US20110237830A1 - Novel catalyst mixtures - Google Patents

Novel catalyst mixtures Download PDF

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Publication number
US20110237830A1
US20110237830A1 US12/830,338 US83033810A US2011237830A1 US 20110237830 A1 US20110237830 A1 US 20110237830A1 US 83033810 A US83033810 A US 83033810A US 2011237830 A1 US2011237830 A1 US 2011237830A1
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United States
Prior art keywords
catalyst
helper
active element
helper catalyst
conversion
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US12/830,338
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Richard Isaac Masel
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Dioxide Materials Inc
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Dioxide Materials Inc
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Priority to US12/830,338 priority Critical patent/US20110237830A1/en
Priority to EP11713569.9A priority patent/EP2553147B1/en
Priority to JP2013501536A priority patent/JP2013525088A/ja
Priority to CN201180023851.2A priority patent/CN102892929B/zh
Priority to PCT/US2011/030098 priority patent/WO2011120021A1/en
Priority to AU2011230545A priority patent/AU2011230545C1/en
Priority to CA2794105A priority patent/CA2794105C/en
Priority to KR1020127027866A priority patent/KR101721287B1/ko
Priority to US13/174,365 priority patent/US9566574B2/en
Priority to BR112013000261A priority patent/BR112013000261A2/pt
Priority to JP2013518759A priority patent/JP6059140B2/ja
Priority to CN201180033161.5A priority patent/CN102971451B/zh
Priority to CA2802893A priority patent/CA2802893C/en
Priority to KR1020137002749A priority patent/KR101801659B1/ko
Priority to PCT/US2011/042809 priority patent/WO2012006240A1/en
Priority to EP11743389.6A priority patent/EP2588647A1/en
Priority to AU2011276362A priority patent/AU2011276362B2/en
Publication of US20110237830A1 publication Critical patent/US20110237830A1/en
Assigned to DIOXIDE MATERIALS, INC. reassignment DIOXIDE MATERIALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MASEL, RICHARD I.
Priority to US13/445,887 priority patent/US9012345B2/en
Priority to US13/626,873 priority patent/US8956990B2/en
Priority to US13/775,245 priority patent/US9193593B2/en
Priority to US14/035,935 priority patent/US9181625B2/en
Assigned to DIOXIDE MATERIALS, INC. reassignment DIOXIDE MATERIALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROSEN, BRIAN A., MASEL, RICHARD
Priority to US14/591,902 priority patent/US9464359B2/en
Priority to US14/592,246 priority patent/US10023967B2/en
Priority to US14/684,145 priority patent/US9555367B2/en
Priority to US14/704,934 priority patent/US9481939B2/en
Priority to US14/704,935 priority patent/US9370773B2/en
Assigned to DIOXIDE MATERIALS, INC. reassignment DIOXIDE MATERIALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MASEL, RICHARD I., ROSEN, BRIAN A.
Assigned to DIOXIDE MATERIALS, INC. reassignment DIOXIDE MATERIALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROSEN, BRIAN
Priority to US14/948,206 priority patent/US9790161B2/en
Priority to JP2015232576A priority patent/JP6254565B2/ja
Priority to US15/090,477 priority patent/US9580824B2/en
Priority to US15/158,227 priority patent/US9945040B2/en
Priority to US15/226,894 priority patent/US9957624B2/en
Priority to US15/260,213 priority patent/US10047446B2/en
Priority to JP2016238639A priority patent/JP6449839B2/ja
Priority to US15/400,712 priority patent/US9815021B2/en
Priority to US15/400,775 priority patent/US9849450B2/en
Priority to US15/724,933 priority patent/US10173169B2/en
Assigned to UNITED STATES DEPARTMENT OF ENERGY reassignment UNITED STATES DEPARTMENT OF ENERGY CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: DIOXIDE MATERIALS, INC.
Abandoned legal-status Critical Current

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    • 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
    • B01J31/0278—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
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—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
    • B01J31/0289—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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    • C—CHEMISTRY; METALLURGY
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    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
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    • C—CHEMISTRY; METALLURGY
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    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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    • G—PHYSICS
    • G01—MEASURING; TESTING
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    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/004—CO or CO2
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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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/10—Process efficiency
    • 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 formic acid.
