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  Tracking heterogeneous structural motifs and the redox behaviour of copper-zinc nanocatalysts for the electrocatalytic CO2 reduction using operando time resolved spectroscopy and machine learning

Rüscher, M., Herzog, A., Timoshenko, J., Jeon, H., Frandsen, W., Kühl, S., et al. (2022). Tracking heterogeneous structural motifs and the redox behaviour of copper-zinc nanocatalysts for the electrocatalytic CO2 reduction using operando time resolved spectroscopy and machine learning. Catalysis Science & Technology, 12(9), 3028-3043. doi:10.1039/D2CY00227B.

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 Creators:
Rüscher, Martina1, Author              
Herzog, Antonia1, Author              
Timoshenko, Janis1, Author              
Jeon, Hyosang1, Author              
Frandsen, Wiebke1, Author              
Kühl, Stefanie1, Author              
Roldan Cuenya, Beatriz1, Author              
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1Interface Science, Fritz Haber Institute, Max Planck Society, ou_2461712              

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 Abstract: Copper-based catalysts are established catalytic systems for the electrocatalytic CO2 reduction reaction (CO2RR), where wasteful CO2 is converted into valuable industrial resources, such as energy-dense C2+ products, using energy from renewable sources. However, better control over the catalyst selectivity, especially at industrially relevant high current density conditions is needed to expedite the economically viability of the CO2RR. For this purpose, bimetallic materials, where copper is combined with a secondary metal, comprise a promising and a highly tunable catalyst for CO2RR. However, the synergy between copper and the selected secondary metal species, the evolution of the bimetallic structural motifs under working conditions and the effect of the secondary metal on the kinetics of the Cu redox behavior require careful investigation. Here, we employ operando quick X-ray absorption spectroscopy (QXAFS), coupled with machine-learning based data analsysis and surface-enhanced Raman spectroscopy (SERS) to investigate the time-dependent chemical and structural changes in catalysts derived from shape-selected Zn/Cu2O nanocubes under CO2RR conditions at current densities up to -500 mA/cm2. We furthermore relate the transformation observed under working conditions to the catalytic activity and selectivity and correlate potential-dependent surface and subsurface processes. We report that the addition of Zn to a Cu-based catalyst has crucial impact on the kinetics of subsurface processes, while redox processes of the Cu surface layer remain largely unaffected. Interestingly, the presence of Zn was found to contribute to the stabilization of cationic Cu(I) species, which is of catalytic relevance since Cu(0)/Cu(I) interfaces have been reported beneficial for the efficient CO2 conversion to complex multicarbon products. At the same time, we attribute the increase of the C2+ product selectivity to the formation of Cu-rich CuZn alloys in samples with low Zn content, while Zn-rich alloy phases result in an increased formation of CO paralleled by an increase of the parasitic hydrogen evolution reaction.

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Language(s): eng - English
 Dates: 2022-01-212022-03-102022-03-102022-05-07
 Publication Status: Published in print
 Pages: 16
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/D2CY00227B
 Degree: -

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Project name : OPERANDOCAT - In situ and Operando Nanocatalysis: Size, Shape and Chemical State Effects
Grant ID : 725915
Funding program : Horizon 2020 (H2020)
Funding organization : European Commission (EC)

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Title: Catalysis Science & Technology
  Other : Catal. Sci. Technol.
Source Genre: Journal
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Publ. Info: Cambridge : Royal Society of Chemistry
Pages: 16 Volume / Issue: 12 (9) Sequence Number: - Start / End Page: 3028 - 3043 Identifier: ISSN: 2044-4753
CoNE: https://pure.mpg.de/cone/journals/resource/2044-4753