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Understanding of Strain Effects in the Electrochemical Reduction of CO 2 : Using Pd Nanostructures as an Ideal Platform
Author(s) -
Huang Hongwen,
Jia Huanhuan,
Liu Zhao,
Gao Pengfei,
Zhao Jiangtao,
Luo Zhenlin,
Yang Jinlong,
Zeng Jie
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201612617
Subject(s) - catalysis , faraday efficiency , electrochemistry , reversible hydrogen electrode , materials science , density functional theory , nanostructure , chemical physics , adsorption , electrode , valence (chemistry) , octahedron , strain (injury) , nanotechnology , chemical engineering , chemistry , computational chemistry , crystallography , crystal structure , working electrode , medicine , biochemistry , organic chemistry , engineering
Tuning the surface strain of heterogeneous catalysts represents a powerful strategy to engineer their catalytic properties by altering the electronic structures. However, a clear and systematic understanding of strain effect in electrochemical reduction of carbon dioxide is still lacking, which restricts the use of surface strain as a tool to optimize the performance of electrocatalysts. Herein, we demonstrate the strain effect in electrochemical reduction of CO 2 by using Pd octahedra and icosahedra with similar sizes as a well‐defined platform. The Pd icosahedra/C catalyst shows a maximum Faradaic efficiency for CO production of 91.1 % at −0.8 V versus reversible hydrogen electrode (vs. RHE), 1.7‐fold higher than the maximum Faradaic efficiency of Pd octahedra/C catalyst at −0.7 V (vs. RHE). The combination of molecular dynamic simulations and density functional theory calculations reveals that the tensile strain on the surface of icosahedra boosts the catalytic activity by shifting up the d ‐band center and thus strengthening the adsorption of key intermediate COOH*. This strain effect was further verified directly by the surface valence‐band photoemission spectra and electrochemical analysis.