Electronic Modulation between Tungsten Nitride and Cobalt Dopants for Enhanced Hydrogen Evolution Reaction at a Wide Range of pH
Electronic Modulation between Tungsten Nitride and Cobalt Dopants for Enhanced Hydrogen Evolution Reaction at a Wide Range of pH
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DOI：
10.1002/cctc.202000391
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发表时间：
2020-06
期刊：
影响因子：
4.5
通讯作者：
Zhizhong Liu;Xuming Zhang;Hao Song;Yixuan Yang;Yang Zheng;B. Gao;Jijiang Fu;P. Chu;K. Huo
中科院分区：
文献类型：
--
作者：
Zhizhong Liu;Xuming Zhang;Hao Song;Yixuan Yang;Yang Zheng;B. Gao;Jijiang Fu;P. Chu;K. Huo
具有铂类化学性质的过渡金属氮化物是重要的电催化剂，氮化钨（WN）是一种良好的加氢脱氮和加氢脱硫催化剂，但其析氢反应（HER）的催化活性较差，因为其不利的d能带电子结构导致与吸附氢的强相互作用。本文报道了在碳布上生长的Co掺杂纳米线阵列，结果表明Co掺杂剂不仅作为活性位点，而且由于电子从W转移到Co，通过降低W位d带中心的位置来增加W位的活性。密度泛函理论（DFT）和态密度（DOS）计算证实，增强的HER性能归因于W的d带中心的调制和引入的Co掺杂剂，从而促进了HER过程。电子调制的结果为高活性电催化剂的设计提供了新的思路。
Transition metal nitrides with Pt‐like chemical properties are important electrocatalysts and tungsten nitride (WN) is a good hydrodenitrogenation and hydrodesulfurization catalyst but its catalytic activity for hydrogen evolution reaction (HER) is poor because of the unfavourable d‐band electronic structure resulting in strong interactions with adsorbed hydrogen. Herein, Co doped WN nanowire arrays grown on carbon cloth are reported and the result shows that Co dopants not only act as active sites, but also increase activity of W sites by downshifting the position of d‐band centre of W sites as a result of the electron transfer from W to Co. Density‐functional theory (DFT) and density of states (DOS) calculations confirm that the enhanced HER performance is attributed to the modulation of the d‐band center of W and introduced Co dopants both consequently facilitating the HER process. The results on electronic modulation provide insights into the design of electrocatalysts with high activity.