P-band center theory guided activation of MoS_(2) basal S sites for pHuniversal hydrogen evolution  

作　　者：Chao Meng Yuanfeng Gao Yue Zhou Kang Sun Yanmin Wang Ye Han Qianqian Zhao Xuemin Chen Han Hu Mingbo Wu 

机构地区：[1]State Key Laboratory of Heavy Oil Processing,Institute of New Energy,China University of Petroleum(East China),Qingdao 266580,China [2]College of Electrical Engineering and Automation,Shandong University of Science and Technology,Qingdao 266590,China [3]College of Energy Storage Technology,Shandong University of Science and Technology,Qingdao 266590,China [4]Institute of Chemical Industry of Forest Products,Chinese Academy of Forestry,Nanjing 210042,China [5]School of Materials Science and Engineering,Shandong University of Science and Technology,Qingdao 266590,China [6]College of Science,Hebei University of Science and Technology,Shijiazhuang 050018,China

出　　处：《Nano Research》2023年第5期6228-6236,共9页纳米研究（英文版）

基　　金：the National Natural Science Foundation of China(Nos.51901115 and 51802075);the Shandong Provincial Natural Science Foundation,China(Nos.ZR2019PEM001,ZR2019BB009,and ZR2020ZD08);the Young Talents Program in University of Hebei Province,China(No.BJ2019002).

摘　　要：The edge S sites of thermodynamically stable 2H MoS_(2)are active for hydrogen evolution reaction(HER)but the active sites are scarce.Despite the dominance of the basal S sites,they are generally inert to HER because of the low p-band center.Herein,we reported a synergistic combination of phase engineering and NH_(4)^(+) intercalation to promote the HER performance of MoS_(2).The rational combination of 1T and 2H phases raises the p-band center of the basal S sites while the intercalated NH4+ions further optimize and stabilize the electronic band of these sites.The S sites with regulated band structures afford moderate hydrogen adsorption,thus contributing to excellent HER performance over a wide pH range.In an acid medium,this catalyst exhibits a low overpotential of 169 mV at 10 mA·cm^(−2)and Tafel slope of 39 mV·dec^(−1)with robust stability,superior to most of recently reported MoS_(2)-based non-noble catalysts.The combined use of in/ex-situ characterizations ravels that the appearance of more unpaired electrons at the Mo 4d-orbital reduces the d-band center which upshifts the p-band center of the adjacent S for essentially improved HER performance.This work provides guidelines for the future development of layered transition-metal-dichalcogenide catalysts.

关 键 词：molybdenum disulfide p-orbital electron structure basal S sites hydrogen evolution synergistic mechanism 

分 类 号：O64[理学—物理化学]