Understanding
the Intrinsic Mechanism of High-Performance Electrocatalytic Nitrogen
Fixation by Heterogenization of Homonuclear Dual Atom Catalyst
Yuefei Zhang1,2#, Yu Yang1,2#, Yu
Zhang,3,4, Xuefei Liu1,2*, Wenjun
Xiao1,2, Degui Wang1,2, Gang
Wang1,2, Zhen Wang1,2, Jinshun
Bi1,2*, Jin-Cheng Liu5,6,*, Xun Zhou1,2, Wentao Wang7,*
1 School of Integrated Circuit, Guizhou Normal
University, Guiyang, 550025, China.
2 School of physics and electronic science, Guizhou
Normal University, Guiyang 550025, China.
3Jincheng Research Institute of Opto-mechatronics
Industry.
4Shanxi Key Laboratory of Advanced Semiconductor
Optoelectronic Devices and Integrated Systems.
5 Center for Rare Earth and Inorganic Functional
Materials, School of Materials Science and Engineering & National
Institute for Advanced Materials, Nankai University, Tianjin 300350,
China
6 Haihe Laboratory of Sustainable Chemical
Transformations, Tianjin 300192, China
7 Guizhou Provincial Key Laboratory of Computational
Nano-Material Science, Guizhou Education University, Guiyang, 550018,
China;
* Corresponding author; # Contributed equally to this
work.
Email: 201307129@gznu.edu.cn(X.L.); bijinshun@gznu.edu.(J.B.);
liujincheng@nankai.edu.cn(J.L.), wuli8@163.com(W. W);
Abstract: A heteronuclear dual transition metal atom catalyst
is a promising strategy to solve and relieve the increasing energy and
environment crisis. However, the role of each atom still does not
efficiently differentiate due to the high activity but low detectivity
of each transition metal in the synergistic catalytic process when
considering the influence of heteronuclear induced atomic difference for
each transition metal atom, thus seriously hindering intrinsic mechanism
finding. Herein, we proposed coordinate environment vary induced
heterogenization of homonuclear dual transition metal, which inherits
the advantage of heteronuclear transition metal atom catalyst but also
controls the variable of the two atoms to explore the underlying
mechanism. Based on this proposal, employing density functional theory
study and machine learning, 23 kinds of homonuclear transition metals
are doping in four asymmetric C3N for heterogenization
to evaluate the underlying catalytic mechanism. Our results demonstrate
that five catalysts exhibit excellent catalytic performance with a low
limiting potential of -0.28 to -0.48 V. In the meantime, a new
mechanism, ’capture-charge distribution-recapture-charge
redistribution’, is developed for both side-on and end-on configuration.
More importantly, the pronate site of the first hydrogenation is
identified based on this mechanism. Our work not only initially makes a
deep understanding of the transition dual metal-based heteronuclear
catalyst indirectly but also broadens the development of complicated
homonuclear dual atom catalysts in the future.