  • an electrochemical cell contains an anode ( 50 ), a cathode ( 51 ) and an electrolyte ( 53 ) as indicated in FIG. 1 .
  • Catalysts are placed on the anode, and or cathode and or in the electrolyte to promote desired chemical reactions.
  • reactants or a solution containing reactants is fed into the cell.
  • a voltage is applied between the anode and the cathode, to promote an electrochemical reaction.
  • a reactant comprising CO 2 , carbonate or bicarbonate is fed into the cell.
  • a voltage is applied to the cell and the CO 2 reacts to form new chemical compounds. Examples of cathode reactions in The Hori Review include
  • 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, C, In, Sn, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd have all shown activity for CO 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.
  • 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 '134 patent also considers the use of salt (NaCl) as a secondary “catalyst” for CO 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 (i.e. selectivities) for catalytic reactions and high powers for sensors.
  • the catalyst mixture includes at least one Catalytically Active Element, and at least one Helper Catalyst.
  • the Catalytically Active Element and the Helper Catalyst are combined 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 (i.e. selectivity) for CO 2 conversion can be substantially increased.
  • the invention is not limited to catalysts for CO 2 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, chemical reactions in sensors.
  • the invention includes all of these examples.
  • the invention also includes processes using these catalysts.
  • FIG. 1 is a diagram of a typical electrochemical cell.
  • FIG. 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 (CO 2 ) ⁇ intermediate
  • the reaction coordinate indicates the fraction of the reaction that has completed.
  • a high potential for (CO 2 ) ⁇ formation can create a high overpotential for the reaction.
  • FIG. 3 illustrates how the potential could change when a helper catalyst is used.
  • the reaction could go through a CO 2 -EMIM complex rather than a (CO 2 ) ⁇ substantially lowering the overpotential for the reaction.
  • FIGS. 4A , 4 B and 4 C illustrate some of the cations that may be used to form a complex with (CO 2 ) ⁇
  • FIGS. 5A and 5B illustrates some of the anions that may stabilize the (CO 2 ) ⁇ anion.
  • FIG. 6 illustrates some of the neutral molecules that may be used to form a complex with (CO 2 ) ⁇
  • FIG. 7 shows a schematic of a cell used for the experiments in Examples 1, 2, 3, 4 and 5.
  • FIG. 8 shows comparison of the cyclic voltametry 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 CO 2 . Notice the large negative peak associated with CO 2 formation
  • FIG. 9 shows a series of Broad Band Sum Frequency Generation (BB-SFG) taken sequentially as the potential in the cell was scanned from +0. to ⁇ 1.2 with respect to SHE.
  • BB-SFG Broad Band Sum Frequency Generation
  • FIG. 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.
  • FIG. 11 shows a comparison of the cyclic voltametry 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 CO 2 .
  • FIG. 12 shows a comparison of the cyclic voltametry 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 CO 2 .
  • FIG. 13 shows a comparison of the cyclic voltametry 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 CO 2 .
  • FIG. 14 shows a schematic of the sensor.
  • FIG. 15 shows a schematic of where EMBF4 is placed on the sensor.
  • FIG. 16 shows 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.
  • FIG. 17 shows 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 values 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 CO 2 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.
  • 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 CO 2 .
  • 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 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 of 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 CO 2 conversion to a value less than the overpotentials seen when the same Catalytically Active Element is used without the Helper Catalyst.
  • catalysts include 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 CO 2 conversion.
  • Products include one or more of CO, OH ⁇ , HCO ⁇ , H 2 CO, (HCO 2 ) ⁇ , H 2 CO 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 , CH 4 , O 2 , H 2 (COOH) 2 , (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 are include one or more of CO, OH ⁇ , HCO ⁇ , H 2 CO, (HCO 2 ) ⁇ , H 2 CO 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 , CH 4 , O 2 , H 2 (COOH) 2 , (COO ⁇ ) 2 , but the invention is not limited to this list of products.
  • FIGS. 2 and 3 illustrate one possible mechanism by which a Helper Catalyst can enhance the rate of CO 2 conversion.
  • Chandrasekaran, et al. Surface Science, 185, 495-514, 1987
  • the high overpotentials for CO 2 conversion occur because the first step in the electroreduction of CO 2 is the formation of a (CO 2 ) intermediate. It takes energy to form the intermediate as illustrated in FIG. 2 . This results in a high overpotential for the reaction.
