In situ evolved phase and heterostructure boosting nitrate to ammonia synthesis for enhanced energy supply in Zn-NO_(3)^(-)battery  

作　　者：Chunming Yang Feng Yue Tingting Wei Xiang Li Wangchuan Zhu Chuantao Wang Yanzhong Zhen Feng Fu Yucang Liang 

机构地区：[1]Research Institute of Comprehensive Energy Industry Technology,College of Chemistry&Chemical Engineering,Yan’an University,Yan’an 716000,Shaanxi,China [2]Institut für Anorganische Chemie,Eberhard Karls Universität Tübingen,Auf der Morgenstelle 18,D-72076 Tübingen,Germany

出　　处：《Journal of Energy Chemistry》2025年第3期73-83,共11页能源化学(英文版)

基　　金：supported by National Natural Science Foundation of China(22162025);the Youth Innovation Team of Shaanxi Universities;the Open and Innovation Fund of Hubei Three Gorges Laboratory(SK232001);the Regional Innovation Capability Leading Program of Shaanxi(2022QFY07-03,2022QFY07-06);the Shaanxi Province Training Program of Innovation and Entrepreneurship for Undergraduates(S202210719108)。

摘　　要：Revealing the dynamic reconfiguration of catalysts and the evolution of active species during catalysis,elucidating and regulating the reconfiguration mechanism are paramount to the development of highperformance electrochemical nitrate reduction(NO_(3)RR)to ammonia.In-situ characterizations can precisely track reaction process and unveil the origin of activity enhancement.Here,in-situ reconstruction of pre-catalyst Co_(3)O_(4)fabricates a stable heterojunction Co(OH)_(2)/Co_(3)O_(4)to boost NO_(3)RR to ammonia.Insitu generated heterojunction accelerates the transformation of^(*)NO_(3)to^(*)NO_(2),while Co(OH)_(2)promotes the dissociation of water to active*H species for the hydrogenation of^(*)N species,and thereby improving the deoxygenation and hydrogenation ability of NO_(3)RR to NH_(3)and achieving a high Faradaic efficiency(FE)about 96.2%and a high NH_(3)production rate of 218.5μmol h^(-1)mg_(cat)^(-1)at-0.3 V.Density functional theory(DFT)calculations verified that in-situ formed active species Co(OH)_(2)on Co_(3)O_(4)markedly decreased the energy barrier of^(*)NO_(3)→^(*)NO_(2)and accelerated the hydrogenation step of^(*)NH→^(*)NH_(2)→^(*)NH_(3).Co(OH)_(2)/Co_(3)O_(4)heterostructure-based Zn-NO_(3)^(-)cell achieves excellent energy supply(1.22 V),a high ammonia yield rate(48.9μmol h^(-1)cm^(-2)),and a high FE(91%).The establishment of the structure-activity relationship during NO_(3)RR provides guidance for designing advanced electrode materials,and the in-situ evolution of species on the electrode surface unveils the intrinsic nature of improved catalytic performance.

关 键 词：Co(OH)_(2)/Co_(3)O_(4)heterostructure Electrocatalytic nitrate reduction In situ reconstruction Ammonia synthesis Zinc-nitrate battery 

分 类 号：O643.36[理学—物理化学]