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The role of the copper oxidation state in the electrocatalytic reduction of CO2 into valuable hydrocarbons

DOI: 10.1021/acssuschemeng.8b05106 DOI Help

Authors: Juan-Jesús Velasco-Vélez (Max Planck Institute for Chemical Energy Conversion; Fritz-Haber-Institut der Max-Planck-Gesellschaft) , Travis E. Jones (Fritz-Haber-Institut der Max-Planck-Gesellschaft) , Dunfeng Gao (Ruhr-University Bochum; Fritz-Haber-Institute of the Max-Planck Society) , Emilia Carbonio (Fritz-Haber-Institut der Max-Planck-Gesellschaft) , Rosa Arrigo (Diamond Light Source; University of Salford) , Cheng-Jhih Hsu (Tamkang University) , Yu-Cheng Huang (Tamkang University; National Synchrotron Radiation Research Center) , Chung Li Dong (Tamkang University) , Jin-Ming Chen (National Synchrotron Radiation Research Center) , Jyh-Fu Lee (National Synchrotron Radiation Research Center) , Peter Strasser (Technical University Berlin) , Beatriz Roldan-Cuenya (Ruhr-University Bochum; Fritz-Haber-Institute of the Max-Planck Society) , Robert Schloegl (Max Planck Institute for Chemical Energy Conversion; Fritz-Haber-Institut der Max-Planck-Gesellschaft) , Axel Knop-Gericke (Max Planck Institute for Chemical Energy Conversion; Fritz-Haber-Institut der Max-Planck-Gesellschaft) , Cheng-Hao Chuang (Tamkang University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Acs Sustainable Chemistry & Engineering

State: Published (Approved)
Published: November 2018

Abstract: Redox-active copper catalysts with accurately prepared oxidation states (Cu0, Cu+ and Cu2+) and high selectivity to C2 hydrocarbon formation, from electrocatalytic cathodic reduction of CO2, were fabricated and characterized. The electrochemically prepared copper-redox electro-cathodes yield higher activity for the production of hydrocarbons at lower oxidation state. By combining advanced X-ray spectroscopy and in situ micro-reactors it was possible to unambiguously reveal the variation in the complex electronic structure that the catalysts undergo at different stages (i.e. during fabrication and electrocatalytic reactions). It was found that the surface, sub-surface and bulk properties of the electrochemically prepared catalysts are dominated by the formation of copper carbonates on the surface of cupric-like oxides, which prompts catalyst deactivation by restraining effective charge transport. Furthermore, the formation of reduced or partially-reduced copper catalysts yields the key dissociative proton-consuming reactive adsorption of CO2 to produce CO; allowing the subsequent hydrogenation into C2 and C1 products by dimerization and protonation. These results yield valuable information on the variations in the electronic structure that redox-active copper catalysts undergo in the course of the electrochemical reaction, which, under extreme conditions are mediated by thermodynamics but, critically, kinetics dominate near the oxide/metal phase transitions.

Journal Keywords: CO2RR; electrodeposited prepared copper oxides; in situ X-ray spectroscopy; copper carbonate passivation layer; charge transport limitation; DFT calculations; electrocatalytic active reduced copper oxides

Subject Areas: Chemistry, Environment, Energy


Technical Areas:

Added On: 03/12/2018 10:17

Discipline Tags:

Earth Sciences & Environment Sustainable Energy Systems Energy Climate Change Physical Chemistry Catalysis Chemistry Engineering & Technology Organic Chemistry

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