Activity Origins and Design Principles of Nickel-Based Catalysts for Nucleophile Electrooxidation
Activity Origins and Design Principles of Nickel-Based Catalysts for Nucleophile Electrooxidation
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镍基亲核电氧化催化剂的活性起源和设计原理
DOI：
10.1016/j.chempr.2020.07.022
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发表时间：
2020-11-05
期刊：
影响因子：
23.5
通讯作者：
Wang, Shuangyin
中科院分区：
文献类型：
--
作者：
Chen, Wei;Xie, Chao;Wang, Shuangyin
了解电催化剂如何在阳极亲核氧化反应（NOR）中取代水裂解的析氧反应（OER），对制氢和有机电合成的发展至关重要。本文提出β - ni (OH)(2)和NiO的NOR活性来源分别是β - ni (OH)O含有亲电晶格氧和NiO(OH)ads含有亲电吸附氧。对于β - ni (OH)(2)， NOR是一个两步单电子反应，包括电催化脱氢反应和自发亲核试剂脱氢反应。因此，β - ni (OH)(2)的NOR活性可以通过调整晶格氧配体环境来显著调节。对于β - co0.1 ni0.9 (OH)(2)，不同亲核试剂对NOR的起效电位接近1.29 V (1 M KOH)，打破了大多数镍基催化剂的起效电位接近1.35 V的瓶颈。总之，我们确定了活性来源，并提出了镍基NOR催化剂的设计原则。这为NOR和有机电合成在实际工业应用中的发展提供了理论指导。
Understanding how electrocatalysts function in a nucleophile oxidation reaction (NOR) on anode, replacing the oxygen evolution reaction (OER) of water splitting, is vital to the development of hydrogen generation and organic electrosynthesis. Here, we propose that for beta-Ni(OH)(2) and NiO, the NOR activity origins are beta-Ni(OH)O containing electrophilic lattice oxygen and NiO(OH)ads containing electrophilic adsorption oxygen, respectively. For beta-Ni(OH)(2), NOR is a two-step, one-electron reaction, including an electrogenerated catalyst dehydrogenation reaction and a spontaneous nucleophile dehydrogenation reaction. Therefore, the NOR activity of beta-Ni(OH)(2) can be markedly regulated by tuning the lattice oxygen ligand environment. For beta-Co0.1Ni0.9(OH)(2), the onset potential of NOR with different nucleophiles is similar to 1.29 V (1 M KOH), which breaks the bottleneck of similar to 1.35 V for most nickel-based catalysts. Overall, we identify the activity origins and propose the design principles of nickel-based catalysts for NOR. These provide theoretical guidance for the development of NOR and organic electrosynthesis in practical industrial applications.