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 

机构地区：[1]State Key laboratory of Fine Chemicals,Frontier Science Center for Smart Materials,School of Chemistry,Dalian University of Technology,Dalian 116024,China

出　　处：《Nano Research》2024年第3期1094-1100,共7页纳米研究（英文版）

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).

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.

关 键 词：broken D4h single nickel sites oxygen reduction H_(2)O_(2)production 

分 类 号：O64[理学—物理化学]