  • FIG. 3 illustrates what might happen if a solution containing 1-ethyl-3-methylimidazolium (EMIM + ) cations is added to the mixture.
  • EMIM + might be able to form a complex with the (CO 2 ) ⁇ intermediate. In that case, the reaction could proceed via the EMIM + -(CO 2 ) ⁇ complex instead of going through a bare (CO 2 ) ⁇ intermediate as illustrated in FIG. 3 . If the energy to form the EMIM + -(CO 2 ) ⁇ complex is less than the energy to form the (CO 2 ) ⁇ intermediate, the overpotential to for CO 2 conversion could be substantially reduced. Therefore any substance including EMIM + cations could act as a Helper Catalyst for CO 2 conversion.
  • Catalytically Active Element that can catalyze reactions of (CO 2 ) in order to get high rates of CO 2 conversion.
  • Catalysts include at least one of the following Catalytically Active Elements have been previously reported to be active for electrochemical conversion of CO 2
  • FIG. 3 could be drawn for any molecule that could form a complex with (CO 2 ) ⁇ .
  • solutions including one or more of: ionic liquids, deep eutectic solvents, amines, and phosphines, including specifically imidazoniums, pyridiniums, pyrrolidiniums, phosphoniums, ammoniums sulfoniums, prolinates, methioninates, form complexes with CO 2 . Consequently, they may serve as Helper Catalysts. Also Davis Jr, et al.
  • salts that show ionic properties. Specific examples include compounds including one or more of Acetocholines, 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.
  • helper catalyst not every substance that forms a complex with (CO 2 ) ⁇ will act as a helper catalyst.
  • Masel (Chemical Kinetics and Catalysis, Wiley 2001, p717-720), notes that when an intermediate binds to a catalyst, the reactivity of the intermediate decreases. If the intermediate bonds too strongly to the catalyst, the intermediate will become unreactive, so the substance will not be effective. This provides a key limitation on substances that act as helper catalysts.
  • the helper catalyst cannot form too strong of a bond with the (CO 2 ) ⁇ that the (CO 2 ) ⁇ is unreactive toward the Catalytically Active Element.
  • the substance to form a complex with the (CO 2 ) ⁇ so is that the complex is stable (i.e. has a negative free energy of formation) at potentials less negative than ⁇ 1 V with respect to 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.
  • Zhao, et al. (The Journal of Supercritical Fluids, 32, 287-291, 2004) examined CO 2 conversion over copper in 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) but FIG. 3 in Zhao et al shows that the BMIM-PF6 did NOT lower the overpotential for the reaction (i.e. the BMIM-PF6 did not act as a Helper Catalyst)/ This may be because the BMIM-PF6 formed such a strong bond to the (CO 2 ) ⁇ that the CO 2 was unreactive with the copper.
  • BMIM-PF6 1-n-butyl-3-methylimidazolium hexafluorophosphate
  • BMIM-Br 1-butyl-3-methylimidazolium bromide
  • Solutions consisting of one or more of the cations in FIG. 4 , the anions in FIG. 5 , the neutral species in FIG. 6 , where R1, R2 and R3 include H, OH or any ligand containing at least on carbon atom are believed to form complexes with CO 2 or (CO 2 ⁇ .
  • Specific examples include: imidazoniums, pyridiniums, pyrrolidiniums, phosphoniums, ammoniums and sulfoniums, prolinates, methioninates. All of these examples might be able to be used as Helper Catalysts for CO 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.
  • 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 ii) an electrolyte
  • iii) an additive to any component of the system iii) an additive to any component of the system
  • something that is bound to at least one of the catalysts in a system iv
  • 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)'s 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 has approximately 99.999% by weight of Helper Catalyst, and the helper catalyst can be an order of magnitude more concentrated.
  • the range of Helper Catalyst concentrations for the invention here may be 0.0000062% to 99.9999%
  • FIG. 3 only considered the electrochemical conversion of CO 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 , I 2 , NaOH, KOH, NaClO, NaClO 3 , KClO 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 vii) block side reactions.
  • 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.
  • EMIM-BF 4 1-ethyl-3-Methylimidazoilum Tetrafluoroborate
  • the cell consisted of a Three neck flask ( 101 ), to hold the anode ( 108 ), and the cathode ( 109 ).
