Microwave-assisted exploration of the electron configuration-dependent electrocatalytic urea oxidation activity of 2D porous NiCo_(2)O_(4) spinel  

作　　者：Jun Wan Zhiao Wu Guangyu Fang Jinglin Xian Jiao Dai Jiayue Guo Qingxiang Li Yongfei You Kaisi Liu Huimin Yu Weilin Xu Huiyu Jiang Minggui Xia Huanyu Jin 

机构地区：[1]State Key Laboratory of New Textile Materials and Advanced Processing Technologies,Hubei Key Laboratory of Biomass Fibers and Eco-Dyeing&Finishing,Wuhan Textile University,Wuhan 430200,Hubei,China [2]Institute for Sustainability,Energy and Resources,The University of Adelaide,Adelaide,SA 5005,Australia [3]Future Industries Institute,University of South Australia,Mawson Lakes Campus,Adelaide,SA 5095,Australia

出　　处：《Journal of Energy Chemistry》2024年第4期226-235,共10页能源化学（英文版）

基　　金：financial support from the National Natural Science Foundation of China(52203070);the Open Fund of State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2022005);the Open Fund of Hubei Key Laboratory of Biomass Fiber and Ecological Dyeing and Finishing(STRZ202203);the financial support provided by the China Scholarship Council(CSC)Visiting Scholar Program;financial support from Institute for Sustainability,Energy and Resources,The University of Adelaide,Future Making Fellowship。

摘　　要：Urea holds promise as an alternative water-oxidation substrate in electrolytic cells.High-valence nickelbased spinel,especially after heteroatom doping,excels in urea oxidation reactions(UOR).However,traditional spinel synthesis methods with prolonged high-temperature reactions lack kinetic precision,hindering the balance between controlled doping and highly active two-dimensional(2D)porous structures design.This significantly impedes the identification of electron configuration-dependent active sites in doped 2D nickel-based spinels.Herein,we present a microwave shock method for the preparation of 2D porous NiCo_(2)O_(4)spinel.Utilizing the transient on-off property of microwave pulses for precise heteroatom doping and 2D porous structural design,non-metal doping(boron,phosphorus,and sulfur)with distinct extranuclear electron disparities serves as straightforward examples for investigation.Precise tuning of lattice parameter reveals the impact of covalent bond strength on NiCo_(2)O_(4)structural stability.The introduced defect levels induce unpaired d-electrons in transition metals,enhancing the adsorption of electron-donating amino groups in urea molecules.Simultaneously,Bode plots confirm the impact mechanism of rapid electron migration caused by reduced band gaps on UOR activity.The prepared phosphorus-doped 2D porous NiCo_(2)O_(4),with optimal electron configuration control,outperforms most reported spinels.This controlled modification strategy advances understanding theoretical structure-activity mechanisms of high-performance 2D spinels in UOR.

关 键 词：2D materials SPINEL Microwave ELECTROCATALYSIS Urea oxidation reaction 

分 类 号：O643.36[理学—物理化学]