Asymmetrically ligated single atomic nickel sites for efficient hydrogen peroxide electrosynthesis

作     者：Xusheng Cheng Jinwen Hu Wenzhe Shang Jingya Guo Cuncun Xin Songlin Zhang Suchan Song Wei Liu Yantao Shi 

作者机构：State Key laboratory of Fine ChemicalsFrontier Science Center for Smart MaterialsSchool of ChemistryDalian University of TechnologyDalian 116024China 

出 版 物：《Nano Research》 (纳米研究（英文版）)

年 卷 期：2024年第17卷第3期

页      面：1094-1100页

核心收录：

学科分类：07[理学] 070304[理学-物理化学(含∶化学物理)] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 0702[理学-物理学] 

基　　金：supported by the National Natural Science Foundation of China(Nos.22002013 and 52272193) the Fundamental Research Funds for the Central Universities(Nos.DUT22LAB602 and DUT20RC(3)021) Liao Ning Revitalization Talents Program(No.XLYC2008032). 

主　　题：broken D4h single nickel sites oxygen reduction H_(2)O_(2)production 

摘      要：Atomic transition-metal-nitrogen-carbon electrocatalysts hold great promise as alternatives to benchmark Pt in the oxygen reduction reaction.The pristine metal centers with quasi square-planar D_(4h) configuration,however,still suffer from unfavorable energetics and thereby strong activity/selectivity trade-off during the catalytic process.Here we present a ligand-field engineering of single-atom Ni-N-C catalysts to boost the sluggish kinetics via rationally constructing prototypical asymmetrically ligated Ni-N_(3)O_(1) sites.The as-obtained Ni-supported multi-walled carbon nanotubes with molten salt-treated(defined as Ni/CNS)catalyst delivered an excellent H_(2)O_(2) selectivity(90%)within a wide potential window(0.2–0.7 V vs.reversible hydrogen electrode(RHE))and robust stability(for 10 h)in alkaline medium.Combined electron paramagnetic resonance and theoretical analysis rationalize this finding and demonstrate that the broken symmetry facilitates the electron transfer of a σ* to O–O orbital as compared to the Ni-N_(4) counterpart,playing an indispensable role in efficient O_(2) activation.