Insights into the Low Overpotential Electroreduction of CO2 to CO on a Supported Gold Catalyst in an Alkaline Flow Electrolyzer

Cost competitive electroreduction of CO2 to CO requires electrochemical systems that exhibit partial current density (jCO) exceeding 150 mA cm–2 at cell overpotentials (|ηcell|) less than 1 V. However, achieving such benchmarks remains difficult. Here, we report the electroreduction of CO2 on a supported gold catalyst in an alkaline flow electrolyzer with performance levels close to the economic viability criteria. Onset of CO production occurred at cell and cathode overpotentials of just −0.25 and −0.02 V, respectively. High jCO (∼99, 158 mA cm–2) was obtained at low |ηcell| (∼0.70, 0.94 V) and high CO energetic efficiency (∼63.8, 49.4%). The performance was stable for at least 8 h. Additionally, the onset cathode potentials, kinetic isotope effect, and Tafel slopes indicate the low overpotential production of CO in alkaline media to be the result of a pH-independent rate-determining step (i.e., electron transfer) in contrast to a pH-dependent overall process.

[1]  T. Fujigaya,et al.  Gold Nanoparticles on Polymer-Wrapped Carbon Nanotubes: An Efficient and Selective Catalyst for the Electroreduction of CO2. , 2017, Chemphyschem : a European journal of chemical physics and physical chemistry.

[2]  Ferenc Darvas,et al.  Continuous-flow electroreduction of carbon dioxide , 2017 .

[3]  N. Russo,et al.  Syngas production from electrochemical reduction of CO2: current status and prospective implementation , 2017 .

[4]  R. Lal,et al.  Introduction to Global Carbon Cycling: An Overview of the Global Carbon Cycle , 2017 .

[5]  Y. Surendranath,et al.  Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels. , 2016, Angewandte Chemie.

[6]  F. Jiao,et al.  Electrochemical CO2 reduction: Electrocatalyst, reaction mechanism, and process engineering , 2016 .

[7]  A. Bell,et al.  Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO2 over Ag and Cu. , 2016, Journal of the American Chemical Society.

[8]  M. Fontecave,et al.  CO2 Reduction to CO in Water: Carbon Nanotube-Gold Nanohybrid as a Selective and Efficient Electrocatalyst. , 2016, ChemSusChem.

[9]  Byoungsu Kim,et al.  A Gross-Margin Model for Defining Technoeconomic Benchmarks in the Electroreduction of CO2. , 2016, ChemSusChem.

[10]  J. Nørskov,et al.  Barriers of Electrochemical CO2 Reduction on Transition Metals , 2016 .

[11]  Wilson A. Smith,et al.  Selective and Efficient Reduction of Carbon Dioxide to Carbon Monoxide on Oxide-Derived Nanostructured Silver Electrocatalysts. , 2016, Angewandte Chemie.

[12]  A. Gewirth,et al.  Observation of an Inverse Kinetic Isotope Effect in Oxygen Evolution Electrochemistry , 2016 .

[13]  Y. Surendranath,et al.  Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity , 2016, Proceedings of the National Academy of Sciences.

[14]  Joshua M. Spurgeon,et al.  New trends in the development of heterogeneous catalysts for electrochemical CO2 reduction , 2016 .

[15]  Christopher J. Chang,et al.  A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction. , 2016, Journal of the American Chemical Society.

[16]  Paul J. A. Kenis,et al.  Carbon nanotube containing Ag catalyst layers for efficient and selective reduction of carbon dioxide , 2016 .

[17]  Xun Lu,et al.  The effect of electrolyte composition on the electroreduction of CO2 to CO on Ag based gas diffusion electrodes. , 2016, Physical chemistry chemical physics : PCCP.

[18]  T. Fujigaya,et al.  Growth and Deposition of Au Nanoclusters on Polymer-wrapped Graphene and Their Oxygen Reduction Activity , 2016, Scientific Reports.

[19]  N. Marković,et al.  Evidence for Decoupled Electron and Proton Transfer in the Electrochemical Oxidation of Ammonia on Pt(100). , 2016, The journal of physical chemistry letters.

[20]  Antonio J. Martín,et al.  Towards sustainable fuels and chemicals through the electrochemical reduction of CO2: lessons from water electrolysis , 2015 .

[21]  Paul J. A. Kenis,et al.  Influence of dilute feed and pH on electrochemical reduction of CO2 to CO on Ag in a continuous flow electrolyzer , 2015 .

