Constructing ultrafine monodispersed Co_(2)P/(0.59-Cu_(3)P)on Cu doped CoZn-ZIF derived porous N-doped carbon for highly efficient dehydrogenation of ammonia borane  

作　　者：Yinze Yang Liqing Zhao Xiangyang Gao Yafei Zhao 

机构地区：[1]School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,China [2]State Key Laboratory of Electroanalytical Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China [3]School of Environmental Engineering and Chemistry,Luoyang Institute of Science and Technology,Luoyang 471023,China [4]Key Laboratory of Artificial Micro,Nano-structures of Ministry of Education,School of Physics and Technology,Wuhan University,Wuhan 430072,China

出　　处：《Nano Research》2023年第5期6687-6700,共14页纳米研究（英文版）

基　　金：the National Natural Science Foundation of China(Nos.U20041100 and 21706242);Science and Technology Project of Henan Province(No.212102110068).

摘　　要：Rational construction of highly dispersed,small size,low cost catalysts for release of hydrogen from ammonia borane(AB)is regarded as a prospective approach for promoting the development of upcoming hydrogen economy.However,the high price and scarcity of precious metal catalysts impose restrictions on their large-scale application.To this end,with the aid of a Cu doped CoZn-zeolitic imidazolate frameworks(ZIFs)template strategy,we successfully construct ultrafine monodispersed Co_(2)P/(0.59-Cu_(3)P)on CoZn-ZIF derived porous N-doped carbon(Co_(2)P/(0.59-Cu_(3)P)-NC)as an efficient non-noble-metal catalyst.Specifically,Co and Cu atoms can be geometrically separated to high degree due to the presence of Zn in the CuCoZn-ZIF precursor,evaporation of Zn during pyrolysis can generate porous structure with the framework well maintained.The results show that porous Co_(2)P/(0.59-Cu_(3)P)-NC bimetallic phosphide exhibits large specific surface area,hierarchical pore structure,well-exposed active sites.Based on the kinetics analyses and ion effects,the catalyst has achieved an unprecedentedly high total turnover frequency(TOF)of 798 mol·molcat^(−1)·min^(−1)in 0.4 M NaOH solution at 298 K,which surpasses all the ever-reported transition-metal phosphides catalysts for hydrogen generation from AB.Experiments and theoretical studies confirm that the highly porous structure of the support,the ultrafine and high dispersion of nanoparticles,the N/P doping and their synergistic effects(e.g.,M-P,M-N,N-C,M-M',M-support)jointly induce strong electron transfer,which can reduce the reaction energy barrier and enhance their interaction with AB,thus correspondingly obtaining excellent catalytic performance.The mechanism and strategy presented in this work pave an avenue for the design of non-noble metal catalyst for hydrogen energy system.

关 键 词：non-noble metal transition-metal phosphides porous N-doped carbon hydrogen evolution ammonia borane catalytic hydrolysis 

分 类 号：O64[理学—物理化学]