  • 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 Fc/Fc + redox couple.
  • a conversion factor of +535 was used convert our potential axis to reference the Standard Hydrogen Electrode (SHE).
  • a 25 ⁇ 25 mm Platinum gauze (size 52) ( 113 ) was connected to the anode while a 0.33 cm 2 polycrystalline gold plug ( 115 ) was connected to the cathode.
  • a catalyst ink comprising a Catalytically Active Element platinum was first prepared as follows: First 0.0056 grams of Johnson-Matthey Hispec 1000 platinum black purchased from Alfa-Aesar was mixed with 1 grams of milipore water and sonicating for 10 minutes to produce a solution containing a 5.6 mg/ml suspension of platinum black in Millipore water. A 25 ⁇ l drop of the ink was placed on the gold plug 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, a platinum, on a gold plug. The gold plug was mounted into the three neck flask ( 101 ).
  • EMIM-BF 4 EMD chemicals
  • concentration of water in the ionic liquid after this procedure was found to be ca. 90 mM by conducting a Karl-Fischer titration. (i.e. the ionic liquid contained 99.9999% of helper catalyst) 13 grams of the EMIM-BF 4 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-BF 4
  • Next ultra-high-purity (UHP) Argon was fed through the sparging tube ( 104 ) and glass frit ( 112 ) for 2 hours at 200 sccm to further remove any moisture picked up by contact with the air.
  • the cathode was connected to the working electrode connection in a SI 1287 Solatron 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 1V vs. SHE and then back to ⁇ 1.5 volts versus SHE thirty times at a scan rate of 50 mV/s. The current produced during the last scan is labeled as the “blank” scan in FIG. 8 .
  • SHE standard hydrogen electrode
  • BB-SFG broad-band sum frequency generation
  • Tables 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 (i.e. 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 CO 2 . Notice that all of the values are more negative than ⁇ 0.9 V. By comparison, FIG. 8 shows that CO 2 conversion starts at ⁇ 0.2 V with respect to 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 Active Element, Helper Catalyst Mixtures are advantageous for CO 2 conversion.
  • FIG. 9 shows a series of BB-SFG spectra taken during the reaction. Notice the peak at 2350 cm ⁇ 1 . This peak corresponds to the formation of a stable complex between the Helper Catalyst and (CO 2 ) ⁇ . It is significant that the peak starts at ⁇ 0.1 with respect to SHE. According to The Hori Review, (CO 2 ) ⁇ is thermodynamically unstable unless the potential is more negative than ⁇ 1.2 V with respect to SHE on platinum. Yet FIG. 9 shows that the complex between EMIM-BF 4 and (CO 2 ) ⁇ is stable at ⁇ 0.1 V with respect to SHE.
  • (CO 2 ) ⁇ is the rate determining step in CO 2 conversion to CO, OH ⁇ , HCO ⁇ , H 2 CO, (HCO 2 ) ⁇ , H 2 CO 3 , CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO ⁇ , CH 3 COOH, C 2 H 6 , CH 4 , O 2 , H 2 , (COOH) 2 , (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 (CO 2 ) ⁇ is thermodynamically unstable at low potentials, which leads to a high overpotential for the reaction as indicated in FIG. 2 .
  • the data in FIG. 9 shows that one can form the EMIM-BF4-(CO 2 ) complex at low potentials.
  • the complex is thermodynamically.
  • the reaction can follow a low energy pathway for CO 2 conversion to CO, OH ⁇ , HCO ⁇ , H 2 CO, (HCO 2 ) ⁇ , H 2 CO 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 , CH 4 , O 2 , H 2 , (COOH) 2 , (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 FIG. 3 .
  • This example shows that water additions speed the formation of CO.
  • the experiment used the Cell and procedures in Example 1, with the following exception: a solution containing 98.55% EMIM-BF4 and 0.45% water was substituted for the 99.9999% EMIM-BF4 used in Example 1, the potential was held for 10 or 30 minutes at ⁇ 0.6V with respect to RHE, and then the potential was ramped positively at 50 mV/sec.
  • FIG. 10 shows the result. Notice the peak at between 1.2 and 1.5 eV. This is the peak associated with CO formation and is much larger than in example 1. Thus the addition of water has accelerated the formation of CO presumably by acting as a reactant.
