Theoretical study on the application of the largest aluminum-pyrazole ring in electrochemical nitrogen reduction reaction  

作　　者：Zirui Wang Sihao Shen Yupeng Han Weihui Fang Qiaohong Li Jian Zhang 

机构地区：[1]State Key Laboratory of Structural Chemistry.Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]School of Physical Science and Technology,ShanghaiTech University,Shanghai 201210,China [3]Chinese Academy of Sciences,University of Chinese Academy of Sciences,Beijing 100049,China [4]Fujian College,University of Chinese Academy of Sciences,Fuzhou 350002,China

出　　处：《Chinese Chemical Letters》2023年第12期339-342,共4页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.92161105 and 92061104);Natural Science Foundation of Fujian Province(Nos.2021j06035 and 2021J01525);Youth Innovation Promotion Association CAS(No.Y2021081).

摘　　要：Electrochemical nitrogen reduction reaction(NRR)is a mild and sustainable method for ammonia synthesis.Therefore,developing high activity,selectivity,and economic efficiency catalysts with considering the synergistic effects between catalysts and carriers to design novel structural models is very important.Considering the non-noble metal NRR catalyst,Mo3,we tried to find a suitable carrier which is stable and economical.Herein,we used the largest atomically precise aluminum-pyrazole ring(AlOC-69)to date(diameter up to 2.3 nm).The larger ring cavities and the presence of abundant hydroxy groups make AlOC-69 an ideal molecular carrier model and provide a basis for studying its structure-activity relationship.The formation energy(-0.76eV)and stable Mo-0 bonds indicate that Mo_(3)can be stabilized on the Al_(10)O_(10)surface.Additionally,N_(2)has fully activated due to the strong interaction between the p-orbital of N and the d-orbital of Mo.The low limiting potential(-0.28V)emerges that Mo_(3)@Al_(10)O_(10)has ideal catalytic activity and selectivity.This research provides a promising catalyst model and an understanding of its catalytic process at the atomic level,providing a new approach for the co-design of catalyst and carrierin NRR.

关 键 词：Nitrogen reduction reaction Hydrogen evolution reaction ELECTROCATALYSTS Densityfunctional theory Aluminum-pyrazolering Metal catalyst 

分 类 号：TQ113.2[化学工程—无机化工] O643.36[理学—物理化学]