Operando Surface-Enhanced Infrared Spectroscopy Connects Interfacial Dynamics with Reaction Kinetics During Electrochemical CO2 Reduction on Copper

Matthews, Jesse E.; Avilés Acosta, Jaime E.; Lee, Sang-Won; Oh, Dongrak; Lin, Tiras Y.; Yap, Kyra K.; Chen, Junjie; Jang, Ji-Wook; Lee, Dong Un; Nielander, Adam C.; Jaramillo, Thomas F.

doi:10.1021/acscatal.4c05532

Operando Surface-Enhanced Infrared Spectroscopy Connects Interfacial Dynamics with Reaction Kinetics During Electrochemical CO₂ Reduction on Copper

Journal Article · Wed Dec 18 00:00:00 EST 2024 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.4c05532· OSTI ID:2497909

Matthews, Jesse E. ^[1]; Avilés Acosta, Jaime E. ^[2]; Lee, Sang-Won ^[1]; ^[3]; ^[4]; ^[1]; ^[1]; ^[5]; ^[1]; Nielander, Adam C. ^[6]; ^[1]

Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States)
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)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Ulsan National Institute of Science and Technology (UNIST), Ulsan (Korea, Republic of)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis

The reaction microenvironment plays a key role in dictating the selectivity of electrochemical CO₂ 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 CO₂ under faster mass transport corresponding to higher rates of CO₂ 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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC52-07NA27344; SC0021266

OSTI ID:: 2497909

Report Number(s):: LLNL--JRNL-866547; 1101456

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 1 Vol. 15; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Operando Surface-Enhanced Infrared Spectroscopy Connects Interfacial Dynamics with Reaction Kinetics During Electrochemical CO2 Reduction on Copper

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