Morphology and mechanism of highly selective Cu(II) oxide nanosheet catalysts for carbon dioxide electroreduction
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- s41467-021-20961-7
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Cu oxides catalyze the electrochemical carbon dioxide reduction reaction (CO2RR) to hydrocarbons and oxygenates with favorable selectivity. Among them, the shape-controlled Cu oxide cubes have been most widely studied. In contrast, we report on novel 2-dimensional (2D) Cu(II) oxide nanosheet (CuO NS) catalysts with high C2+ products, selectivities (> 400 mA cm−2) in gas diffusion electrodes (GDE) at industrially relevant currents and neutral pH. Under applied bias, the (001)-orientated CuO NS slowly evolve into highly branched, metallic Cu0 dendrites that appear as a general dominant morphology under electrolyte flow conditions, as attested by operando X-ray absorption spectroscopy and in situ electrochemical transmission electron microscopy (TEM). Millisecond-resolved differential electrochemical mass spectrometry (DEMS) track a previously unavailable set of product onset potentials. While the close mechanistic relation between CO and C2H4 was thereby confirmed, the DEMS data help uncover an unexpected mechanistic link between CH4 and ethanol. We demonstrate evidence that adsorbed methyl species, *CH3, serve as common intermediates of both CH3H and CH3CH2OH and possibly of other CH3-R products via a previously overlooked pathway at (110) steps adjacent to (100) terraces at larger overpotentials. Our mechanistic conclusions challenge and refine our current mechanistic understanding of the CO2 electrolysis on Cu catalysts.
| Originalsprog | Engelsk |
|---|---|
| Artikelnummer | 794 |
| Tidsskrift | Nature Communications |
| Vol/bind | 12 |
| Udgave nummer | 1 |
| Antal sider | 12 |
| ISSN | 2041-1723 |
| DOI | |
| Status | Udgivet - dec. 2021 |
Bibliografisk note
Funding Information:
The research leading to these results has recieved funding from the European Union’s Horizon 2020 research and innovation programme under grant No. 101006701, Eco-Fuel. The authors are grateful for partial support by the German Federal Ministry of Education and Research (Bundesministerium für Bildung und Forschung, BMBF) under grant #03SF0523A/B/C–CO2EKAT. We acknowledge funding from the Germans National Science Foundation (Deutsche Forschungsgemeinschaft) through grant STR 596/5-2. H.D. acknowledges support by the BMBF in the IN-SITU-XAS and OPERANDO-XAS projects. We acknowledge the Helmholtz Zentrum Berlin (HZB) for providing experimental infrastructure and allocating beamtime at beamline KMC-3 of the BESSY synchrotron; we thank Ivo Zizak and further BESSY staff for their support. We thank Dr. Tore Niermann and Dipl. Ing. Sören Selve from Zentraleinrichtung für Elektronenmikroskopie (ZELMI) of the Technical University Berlin for their support with HR-TEM measurements. We acknowledge Dr. Fabio Dionigi from Technical University Berlin and Jakub Drnec at ID 31 from European Synchrotron Radiation Facility (ESRF) for their help on with the preparation of WAXS measurements, and Dr. Vadim Sikolenko for his help with the operando XAS experiments. AB and JR acknowledges the Danish National Research Foundation centers of excellence, The Center for High Entropy Alloys Catalysis (Project DNRF149).
Publisher Copyright:
© 2021, The Author(s).
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