Accelerating water dissociation kinetics of Ni3N by tuning interfacial orbital coupling  

作　　者：Yishang Wu Yufang Xie Shuwen Niu Yipeng Zang Jinyan Cai Zenan Bian Xuanwei Yin Yanyan Fang Da Sun Di Niu Zheng Lu Amirabbas Mosallanezhad Huijuan Wang Dewei Rao Hongge Pan Gongming Wang 

机构地区：[1]Hefei National Laboratory for Physical Science at the Microscale,Department of Chemistry,University of Science and Technology of China,Hefei 230026,China [2]Experimental Center of Engineering and Material Science,University of Science and Technology of China,Hefei 230026,China [3]School of Materials Science and Engineering,Jiangsu University,Zhenjiang 212013,China [4]Institute of Science and Technology for New Energy,Xi’an Technological University,Xi’an 710021,China [5]School of Materials Science and Engineering,State Key Laboratory of Silicon Materials,Zhejiang University,Hangzhou 310027,China

出　　处：《Nano Research》2021年第10期3458-3465,共8页纳米研究（英文版）

基　　金：The work was supported by the National Natural Science Foundation of China(Nos.21771169 and 11722543);the National Key Research and Development Program of China(No.2017YFA0206703);Anhui Provincial Natural Science Foundation(No.BJ2060190077);Collaborative Innovation Program of Hefei Science Center,CAS,and the Fundamental Research Funds for the Central Universities(Nos.WK2060190074,WK2060190081,WK2310000066,and WK2060000015).

摘　　要：The high unoccupied d band energy of Ni_(3)N basically results in weak orbital coupling with water molecule,consequently leading to slow water dissociation kinetics.Herein,we demonstrate Cr doping can downshift the unoccupied d orbitals and strengthen the interfacial orbital coupling to boost the water dissociation kinetics.The prepared Cr-Ni_(3)N/Ni displays an impressive overpotential of 37 mV at 10 mA·cmgeo-2,close to the benchmark Pt/C in 1.0 M KOH solution.Refined structural analysis reveals the Cr dopant exists as the Cr-N_(6)states and the average d band energy of Ni_(3)N is also lowered.Density functional theory calculation further confirms the downshifted d band energy can strengthen the orbital coupling between the unpaired electrons in O 2p and the unoccupied state of Ni 3d,which thus facilitates the water adsorption and dissociation.The work provides a new concept to achieve on-demand functions for hydrogen evolution catalysis and beyond,by regulating the interfacial orbital coupling.

关 键 词：unoccupied d orbitals Ni_(3)N Cr-N_(6)doping interfacial orbital coupling hydrogen evolution reaction 

分 类 号：O64[理学—物理化学]