DataVXAdvanced Energy MaterialsPaper
journal article·2022-02Open access

Determining Structure‐Activity Relationships in Oxide Derived CuSn Catalysts During CO 2 Electroreduction Using X‐Ray Spectroscopy

Laura C. Pardo Pérez, Alexander Arndt, Sasho Stojkovikj, Ibbi Y. Ahmet, Joshua T. Arens, Federico Dattila, Robert Wendt, Ana Guilherme Buzanich, Martin Radtke, Veronica Davies, Katja Höflich, Eike Köhnen, Philipp Tockhorn, Ronny Golnak, Jie Xiao, Götz Schuck, Markus Wollgarten, Núria López, Matthew T. Mayer

Advanced Energy Materials· Volume 12· Issue 5
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Abstract

Abstract The development of earth‐abundant catalysts for selective electrochemical CO 2 conversion is a central challenge. CuSn bimetallic catalysts can yield selective CO 2 reduction toward either CO or formate. This study presents oxide‐derived CuSn catalysts tunable for either product and seeks to understand the synergetic effects between Cu and Sn causing these selectivity trends. The materials undergo significant transformations under CO 2 reduction conditions, and their dynamic bulk and surface structures are revealed by correlating observations from multiple methods—X‐ray absorption spectroscopy for in situ study, and quasi in situ X‐ray photoelectron spectroscopy for surface sensitivity. For both types of catalysts, Cu transforms to metallic Cu 0 under reaction conditions. However, the Sn speciation and content differ significantly between the catalyst types: the CO‐selective catalysts exhibit a surface Sn content of 13 at. % predominantly present as oxidized Sn, while the formate‐selective catalysts display an Sn content of ≈70 at. % consisting of both metallic Sn 0 and Sn oxide species. Density functional theory simulations suggest that Sn δ+ sites weaken CO adsorption, thereby enhancing CO selectivity, while Sn 0 sites hinder H adsorption and promote formate production. This study reveals the complex dependence of catalyst structure, composition, and speciation with electrochemical bias in bimetallic Cu catalysts.
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Research context

Catalysis & surfaces

OpenAlex topics: CO2 Reduction Techniques and Catalysts · Ionic liquids properties and applications · Advanced Thermoelectric Materials and Devices

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Young Investigator Group Electrochemical Conversion of CO2 Helmholtz‐Zentrum Berlin für Materialien und Energie GmbH Hahn‐Meitner‐Platz 1 14109 Berlin Germany

Institut für Chemie & Biochemie Freie Universität Berlin Arnimallee 22 14195 Berlin Germany

Institute for Solar Fuels Helmholtz‐Zentrum Berlin für Materialien und Energie GmbH Hahn‐Meitner‐Platz 1 14109 Berlin Germany

Institute of Chemical Research of Catalonia (ICIQ) The Barcelona Institute of Science and Technology (BIST) Av. Països Catalans 16 Tarragona 43007 Spain

Division 6.3 Structure Analysis Bundesanstalt für Materialforschung und ‐prüfung (BAM) Richard‐Willstätter‐Straße 11 12489 Berlin Germany

Young Investigator Group Perovskite Tandem Solar Cells Helmholtz‐Zentrum Berlin für Materialien und Energie GmbH Kekuléstraße 5 12489 Berlin Germany

Department Highly Sensitive X‐ray Spectroscopy Helmholtz‐Zentrum Berlin für Materialien und Energie GmbH Albert‐Einstein‐Straße 15 12489 Berlin Germany

Department Structure and Dynamics of Energy Materials Helmholtz‐Zentrum Berlin für Materialien und Energie GmbH Hahn‐Meitner‐Platz 1 14109 Berlin Germany

Funding

Helmholtz Energy Materials Foundry · European Commission · Ministerio de Ciencia e Innovación · Barcelona Supercomputing Center · H2020 Leadership in Enabling and Industrial Technologies · Helmholtz-Gemeinschaft

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