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Title: Electrocatalytic process for carbon dioxide conversion

An electrocatalytic process for carbon dioxide conversion includes combining a Catalytically Active Element and Helper Catalyst in the presence of carbon dioxide, allowing a reaction to proceed to produce a reaction product, and applying electrical energy to said reaction to achieve electrochemical conversion of said reactant to said reaction product. The Catalytically Active Element can be a metal in the form of supported or unsupported particles or flakes with an average size between 0.6 nm and 100 nm. the reaction products comprise at least one of CO, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, (COOH).sub.2, (COO.sup.-).sub.2, and CF.sub.3COOH.
Inventors:
;
Issue Date:
OSTI Identifier:
1342106
Assignee:
Dioxide Materials, Inc. CHO
Patent Number(s):
9,555,367
Application Number:
14/684,145
Contract Number:
SC0004453
Resource Relation:
Patent File Date: 2015 Apr 10
Research Org:
Dioxide Materials, Inc. Boca Raton, FL (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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  • Journal of the American Chemical Society, Vol. 51, Issue 11, p. 3286-3290
  • DOI: 10.1021/ja01386a016

The electrolytic reduction of carbon dioxide to formic acid
journal, September 1971

The influence of platinum crystallite size on the electrochemical reduction of oxygen in phosphoric acid
journal, June 1978

Electrocatalytic reduction of carbon dioxide by using macrocycles of nickel and cobalt
journal, September 1980
  • Fisher, Barbara J.; Eisenberg, Richard
  • Journal of the American Chemical Society, Vol. 102, Issue 24, p. 7361-7363
  • DOI: 10.1021/ja00544a035

Formose sugars from formaldehyde
journal, September 1981

Voltammetry of carbon dioxide: Part I. A general survey of voltammetry at different electrode materials in different solvents
journal, June 1983
  • Eggins, Brian R.; McNeill, Joanne
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 148, Issue 1, p. 17-24
  • DOI: 10.1016/S0022-0728(83)80127-2

Development and Commercialization of the Monsanto Electrochemical Adiponitrile Process
journal, January 1984
  • Danly, D. E.
  • Journal of The Electrochemical Society, Vol. 131, Issue 10, p. 435C-442C
  • DOI: 10.1149/1.2115324

The effect of quaternary ammonium salts on the anodic oxidation of ethanol
journal, February 1985

Selective Formation of Formic Acid, Oxalic Acid, and Carbon Monoxide by Electrochemical Reduction of Carbon Dioxide
journal, July 1987
  • Ikeda, Shoichiro; Takagi, Takehiko; Ito, Kaname
  • Bulletin of the Chemical Society of Japan, Vol. 60, Issue 7, p. 2517-2522
  • DOI: 10.1246/bcsj.60.2517

In-situ spectroscopic investigation of adsorbed intermediate radicals in electrochemical reactions: CO2 on platinum
journal, July 1987

The electrochemical reduction of CO2 to CH4 and C2H4 at Cu/Nafion electrodes (solid polymer electrolyte structures)
journal, January 1988
  • Dewulf, David W.; Bard, Allen J.
  • Catalysis Letters, Vol. 1, Issue 1-3, p. 73-79
  • DOI: 10.1007/BF00765357

Electrochemical and Surface Studies of Carbon Dioxide Reduction to Methane and Ethylene at Copper Electrodes in Aqueous Solutions
journal, January 1989
  • DeWulf, David W.
  • Journal of The Electrochemical Society, Vol. 136, Issue 6, p. 1686-1691
  • DOI: 10.1149/1.2096993

Particle Size Effects for Oxygen Reduction on Highly Dispersed Platinum in Acid Electrolytes
journal, January 1990
  • Kinoshita, K.
  • Journal of The Electrochemical Society, Vol. 137, Issue 3, p. 845-848
  • DOI: 10.1149/1.2086566

Electrochemical Reduction of Carbon Dioxide on Various Metal Electrodes in Low-Temperature Aqueous KHCO3 Media
journal, January 1990
  • Azuma, Masashi; Hashimoto, Kazuhito; Hiramoto, Masahiro
  • Journal of The Electrochemical Society, Vol. 137, Issue 6, p. 1772-1778
  • DOI: 10.1149/1.2086796

Isolation of Nucleic Acids Using Silica-Gel Based Membranes: Methods Based on the Use of QIAamp Spin Columns
book, January 1997

