Tailored Selectivity for CO and C<sub>2+</sub> in CO<sub>2</sub> Reduction: Insights into the Dynamic Evolution of Electrocatalysts
Abstract
AbstractControlling product selectivity in electrochemical CO2 reduction (eCO2R) is critical for efficient CO2 conversion. However, the dynamic structural changes of Cu‐based catalysts during operation complicate mechanistic understanding. Here, we investigate fluorine‐modified copper pre‐catalysts with varying doping levels and reveal how their structural evolution governs eCO2R activity and selectivity. Through operando spectroscopy characterizations and theoretical simulations, we show that fluorine leaches rapidly during electrolysis, transforming Cu2⁺ precursors into metallic Cu⁰ with distinct local structures. Cu‐F‐4, with the lowest coordination number, exhibits high eCO2R activity and favors CO formation with a Faradaic efficiency (FECO) of 81% at −0.45 V. In contrast, Cu‐F‐1, enriched in grain boundaries and Cu(100) facets, achieves a high FEC2+ of 80% at −0.65 V. Differences in local pH, *OH coverage, and *CO binding energies further modulate catalytic pathways. Our findings highlight the importance of dynamic catalyst reconstruction in steering product selectivity and offer design principles for advancing CO2‐to‐chemicals conversion.
Article Details
Authors (13)
Lu Liu
Yuke Li
Department of Mechanical and Industrial Engineering
Kher Ai Chiaw
Institute of Sustainability for Chemicals, Energy and Environment (ISCE2) Agency of Science, Technology, and Research (A*STAR) Singapore 627833 Singapore
Shibo Xi
Shuying Cheng
Institute of Sustainability for Chemicals, Energy and Environment (ISCE2) Agency of Science, Technology, and Research (A*STAR) Singapore 627833 Singapore
Shashikant U. Dighe
Institute of Sustainability for Chemicals, Energy and Environment (ISCE2) Agency of Science, Technology, and Research (A*STAR) Singapore 627833 Singapore
Huaiyu Chang
Boon Ying Tay
Institute of Sustainability for Chemicals, Energy and Environment (ISCE2) Agency of Science, Technology, and Research (A*STAR) Singapore 627833 Singapore
Mingwu Tan
Kuo‐Wei Huang
Center for Renewable Energy and Storage Technologies (CREST) KAUST Catalysis Center (KCC) Physical Science and Engineering Division King Abdullah University of Science and Technology Thuwal 23955 Saudi Arabia
Linfei Lai
Jiangsu Natl Synergist Innovat Ctr, Adv Mat SICAM, Key Lab Flexible Nanjing Tech University Elect, 5 XinMofan Rd Nanjing 210009 P.R China
Yingqing Ou
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Lili Zhang