Valence Engineering via Dual-Cation and Boron Doping in Pyrite Selenide for Highly Efficient Oxygen Evolution
Valence Engineering via Dual-Cation and Boron Doping in Pyrite Selenide for Highly Efficient Oxygen Evolution
复制标题
通过黄铁矿硒化物中的双阳离子和硼掺杂进行化合价工程，以实现高效析氧
DOI：
10.1021/acsnano.9b04956
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发表时间：
2019
期刊：
影响因子：
17.1
通讯作者：
Chai Yang
中科院分区：
文献类型：
--
作者：
Zuo Yunpeng;Rao Dewei;Ma Sainan;Li Tingting;Tsang Yuen Hong;Kment Stepan;Chai Yang
价态工程已被证明是修饰催化剂电子性质和提高其析氧活性的有效方法，但有限的元素数量限制了催化剂的结构多样性和活性位点。此外，催化剂的性能和稳定性也受到催化体系中阳离子溶解、成熟或晶体迁移的极大限制。本文采用一种广泛应用的技术，通过双阳离子取代和硼掺杂制备异质外延硒化黄铁矿，以获得更好的活性和稳定性。硒化镍硫铁矿催化剂在10 mA cm - 2下的过电位从543 mV降至279.8 mV， Tafel斜率从161 mV降至59.5 mV / dec1。我们的理论计算表明，阳离子和硼掺杂都能有效地优化OER中间体的吸附能，促进杂原子间的电荷转移，提高其OER性能。这项工作强调了使用多种元件调制表面电子结构的重要性，并为用价工程最小化活度损失提供了一般指导。
Valence engineering has been proved an effective approach to modify the electronic property of a catalyst and boost its oxygen evolution reaction (OER) activity, while the limited number of elements restricts the structural diversity and the active sites. Also, the catalyst performance and stability are greatly limited by cationic dissolution, ripening, or crystal migration in a catalytic system. Here we employed a widely used technique to fabricate heteroepitaxial pyrite selenide through dual-cation substitution and a boron dopant to achieve better activity and stability. The overpotential of Ni-pyrite selenide catalyst is decreased from 543 mV to 279.8 mV at 10 mA cm–2with a Tafel slope from 161 to 59.5 mV dec–1. Our theoretical calculations suggest both cation and boron doping can effectively optimize adsorption energy of OER intermediates, promote the charge transfer among the heteroatoms, and improve their OER property. This work underscores the importance of modulating surface electronic structure with the use of multiple elements and provides a general guidance on the minimization of activity loss with valence engineering.