Electrochemical Reduction of Carbon Dioxide at Various Metal Electrodes in Aqueous Potassium Hydrogen Carbonate Solution
journal, September 1990
  • Noda, Hidetomo; Ikeda, Shoichiro; Oda, Yoshiyuki
  • Bulletin of the Chemical Society of Japan, Vol. 63, Issue 9, p. 2459-2462
  • DOI: 10.1246/bcsj.63.2459

Electrochemical evidence of intermediate formation of adsorbed CO in cathodic reduction of CO2 at a nickel electrode
journal, November 1990

Electrochemical reduction of carbon dioxide catalyzed by [Pd(triphosphine)(solvent)](BF4)2 complexes: synthetic and mechanistic studies
journal, November 1991
  • DuBois, Daniel L.; Miedaner, Alex; Haltiwanger, R. Curtis
  • Journal of the American Chemical Society, Vol. 113, Issue 23, p. 8753-8764
  • DOI: 10.1021/ja00023a023

Activation of carbon dioxide: nickel-catalyzed electrochemical carboxylation of diynes
journal, April 1993
  • Derien, Sylvie; Clinet, Jean Claude; Dunach, Elisabet
  • The Journal of Organic Chemistry, Vol. 58, Issue 9, p. 2578-2588
  • DOI: 10.1021/jo00061a038

A new homogeneous electrocatalyst for the reduction of carbon dioxide to methanol at low overpotential
journal, July 1994
  • Seshadri, Gayatri; Lin, Chao; Bocarsly, Andrew B.
  • Journal of Electroanalytical Chemistry, Vol. 372, Issue 1-2, p. 145-150
  • DOI: 10.1016/0022-0728(94)03300-5

Particle size effect for oxygen reduction and methanol oxidation on Pt/C inside a proton exchange membrane
journal, August 1994
  • Kabbabi, A.; Gloaguen, F.; Andolfatto, F.
  • Journal of Electroanalytical Chemistry, Vol. 373, Issue 1-2, p. 251-254
  • DOI: 10.1016/0022-0728(94)03503-2

Work functions of metal clusters
journal, December 1994
  • Meiwes-Broer, K. H.
  • Hyperfine Interactions, Vol. 89, Issue 1, p. 263-269
  • DOI: 10.1007/BF02064511

Electrochemical Reduction of Liquid CO2: Drastic Enhancement of Current Density
journal, January 1994
  • Saeki, Tomonori
  • Journal of The Electrochemical Society, Vol. 141, Issue 9, p. L130-L132
  • DOI: 10.1149/1.2055178

Electroreduction of carbon dioxide on palladium electrodes at potentials higher than the reversible hydrogen potential
journal, August 1994
  • Podlovchenko, B. I.; Kolyadko, E. A.; Lu, Shigan
  • Journal of Electroanalytical Chemistry, Vol. 373, Issue 1-2, p. 185-187
  • DOI: 10.1016/0022-0728(94)03324-2

Influence of substituted benzaldehydes and their derivatives as inhibitors for hydrogen evolution in lead/acid batteries
journal, February 1995

Two routes to formaldehyde from formic acid on TiO2(001) surfaces
journal, March 1996

Improved yields of oxalate, glyoxylate and glycolate from the electrochemical reduction of carbon dioxide in methanol
journal, January 1997
  • Eggins, B. R.; Ennis, C.; McConnell, R.
  • Journal of Applied Electrochemistry, Vol. 27, Issue 6, p. 706-712
  • DOI: 10.1023/A:1018444022321

High performance RuPd catalysts for CO2 reduction at gas-diffusion electrodes
journal, June 1997
  • Furuya, Nagakazu; Yamazaki, Tsuyoshi; Shibata, Masami
  • Journal of Electroanalytical Chemistry, Vol. 431, Issue 1, p. 39-41
  • DOI: 10.1016/S0022-0728(97)00159-9

Electrochemical reduction of CO2 on single crystal electrodes of silver Ag(111), Ag(100) and Ag(110)
journal, December 1997
  • Hoshi, Nagahiro; Kato, Makiko; Hori, Yoshio
  • Journal of Electroanalytical Chemistry, Vol. 440, Issue 1-2, p. 283-286
  • DOI: 10.1016/S0022-0728(97)00447-6