  • Example 2 The experiment used the cell and procedures in Example 1, with the following exceptions: ii) A 10.3% by weight of a Helper Catalyst, choline iodide in water solution was substituted for the 1-ethyl-3-methylimidazolium tetrafluoroborate and ii) a 0.25 cm 2 Pd foil purchased from Alfa Aesar was substituted for the gold plug and platinum black on the cathode, and a silver/silver chloride reference was used.
  • FIG. 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 CO 2 on palladium in the absence of the Helper Catalyst.
  • the helper catalyst has lowered the overpotential for CO 2 formation by about 0.5 V.
  • the next example is to demonstrate that the invention can be practiced using a third Helper Catalyst, choline chloride.
  • Example 3 The experiment used the Cell and procedures in Example 3, with the following exception: a 6.5% by weight choline chloride in water solution was substituted for choline iodide solution.
  • FIG. 12 shows a comparison of the cyclic voltametry for a blank scan where i) the water-choline chloride mixture was sparged with argon and ii) a scan where the water-choline iodide mixture was sparged with CO 2 . Notice the negative going peaks starting at about ⁇ 0.6. This shows that CO 2 is being reduced at ⁇ 0.6 V.
  • Table 2 indicates that one needs to use a voltage more negative than ⁇ 1.2 V is needed to convert CO 2 on palladium in the absence of the Helper Catalyst. Thus, the overpotential for CO 2 conversion has been lowered by 0.6 V by the Helper Catalyst.
  • the next example is to demonstrate that the invention can be practiced using a third metal, nickel.
  • 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.
  • FIG. 13 shows a comparison of the cyclic voltametry 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 CO 2 . Notice the negative going peaks starting at about ⁇ 0.6. This shows that CO 2 is being reduced at ⁇ 0.6 V.
  • Table 2 indicates that one needs to use a voltage more negative than ⁇ 1.48 V is needed to convert CO 2 on nickel in the absence of the Helper Catalyst. Thus, the Helper Catalyst has lowered the overpotential for CO 2 conversion.
  • 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 indicate that carbon monoxide is the major product during CO 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 tremendiously enhanced the selectivity of the reaction toward CO and formate.
  • the sensor will be a simple electrochemical device where an in 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 no CO 2 present, the resistance will be high, but not infinite because of leakage currents. When CO 2 is present, the Active Element, Helper Catalyst Mixture may catalyze the conversion of CO 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, 500 ⁇ m thick, ⁇ 100> oriented, 1-5 ⁇ cm nominal resistivity) which was purchased with a 500 nm thermal oxide layer.
  • a substrate made from a 100 mm Silicon wafer (Silicon Quest, 500 ⁇ m thick, ⁇ 100> oriented, 1-5 ⁇ cm nominal resistivity) which was purchased with a 500 nm thermal oxide layer.
  • 170 ⁇ chromium was deposited by DC magnetron sputtering ( ⁇ 10 ⁇ 2 Ton of argon background pressure).
  • 1000 ⁇ 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 FIG. 14 .
  • the device consisted of an anode ( 200 ) and cathode ( 201 ) separated by a 6 ⁇ m gap, wherein the anode and cathode were coated with a Catalytically Active element, gold. At this point the sensor could not detect CO 2 .
  • EMIM BF 4 ( 202 ) was added over the junction as shown FIG. 15 .
  • the device was mounted into a sensor test cell with wires running from the anode and cathode.
  • the anode and cathode were connected to a SI 1287 Solatron electrical interface, and the catalysts were condition by sweeping from o volts to 5 volts at 0.1 V/sec and then back again. The process was repeated 16 times. Then the sensor was exposed to either nitrogen, oxygen, dry air or pure CO 2 , and the sweeps were recorded. The last sweep is shown in FIG. 16 . Notice that there is a sizable peak at an applied voltage of 4 volts in pure CO 2 . That peak is associated with the electrochemical conversion of CO 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 CO 2 . Further the peak grows as the CO 2 concentration increases. Thus, the sensor can be used to detect the presence of CO 2 .
  • FIG. 17 shows that less voltage is needed to maintain the current when CO 2 is added to the cell. This shows that the sensor that include an Active Element, Helper Catalyst Mixture responds to the presence of CO 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 CO 2 sensors. This is a key advantage for many applications.
  • This example also illustrates that the invention can be practiced with a third active element, gold.

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