Operando Surface-Enhanced Infrared Spectroscopy Connects Interfacial Dynamics with Reaction Kinetics During Electrochemical CO 2 Reduction on Copper

Matthews, Jesse E. [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis]; Avilés Acosta, Jaime E. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States)]; Lee, Sang-Won [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis]; Oh, Dongrak [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Ulsan National Institute of Science and Technology (UNIST), Ulsan (Korea, Republic of)] (ORCID:0000000348630477); Lin, Tiras Y. [Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)] (ORCID:0000000233779933); Yap, Kyra K. [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis] (ORCID:000000018861993X); Chen, Junjie [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis] (ORCID:0000000209541028); Jang, Ji-Wook [Ulsan National Institute of Science and Technology (UNIST), Ulsan (Korea, Republic of)] (ORCID:0000000312511011); Lee, Dong Un [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis] (ORCID:0000000175915350); Nielander, Adam C. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis]; Jaramillo, Thomas F. [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis] (ORCID:0000000199000622)

doi:10.1021/acscatal.4c05532

DOE OSTI · 2497909

Operando Surface-Enhanced Infrared Spectroscopy Connects Interfacial Dynamics with Reaction Kinetics During Electrochemical CO 2 Reduction on Copper

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Abstract

The reaction microenvironment plays a key role in dictating the selectivity of electrochemical CO 2 reduction. However, understanding the chemical nature of this microenvironment under operating conditions remains a substantial challenge. For this study, we employed attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) in operando for simultaneous measurements of reaction kinetics and concentrations of reactants and intermediates at the reaction interface, all under controlled mass transport conditions. These operando measurements enable direct correlations between the reaction microenvironment, mass transport, and kinetics for a Cu electrocatalyst, such as higher local concentrations of CO 2 under faster mass transport corresponding to higher rates of CO 2 reduction. We observed that faster mass transport decreased the *CO coverage at less negative potentials (-0.6 V RHE ) and increased the *CO coverage at more negative potentials (-1.1 V RHE ). We developed a transport-coupled kinetic model that captures these spectroscopic observations and provides insight into the processes controlling interfacial concentrations of reactants and intermediates, aiding future efforts toward tailoring reaction microenvironments.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ATR-SEIRAS CO2 reduction Energy - Conversion, Energy electrocatalysis microenvironment operando spectroscopy

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Matthews, Jesse E. [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis], Avilés Acosta, Jaime E. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States)], Lee, Sang-Won [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis], Oh, Dongrak [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Ulsan National Institute of Science and Technology (UNIST), Ulsan (Korea, Republic of)] (ORCID:0000000348630477), Lin, Tiras Y. [Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)] (ORCID:0000000233779933), Yap, Kyra K. [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis] (ORCID:000000018861993X), Chen, Junjie [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis] (ORCID:0000000209541028), Jang, Ji-Wook [Ulsan National Institute of Science and Technology (UNIST), Ulsan (Korea, Republic of)] (ORCID:0000000312511011), Lee, Dong Un [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis] (ORCID:0000000175915350), Nielander, Adam C. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis], Jaramillo, Thomas F. [Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis] (ORCID:0000000199000622). 2024-12-18. Operando Surface-Enhanced Infrared Spectroscopy Connects Interfacial Dynamics with Reaction Kinetics During Electrochemical CO 2 Reduction on Copper. https://doi.org/10.1021/acscatal.4c05532

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