Reduction of carbon dioxide on ruthenium oxide and modified ruthenium oxide electrodes in 0.5 M NaHCO3
journal, January 1997
  • Popić, J. P.; Avramov-Ivić, M. L.; Vuković, N. B.
  • Journal of Electroanalytical Chemistry, Vol. 421, Issue 1-2, p. 105-110
  • DOI: 10.1016/S0022-0728(96)04823-1

Structure of Chemisorbed Sulfur on a Pt(111) Electrode
journal, January 1997
  • Sung, Y.-E.; Chrzanowski, W.; Zolfaghari, A.
  • Journal of the American Chemical Society, Vol. 119, Issue 1, p. 194-200
  • DOI: 10.1021/ja962637h

Electrochemical conversion of carbon dioxide to formic acid on Pb in KOH/methanol electrolyte at ambient temperature and pressure
journal, December 1998

Effect of surface order on adsorption of sulfate ions on silver electrodes
journal, January 1998
  • Smoliński, Sławomir; Zelenay, Piotr; Sobkowski, Jerzy
  • Journal of Electroanalytical Chemistry, Vol. 442, Issue 1-2, p. 41-47
  • DOI: 10.1016/S0022-0728(97)00469-5

Effect of additives in zinc alloy powder on suppressing hydrogen evolution
journal, July 1998

Electrochemical reduction of carbon dioxide to ethylene with high Faradaic efficiency at a Cu electrode in CsOH/methanol
journal, September 1999

Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis
journal, August 1999
  • Welton, Thomas
  • Chemical Reviews, Vol. 99, Issue 8, p. 2071-2084
  • DOI: 10.1021/cr980032t

Electrochemical reduction of carbon dioxide at a series of platinum single crystal electrodes
journal, August 2000

Palladium-Catalyzed Reppe Carbonylation
journal, November 2001
  • Kiss, Gabor
  • Chemical Reviews, Vol. 101, Issue 11, p. 3435-3456
  • DOI: 10.1021/cr010328q

Electrochemical reduction of CO2 at copper single crystal Cu(S)-[n(111)×(111)] and Cu(S)-[n(110)×(100)] electrodes
journal, September 2002
  • Takahashi, Ichiro; Koga, Osamu; Hoshi, Nagahiro
  • Journal of Electroanalytical Chemistry, Vol. 533, Issue 1-2, p. 135-143
  • DOI: 10.1016/S0022-0728(02)01081-1

Effects of process conditions and electrode material on reaction pathways for carbon dioxide electroreduction with particular reference to formate formation
journal, December 2003

Model approach to evaluate particle size effects in electrocatalysis: preparation and properties of Pt nanoparticles supported on GC and HOPG
journal, November 2003

Commercially Available Salts as Building Blocks for New Ionic Liquids
book, August 2003
  • Davis, James H.; Fox, Phillip A.; Rogers, Robin D.
  • Ionic Liquids as Green Solvents: Progress and Prospects, p. 100-107
  • DOI: 10.1021/bk-2003-0856.ch009

Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes
journal, May 2003

Electrochemical reduction of carbon dioxide on kinked stepped surfaces of platinum inside the stereographic triangle
journal, January 2003

Role of surface defect sites: from Pt model surfaces to shape-controlled nanoparticles
journal, January 2012
  • Chen, Qing-Song; Vidal-Iglesias, Francisco J.; Solla-Gullón, José
  • Chemical Science, Vol. 3, Issue 1, p. 136-147
  • DOI: 10.1039/C1SC00503K

Comparison of Oxygen Reduction Reaction at Silver Nanoparticles and Polycrystalline Silver Electrodes in Alkaline Solution
journal, May 2012
  • Singh, Poonam; Buttry, Daniel A.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 19, p. 10656-10663
  • DOI: 10.1021/jp301676n

Carboxylation of Terminal Alkynes with Carbon Dioxide Catalyzed by Poly(N-Heterocyclic Carbene)-Supported Silver Nanoparticles
journal, April 2012
  • Yu, Dingyi; Tan, Mei Xuan; Zhang, Yugen
  • Advanced Synthesis & Catalysis, Vol. 354, Issue 6, p. 969-974
  • DOI: 10.1002/adsc.201100934

Linked strategy for the production of fuels via formose reaction
journal, February 2013
  • Deng, Jin; Pan, Tao; Xu, Qing
  • Scientific Reports, Vol. 3, Article No. 1244
  • DOI: 10.1038/srep01244

Monolayers of choline chloride can enhance desired electrochemical reactions and inhibit undesirable ones
journal, April 2013

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