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 β-Ni(OH)₂ and NiO, the NOR activity origins are β-Ni(OH)O containing electrophilic lattice oxygen and NiO(OH)_ads containing electrophilic adsorption oxygen, respectively. For β-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 β-Ni(OH)₂ can be markedly regulated by tuning the lattice oxygen ligand environment. For β-Co_0.1Ni_0.9(OH)₂, the onset potential of NOR with different nucleophiles is ∼1.29 V (1 M KOH), which breaks the bottleneck of ∼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.

理解电催化剂如何在阳极上的亲核氧化反应（NOR）中发挥作用，代替水分解过程中的氧释放反应（OER），对于氢生成和有机电合成的发展至关重要。这里，我们提出，对于的β-Ni（OH）₂和NiO，所述NOR活动起源的β-Ni（OH）含亲电晶格氧和NiO（OH）O_广告含有亲电吸附氧，分别。对于β-Ni（OH）₂，NOR是两步单电子反应，包括电生成的催化剂脱氢反应和自发的亲核试剂脱氢反应。因此，可以通过调节晶格氧配体环境来显着调节β-Ni（OH）₂的NOR活性。对于β-Co_0.1 Ni _0.9（OH）₂，具有不同亲核试剂的NOR的起始电位为〜1.29 V（1 M KOH），这打破了大多数镍基催化剂的〜1.35 V的瓶颈。总体而言，我们确定了活性的起源，并提出了用于NOR的镍基催化剂的设计原则。这些为在实际工业应用中开发NOR和有机电合成提供了理论指导。