Formation of Copper Catalysts for CO2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy.

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)-carbonate/hydroxide is also reported. This study highlights the importance of using oxidized copper precursors for constructing selective CO2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.

[1]  A. Nilsson,et al.  Electroreduction of Carbon Monoxide Over a Copper Nanocube Catalyst: Surface Structure and pH Dependence on Selectivity , 2016 .

[2]  P. Strasser,et al.  Controlling the selectivity of CO2 electroreduction on copper: The effect of the electrolyte concentration and the importance of the local pH , 2016 .

[3]  Seunghwan Lee,et al.  Electrocatalytic Production of C3-C4 Compounds by Conversion of CO2 on a Chloride-Induced Bi-Phasic Cu2O-Cu Catalyst. , 2015, Angewandte Chemie.

[4]  Chao Wang,et al.  Highly Dense Cu Nanowires for Low-Overpotential CO2 Reduction. , 2015, Nano letters.

[5]  B. F. Brown,et al.  Corrosion and Metal Artifacts: A Dialogue Between Conservators and Archaeologists and Corrosion Scientists , 2015 .

[6]  Wilson A. Smith,et al.  Selective electrochemical reduction of CO2 to CO on CuO-derived Cu nanowires. , 2015, Physical chemistry chemical physics : PCCP.

[7]  Matthew W. Kanan,et al.  Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts. , 2015, Journal of the American Chemical Society.

[8]  Anders Nilsson,et al.  High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts. , 2015, Angewandte Chemie.

[9]  Shoushan Fan,et al.  Grain-boundary-dependent CO2 electroreduction activity. , 2015, Journal of the American Chemical Society.

[10]  Chunguang Chen,et al.  Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts , 2015 .

[11]  G. Naterer,et al.  Using XANES to obtain mechanistic information for the hydrolysis of CuCl2 and the decomposition of Cu2OCl2 in the thermochemical Cu–Cl cycle for H2 production , 2015, Journal of Thermal Analysis and Calorimetry.

[12]  Jae Kwang Lee,et al.  Insights into an autonomously formed oxygen-evacuated Cu2O electrode for the selective production of C2H4 from CO2. , 2015, Physical chemistry chemical physics : PCCP.

[13]  Jia‐Xing Lu,et al.  Morphology-controlled CuO nanoparticles for electroreduction of CO2 to ethanol , 2014 .

[14]  G. Mul,et al.  Electrochemical CO2 reduction on Cu2O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons. , 2014, Physical chemistry chemical physics : PCCP.

[15]  Matthew W. Kanan,et al.  Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper , 2014, Nature.

[16]  D. Sokaras,et al.  Structure, Redox Chemistry, and Interfacial Alloy Formation in Monolayer and Multilayer Cu/Au(111) Model Catalysts for CO2 Electroreduction , 2014 .

[17]  Thomas F. Jaramillo,et al.  New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces , 2012 .

[18]  Matthew W Kanan,et al.  CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. , 2012, Journal of the American Chemical Society.

[19]  William J. Durand,et al.  The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction. , 2012, Physical chemistry chemical physics : PCCP.

[20]  Narendra K. Gupta,et al.  Electrochemical reduction of CO2 to hydrocarbons to store renewable electrical energy and upgrade biogas , 2007 .

[21]  N. Lewis,et al.  Powering the planet: Chemical challenges in solar energy utilization , 2006, Proceedings of the National Academy of Sciences.

[22]  Anne C. Co,et al.  A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper , 2006 .

[23]  M. Gattrell,et al.  Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions , 2006 .

[24]  M Newville,et al.  A web-based library of XAFS data on model compounds. , 1999, Journal of synchrotron radiation.

[25]  K. Hodgson,et al.  X-ray absorption edge determination of the oxidation state and coordination number of copper: application to the type 3 site in Rhus vernicifera laccase and its reaction with oxygen , 1987 .

[26]  Chunguang Chen,et al.  Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals , 2015 .

[27]  Jae Kwang Lee,et al.  Insights into autonomously formed oxygen-evacuated Cu 2 O electrode for the selective production of C 2 H 4 from CO 2 , 2014 .

[28]  Christina W. Li,et al.  CO 2 Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu 2 O Films , 2012 .

[29]  C. Sequeira,et al.  Selective electrochemical conversion of CO2 to C2 hydrocarbons , 2010 .

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

[31]  Gareth Kear,et al.  Electrochemical corrosion of unalloyed copper in chloride media––a critical review , 2004 .

[32]  P. Longhi,et al.  Copper in sea-water, potential-pH diagrams , 1973 .