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The Role of the Copper Oxidation State in the Electrocatalytic Reduction of CO2 into Valuable Hydrocarbons

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Velasco Vélez,  Juan
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
Heterogeneous Reactions, Max-Planck-Institute for Chemical Energy Conversion , Stiftstr. 34 - 36 45470 Mülheim an der Ruhr, Germany;

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Jones,  Travis
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

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Gao,  Dunfeng
Interface Science, Fritz Haber Institute, Max Planck Society;
Department of Physics, Ruhr-University Bochum;

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Carbonio,  Emilia
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

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Roldan Cuenya,  Beatriz
Interface Science, Fritz Haber Institute, Max Planck Society;
Department of Physics, Ruhr-University Bochum;

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Schlögl,  Robert
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
Heterogeneous Reactions, Max-Planck-Institute for Chemical Energy Conversion , Stiftstr. 34 - 36 45470 Mülheim an der Ruhr, Germany;

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Knop-Gericke,  Axel
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;
Heterogeneous Reactions, Max-Planck-Institute for Chemical Energy Conversion , Stiftstr. 34 - 36 45470 Mülheim an der Ruhr, Germany;

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Citation

Velasco Vélez, J., Jones, T., Gao, D., Carbonio, E., Arrigo, R., Hsu, C.-J., et al. (2019). The Role of the Copper Oxidation State in the Electrocatalytic Reduction of CO2 into Valuable Hydrocarbons. ACS Sustainable Chemistry & Engineering, 7(1), 1485-1492. doi:10.1021/acssuschemeng.8b05106.


Cite as: https://hdl.handle.net/21.11116/0000-0002-B290-1
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.