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

Eilert, André; Roberts, F. Sloan; Friebel, Daniel; Nilsson, Anders

doi:10.1021/acs.jpclett.6b00367

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

Journal Article · Mon Apr 04 00:00:00 EDT 2016 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.6b00367· OSTI ID:1256341

Eilert, André ^[1]; Roberts, F. Sloan ^[1]; Friebel, Daniel ^[1]; Nilsson, Anders ^[2]

SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering; Stockholm Univ. (Sweden). AlbaNova University Center, Dept. of Physics

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. In conclusion, 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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; US Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: FA9550-10-1-0572; AC02-76SF00515

OSTI ID:: 1256341

Journal Information:: Journal of Physical Chemistry Letters, Vol. 7, Issue 8; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 117 works

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References (30)

Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
Electrochemical reduction of CO₂ to hydrocarbons to store renewable electrical energy and upgrade biogas Gattrell, M.; Gupta, N.; Co, A. Energy Conversion and Management, Vol. 48, Issue 4, p. 1255-1265 https://doi.org/10.1016/j.enconman.2006.09.019	journal	April 2007
Electrochemical CO₂ Reduction on Metal Electrodes Hori, Y.; Vayenas, Constantinos G.; White, Ralph E. Modern Aspects of Electrochemistry, p. 89-189 https://doi.org/10.1007/978-0-387-49489-0_3	book	January 2008
A review of the aqueous electrochemical reduction of CO₂ to hydrocarbons at copper Gattrell, M.; Gupta, N.; Co, A. Journal of Electroanalytical Chemistry, Vol. 594, Issue 1, p. 1-19 https://doi.org/10.1016/j.jelechem.2006.05.013	journal	August 2006
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee21234j	journal	January 2012
CO₂ Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu₂O Films Li, Christina W.; Kanan, Matthew W. Journal of the American Chemical Society, Vol. 134, Issue 17, p. 7231-7234 https://doi.org/10.1021/ja3010978	journal	April 2012
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper Li, Christina W.; Ciston, Jim; Kanan, Matthew W. Nature, Vol. 508, Issue 7497 https://doi.org/10.1038/nature13249	journal	April 2014
Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts Ren, Dan; Deng, Yilin; Handoko, Albertus Denny ACS Catalysis, Vol. 5, Issue 5 https://doi.org/10.1021/cs502128q	journal	March 2015
Insights into an autonomously formed oxygen-evacuated Cu ₂ O electrode for the selective production of C ₂ H ₄ from CO ₂ Kim, Dahee; Lee, Seunghwa; Ocon, Joey D. Physical Chemistry Chemical Physics, Vol. 17, Issue 2 https://doi.org/10.1039/C4CP03172E	journal	January 2015
Highly Dense Cu Nanowires for Low-Overpotential CO₂ Reduction Raciti, David; Livi, Kenneth J.; Wang, Chao Nano Letters, Vol. 15, Issue 10, p. 6829-6835 https://doi.org/10.1021/acs.nanolett.5b03298	journal	September 2015
Electrocatalytic Production of C3-C4 Compounds by Conversion of CO ₂ on a Chloride-Induced Bi-Phasic Cu ₂ O-Cu Catalyst Lee, Seunghwa; Kim, Dahee; Lee, Jaeyoung Angewandte Chemie, Vol. 127, Issue 49 https://doi.org/10.1002/ange.201505730	journal	October 2015
Selective electrochemical reduction of CO ₂ to CO on CuO-derived Cu nanowires Ma, Ming; Djanashvili, Kristina; Smith, Wilson A. Physical Chemistry Chemical Physics, Vol. 17, Issue 32 https://doi.org/10.1039/C5CP03559G	journal	January 2015
Morphology-controlled CuO nanoparticles for electroreduction of CO ₂ to ethanol Chi, Dinghui; Yang, Hengpan; Du, Yanfang RSC Adv., Vol. 4, Issue 70 https://doi.org/10.1039/C4RA05415F	journal	January 2014
Electrochemical CO ₂ reduction on Cu ₂ O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons Kas, Recep; Kortlever, Ruud; Milbrat, Alexander Phys. Chem. Chem. Phys., Vol. 16, Issue 24 https://doi.org/10.1039/c4cp01520g	journal	January 2014
High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders Angewandte Chemie International Edition, Vol. 54, Issue 17 https://doi.org/10.1002/anie.201412214	journal	February 2015
Electroreduction of Carbon Monoxide Over a Copper Nanocube Catalyst: Surface Structure and pH Dependence on Selectivity Roberts, F. Sloan; Kuhl, Kendra P.; Nilsson, Anders ChemCatChem, Vol. 8, Issue 6 https://doi.org/10.1002/cctc.201501189	journal	February 2016
Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals Chen, Chung Shou; Handoko, Albertus D.; Wan, Jane Hui Catalysis Science & Technology, Vol. 5, Issue 1 https://doi.org/10.1039/C4CY00906A	journal	January 2015
Copper in sea-water, potential-pH diagrams Bianchi, G.; Longhi, P. Corrosion Science, Vol. 13, Issue 11 https://doi.org/10.1016/S0010-938X(73)80067-8	journal	January 1973
Electrochemical corrosion of unalloyed copper in chloride media––a critical review Kear, G.; Barker, B. D.; Walsh, F. C. Corrosion Science, Vol. 46, Issue 1 https://doi.org/10.1016/S0010-938X(02)00257-3	journal	January 2004
A web-based library of XAFS data on model compounds Newville, M.; Carroll, S. A.; O'Day, P. A. Journal of Synchrotron Radiation, Vol. 6, Issue 3 https://doi.org/10.1107/S0909049599000795	journal	May 1999
Structure, Redox Chemistry, and Interfacial Alloy Formation in Monolayer and Multilayer Cu/Au(111) Model Catalysts for CO ₂ Electroreduction Friebel, Daniel; Mbuga, Felix; Rajasekaran, Srivats The Journal of Physical Chemistry C, Vol. 118, Issue 15 https://doi.org/10.1021/jp412000j	journal	April 2014
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 Ferrandon, M.; Daggupati, V.; Wang, Z. Journal of Thermal Analysis and Calorimetry, Vol. 119, Issue 2 https://doi.org/10.1007/s10973-014-4240-2	journal	November 2014
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 Kau, Lung Shan; Spira-Solomon, Darlene J.; Penner-Hahn, James E. Journal of the American Chemical Society, Vol. 109, Issue 21 https://doi.org/10.1021/ja00255a032	journal	October 1987
Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P. Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b06227	journal	July 2015
Grain-Boundary-Dependent CO ₂ Electroreduction Activity Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan Journal of the American Chemical Society, Vol. 137, Issue 14 https://doi.org/10.1021/ja5130513	journal	April 2015
The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction Tang, Wei; Peterson, Andrew A.; Varela, Ana Sofia Phys. Chem. Chem. Phys., Vol. 14, Issue 1 https://doi.org/10.1039/C1CP22700A	journal	January 2012
Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions Gupta, N.; Gattrell, M.; MacDougall, B. Journal of Applied Electrochemistry, Vol. 36, Issue 2 https://doi.org/10.1007/s10800-005-9058-y	journal	October 2005
Controlling the selectivity of CO2 electroreduction on copper: The effect of the electrolyte concentration and the importance of the local pH Varela, Ana Sofia; Kroschel, Matthias; Reier, Tobias Catalysis Today, Vol. 260 https://doi.org/10.1016/j.cattod.2015.06.009	journal	February 2016
Selective electrochemical conversion of CO2 to C2 hydrocarbons Gonçalves, M. R.; Gomes, A.; Condeço, J. Energy Conversion and Management, Vol. 51, Issue 1 https://doi.org/10.1016/j.enconman.2009.08.002	journal	January 2010
SIXPack a Graphical User Interface for XAS Analysis Using IFEFFIT Webb, S. M. Physica Scripta https://doi.org/10.1238/Physica.Topical.115a01011	journal	January 2005

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Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels Birdja, Yuvraj Y.; Pérez-Gallent, Elena; Figueiredo, Marta C. Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0450-y	journal	September 2019
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Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO Schreier, Marcel; Héroguel, Florent; Steier, Ludmilla Nature Energy, Vol. 2, Issue 7 https://doi.org/10.1038/nenergy.2017.87	journal	June 2017
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Tunable formation of copper metal, oxide, chloride and hydroxyl chloride nanoparticles from aqueous copper solutions using nanoscale zerovalent iron particles Crane, Richard; Sapsford, Devin Nanomaterials and Nanotechnology, Vol. 9 https://doi.org/10.1177/1847980419886173	journal	January 2019
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In-situ Spectroscopic Techniques as Critical Evaluation Tools for Electrochemical Carbon dioxide Reduction: A Mini Review Adarsh, K. S.; Chandrasekaran, Naveen; Chakrapani, Vidhya Frontiers in Chemistry, Vol. 8 https://doi.org/10.3389/fchem.2020.00137	journal	March 2020

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