[22]  T. Fujigaya,et al.  Enhancement of Platinum Mass Activity at Polymer-Wrapped Carbon Nanotube-Based Fuel Cell Electrocatalysts , 2015 .

[23]  Christos T. Maravelias,et al.  A general framework for the assessment of solar fuel technologies , 2015 .

[24]  J. Greeley,et al.  Exceptional size-dependent activity enhancement in the electroreduction of CO2 over Au nanoparticles. , 2014, Journal of the American Chemical Society.

[25]  Etosha R. Cave,et al.  Insights into the electrocatalytic reduction of CO₂ on metallic silver surfaces. , 2014, Physical chemistry chemical physics : PCCP.

[26]  Sichao Ma,et al.  Silver supported on titania as an active catalyst for electrochemical carbon dioxide reduction. , 2014, ChemSusChem.

[27]  Feng Jiao,et al.  A selective and efficient electrocatalyst for carbon dioxide reduction , 2014, Nature Communications.

[28]  Jiujun Zhang,et al.  A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. , 2014, Chemical Society reviews.

[29]  Paul J. A. Kenis,et al.  Efficient Electrochemical Flow System with Improved Anode for the Conversion of CO2 to CO , 2014 .

[30]  Danièle Revel,et al.  Assessing ‘‘dangerous climate change’’: Required reduction of carbon emissions to protect young people, future generations and nature , 2013 .

[31]  Haifeng Lv,et al.  Monodisperse Au nanoparticles for selective electrocatalytic reduction of CO2 to CO. , 2013, Journal of the American Chemical Society.

[32]  Marc T. M. Koper,et al.  Theory of multiple proton–electron transfer reactions and its implications for electrocatalysis , 2013 .

[33]  Paul J. A. Kenis,et al.  Electrochemical conversion of CO2 to useful chemicals: current status, remaining challenges, and future opportunities , 2013 .

[34]  Fikile R. Brushett,et al.  The Effects of Catalyst Layer Deposition Methodology on Electrode Performance , 2013 .

[35]  Tsuyohiko Fujigaya,et al.  Fuel Cell Electrocatalyst Using Polybenzimidazole‐Modified Carbon Nanotubes As Support Materials , 2013, Advanced materials.

[36]  P. Kenis,et al.  Nanoparticle Silver Catalysts That Show Enhanced Activity for Carbon Dioxide Electrolysis , 2013 .

[37]  Paul J. A. Kenis,et al.  Effect of Cations on the Electrochemical Conversion of CO2 to CO , 2013 .

[38]  Yihong Chen,et al.  Aqueous CO2 reduction at very low overpotential on oxide-derived Au nanoparticles. , 2012, Journal of the American Chemical Society.

[39]  A. Majumdar,et al.  Opportunities and challenges for a sustainable energy future , 2012, Nature.

[40]  M. Gómez-Gallego,et al.  Kinetic Isotope Effects in the Study of Organometallic Reaction Mechanisms , 2011 .

[41]  P. Kenis,et al.  Ionic Liquid–Mediated Selective Conversion of CO2 to CO at Low Overpotentials , 2011, Science.

[42]  Devin T. Whipple.  Microfluidic reactor for the electrochemical reduction of carbon dioxide , 2010 .

[43]  Y. Hori,et al.  Electrochemical CO 2 Reduction on Metal Electrodes , 2008 .

[44]  L. Krishtalik.  Kinetic isotope effect in the hydrogen evolution reaction , 2001 .

[45]  Toshio Tsukamoto,et al.  Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media , 1994 .

[46]  J. A. Crayston,et al.  Electrocatalysts for carbon dioxide reduction (models for methyl co-enzyme M reductase) , 1993 .

[47]  H. Schwarz,et al.  Reduction Potentials of CO- 2 and the Alcohol Radicals. , 1989 .

[48]  K. Chandrasekaran,et al.  In-situ spectroscopic investigation of adsorbed intermediate radicals in electrochemical reactions: CO2− on platinum , 1987 .

[49]  O. Petrii,et al.  Potentials of Zero Charge , 1980 .

[50]  R. Weiss.  Carbon dioxide in water and seawater: the solubility of a non-ideal gas , 1974 .

[51]  B. Conway,et al.  Erratum: Studies on the Hydrogen Evolution Reaction down to -150°C and the Role of Proton Tunneling , 1964 .

[52]  Carbon Dioxide Utilization Electrochemical Conversion of CO 2 – Opportunities and Challenges , 2022 .