CoP-Doped MOF-Based Electrocatalyst for pH-Universal Hydrogen Evolution Reaction
CoP-Doped MOF-Based Electrocatalyst for pH-Universal Hydrogen Evolution Reaction
复制标题
用于 pH 通用析氢反应的 CoP 掺杂 MOF 电催化剂
DOI：
10.1002/anie.201901409
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发表时间：
2019-03-26
影响因子：
16.6
通讯作者：
Yin, Yadong
中科院分区：
文献类型：
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作者：
Liu, Teng;Li, Peng;Yin, Yadong
尽管基于阳离子/阴离子掺杂的过渡金属磷化物（TMP）的电催化剂已被广泛研究用于析氢反应（HER），但性能增强的根源仍然难以捉摸，这主要是由于掺杂剂的随机分散。在此，我们报告了一种可控部分磷化策略，以在钴基金属有机框架（Co-MOF）内生成CoP物种。密度泛函理论计算和实验结果表明，通过N-P/N-Co键从CoP到Co-MOF的电子转移可以导致H2O（Delta G(H2O*)）和氢（Delta G(H*)）的吸附能优化，再加上Co-MOF独特的多孔结构，使得其在1 M磷酸盐缓冲液中在电流密度为10 mA cm(-2)时具有49 mV的过电势。溶液（PBS，pH 7.0）。优异的催化性能超过了几乎所有文献记载的TMP基和非贵金属基电催化剂。此外，CoP/Co-MOF杂化材料在0.5 M H2SO4和1 M KOH中也表现出类似Pt的性能，在10 mA cm(-2)的电流密度下，过电势分别为27和34 mV。
Although electrocatalysts based on transition metal phosphides (TMPs) with cationic/anionic doping have been widely studied for hydrogen evolution reaction (HER), the origin of performance enhancement still remains elusive mainly due to the random dispersion of dopants. Herein, we report a controllable partial phosphorization strategy to generate CoP species within the Co-based metal-organic framework (Co-MOF). Density functional theory calculations and experimental results reveal that the electron transfer from CoP to Co-MOF through N-P/N-Co bonds could lead to the optimized adsorption energy of H2O (Delta G(H2O*)) and hydrogen (Delta G(H*)), which, together with the unique porous structure of Co-MOF, contributes to the remarkable HER performance with an overpotential of 49 mV at a current density of 10 mA cm(-2) in 1 M phosphate buffer solution (PBS, pH 7.0). The excellent catalytic performance exceeds almost all the documented TMP-based and non-noble-metal-based electrocatalysts. In addition, the CoP/Co-MOF hybrid also displays Pt-like performance in 0.5 M H2SO4 and 1 M KOH, with the overpotentials of 27 and 34 mV, respectively, at a current density of 10 mA cm(-2).