the special case in Example 1.
  • Helper Catalyst Mixture that includes palladium and choline chloride to lower the overpotential for electrochemical conversion of C0 2 to formic acid.
  • the cell contained 52 mg of palladium and 65 mg of helper catalyst, so the overall catalyst mixture contained 51% of helper catalyst.
  • Figure 12 shows a comparison of the cyclic voltammetry for a blank scan where i) the water-choline chloride mixture was sparged with argon and ii) a scan where the water-choline chloride mixture was sparged with C0 2 . Notice the negative going peaks starting at about -0.6. This shows that C0 2 is being reduced at -0.6 V. By comparison the data in Table 2 indicates that a voltage more negative than -1.2 V is needed to convert C0 2 on palladium in the absence of the Helper Catalyst. Thus, the overpotential for C0 2 conversion has been lowered by 0.6 V by the Helper Catalyst.
  • the results should not depend on the thickness of the palladium foil. For example if we increase the thickness of the palladium foil by a factor of 10, the active element-helper catalyst mixture would only contain 11% of helper catalyst. If the foil thickness is increased to 0.5 inches, the mixture will contain about 1% of helper catalyst.
  • Helper Catalyst Mixture that includes nickel and choline chloride to lower the overpotential for electrochemical conversion of C0 2 to CO.
  • Example 4 The experiment used the Cell and procedures in Example 4, with the following exception: a nickel foil from Alfa Aesar was substituted for the palladium foil.
  • Figure 13 shows a comparison of the cyclic voltammetry for a blank scan where i) the water-choline chloride mixture was sparged with argon and ii) a scan where the water-choline chloride mixture was sparged with C0 2 . Notice the negative going peaks starting at about -0.6. This shows that C0 2 is being reduced at -0.6 V.
  • the data in Table 2 indicates that a voltage more negative than -1.48 V is needed to convert C0 2 on nickel in the absence of the Helper Catalyst. Thus, the Helper Catalyst has lowered the overpotential for C0 2 conversion.
  • the Helper Catalyst is very effective in improving the selectivity of the reaction.
  • the Hori Review reports that hydrogen is the major product during carbon dioxide reduction on nickel in aqueous solutions. The hydrolysis shows 1.4% selectivity to formic acid, and no selectivity to carbon monoxide.
  • analysis of the reaction products by CV indicates that carbon monoxide is the major product during C0 2 conversion on nickel in the presence of the Helper Catalyst. There may be some formate formation. However, no hydrogen is detected. This example shows that the Helper Catalyst has tremendously enhanced the selectivity of the reaction toward CO and formate.
  • the sensor may be a simple electrochemical device wherein an Active Element, Helper Catalyst Mixture is placed on an anode and cathode in an electrochemical device, then the resistance of the sensor is measured. If there is no C0 2 present, the resistance will be high, but preferably not infinite, because of leakage currents. When C0 2 is present, the Active Element, Helper Catalyst Mixture may catalyze the conversion of C0 2 . That allows more current to flow through the sensor. Consequently, the sensor resistance decreases. As a result, the sensor may be used to detect carbon dioxide.
  • An example sensor was fabricated on a substrate made from a 100 mm silicon wafer (Silicon Quest International, Inc., Santa Clara, CA, USA, 500 ⁇ thick, ⁇ 100> oriented, 1-5 ⁇ -cm nominal resistivity) which was purchased with a 500 nm thermal oxide layer.
  • a chromium was deposited by DC magnetron sputtering ( ⁇ 10-2 Torr of argon background pressure).
  • 1000 A of a Catalytically Active Element, gold was deposited on the chromium and the electrode was patterned via a standard lift-off photolithography process to yield the device shown schematically in Figure 14.
  • the device consisted of an anode (200) and cathode (201) separated by a 6 ⁇ gap, [Note: Figs. 14 and 15 do not include the reference numerals 200, 201, 202 or the mu symbol for ⁇ .] wherein the anode and cathode were coated with a Catalytically Active Element, gold. At this point the sensor could not detect C0 2 .
  • the peak is absent when the sensor is exposed to oxygen or nitrogen, but it is clearly seen when the sensor is exposed to air containing less than 400 ppm of C0 2 . Further the peak grows as the C0 2 concentration increases. Thus, the sensor can be used to detect the presence of C0 2 .
  • Table 4 compares the sensor here to those in the previous literature. Notice that the new sensor uses orders of magnitude less energy than commercial C0 2 sensors. This is a key advantage for many applications.

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