Asymmetric configuration activating lattice oxygen via weakening d-p orbital hybridization for efficient C/N separation in urea overall electrolysis  

作　　者：Chongchong Liu Peifang Wang Bin Hu Xiaoli Liu Rong Huang Gang Zhou 

机构地区：[1]Key Laboratory of Integrated Regulation and Resource Development on Shallow Lake of Ministry of Education,College of Environment,Hohai University,Nanjing 210098,Jiangsu,China

出　　处：《Journal of Energy Chemistry》2024年第5期233-239,共7页能源化学（英文版）

基　　金：supported by Fundamental Research Funds for the Central Universities(B220202062);supported by Key Program of National Natural Science Foundation of China(92047201,92047303,52102237);National Science Funds for Creative Research Groups of China(51421006);supported by Postdoctoral Science Foundations of China and Jiangsu Province(2021M690861,2022T150183,2021K065A)。

摘　　要：Urea oxidation reaction(UOR)is proposed as an exemplary half-reaction in renewable energy applications because of its low thermodynamical potential.However,challenges persist due to sluggish reaction kinetics and complex by-products separation.To this end,we introduce the lattice oxygen oxidation mechanism(LOM),propelling a novel UOR route using a modified CoFe layered double hydroxide(LDH)catalyst termed CFRO-7.Theoretical calculations and in-situ characterizations highlight the activated lattice oxygen(O_(L))within CFRO-7 as pivotal sites for UOR,optimizing the reaction pathway and accelerating the kinetics.For the urea overall electrolysis application,the LOM route only requires a low voltage of 1.54 V to offer a high current of 100 mA cm^(-2) for long-term utilization(>48 h).Importantly,the by-product NCO^(-)−is significantly suppressed,while the CO_(2)2/N_(2) separation is efficiently achieved.This work proposed a pioneering paradigm,invoking the LOM pathway in urea electrolysis to expedite reaction dynamics and enhance product selectivity.

关 键 词：Lattice oxygen Urea oxidation reaction Overall electrolysis Products selectivity 

分 类 号：TQ031[化学工程]