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Oxygen-Inserted Top-Surface Layers of Ni for Boosting Alkaline Hydrogen Oxidation Electrocatalysis

Precisely tailoring the electronic structures of electrocatalysts to achieve an optimum hydroxide binding energy (OHBE) is vital to the alkaline hydrogen oxidation reaction (HOR). As a promising alternative to the Pt-group metals, considerable efforts have been devoted to exploring highly efficient...

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Published in:Journal of the American Chemical Society 2022-07, Vol.144 (28), p.12661-12672
Main Authors: Men, Yana, Su, Xiaozhi, Li, Peng, Tan, Yue, Ge, Chuangxin, Jia, Shuangfeng, Li, Lei, Wang, Jianbo, Cheng, Gongzhen, Zhuang, Lin, Chen, Shengli, Luo, Wei
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container_end_page 12672
container_issue 28
container_start_page 12661
container_title Journal of the American Chemical Society
container_volume 144
creator Men, Yana
Su, Xiaozhi
Li, Peng
Tan, Yue
Ge, Chuangxin
Jia, Shuangfeng
Li, Lei
Wang, Jianbo
Cheng, Gongzhen
Zhuang, Lin
Chen, Shengli
Luo, Wei
description Precisely tailoring the electronic structures of electrocatalysts to achieve an optimum hydroxide binding energy (OHBE) is vital to the alkaline hydrogen oxidation reaction (HOR). As a promising alternative to the Pt-group metals, considerable efforts have been devoted to exploring highly efficient Ni-based catalysts for alkaline HOR. However, their performances still lack practical competitiveness. Herein, based on insights from the molecular orbital theory and the Hammer–Nørskov d-band model, we propose an ingenious surface oxygen insertion strategy to precisely tailor the electronic structures of Ni electrocatalysts, simultaneously increasing the degree of energy-level alignment between the adsorbed hydroxide (*OH) states and surface Ni d-band and decreasing the degree of anti-bonding filling, which leads to an optimal OHBE. Through the pyrolysis procedure mediated by a metal–organic framework at a low temperature under a reducing atmosphere, the obtained oxygen-inserted two atomic-layer Ni shell-modified Ni metal core nanoparticle (Ni@Oi-Ni) exhibits a remarkable alkaline HOR performance with a record mass activity of 85.63 mA mg–1, which is 40-fold higher than that of the freshly synthesized Ni catalyst. Combining CO stripping experiments with ab initio calculations, we further reveal a linear relationship between the OHBE and the content of inserted oxygen, which thus results in a volcano-type correlation between the OH binding strength and alkaline HOR activity. This work indicates that the oxygen insertion into the top-surface layers is an efficient strategy to regulate the coordination environment and electronic structure of Ni catalysts and identifies the dominate role of OH binding strength in alkaline HOR.
doi_str_mv 10.1021/jacs.2c01448
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As a promising alternative to the Pt-group metals, considerable efforts have been devoted to exploring highly efficient Ni-based catalysts for alkaline HOR. However, their performances still lack practical competitiveness. Herein, based on insights from the molecular orbital theory and the Hammer–Nørskov d-band model, we propose an ingenious surface oxygen insertion strategy to precisely tailor the electronic structures of Ni electrocatalysts, simultaneously increasing the degree of energy-level alignment between the adsorbed hydroxide (*OH) states and surface Ni d-band and decreasing the degree of anti-bonding filling, which leads to an optimal OHBE. Through the pyrolysis procedure mediated by a metal–organic framework at a low temperature under a reducing atmosphere, the obtained oxygen-inserted two atomic-layer Ni shell-modified Ni metal core nanoparticle (Ni@Oi-Ni) exhibits a remarkable alkaline HOR performance with a record mass activity of 85.63 mA mg–1, which is 40-fold higher than that of the freshly synthesized Ni catalyst. Combining CO stripping experiments with ab initio calculations, we further reveal a linear relationship between the OHBE and the content of inserted oxygen, which thus results in a volcano-type correlation between the OH binding strength and alkaline HOR activity. 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