Local-strain-induced CO2 adsorption geometries and electrochemical reduction pathway shift

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外文摘要：Unravelling the influence of strain and geometric effects on the electrochemical reduction of carbon dioxide(CO2RR)on Cu-based(or Pd-based)alloys remains challenging due to complex local microenvironment variables.Herein,we employ two PdCu alloys(nanoparticles and nanodendrites)to demonstrate how CO2RR selectivity can shift from CO to HCOO-.Despite sharing consistent phases,exposed crystal facets,and overall oxidative states,these alloys exhibit different local strain profiles due to their distinct geometries.By integrating experimental data,in-situ spectroscopy,and density functional theory calculations,we revealed that CO2 prefers adsorption on tensile-strained areas with carbon-side geometry,following a*COOH-to-CO pathway.Conversely,on some compressive-strained regions induced by the dendrite-like morphology,CO2 adopts an oxygen-side geometry,favoring an *OCHO-to-HCOO pathway due to the downshift of the d-band center.Notably,our findings elucidate a dominant *OCHO-to-HCOO-pathway in catalysts when featuring both adsorption geometries.This research provides a comprehensive model for local environment of bimetallic alloys,and establishes a clear relationship between the CO2RR pathway shift and variation in local strain environments of PdCu alloys.

外文关键词：

local strainCO2 electroreductionpathway shiftPdCu alloys

作者：

Chuhao Liu、Yifan Bu、Yifei Xu、Azhar Mahmood、Jisheng Xie、Yifan Fu、Shiyun Li、Cheng Peng、Yue Wu、Xiao Liang、Ruilong Zong、Wan-Lu Li、Jihan Zhou、Bingjun Xu、Li Niu、Mufan Li

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作者单位：

College of Chemistry and Molecular Engineering,Peking University,Beijing 100871,China

School of Chemistry and Chemical Engineering,Guangzhou University,Guangzhou 510006,China

College of Materials Science and Engineering,Fuzhou University,Fuzhou 350108,China

Department of Chemistry,Tsinghua University,Beijing 100084,China

Department of NanoEngineering,University of California,San Diego,La Jolla 92093,USA

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出版年：

2024

DOI：

10.1093/nsr/nwae191

国家科学评论(英文版)

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ISSN：

年,卷(期)：2024.11(12)