Issue 3, 2022

Efficient modulation of the catalytic performance of electrocatalytic nitrogen reduction with transition metals anchored on N/O-codoped graphene by coordination engineering

Abstract

We for the first time report the discovery of a series of highly efficient electrocatalysts, i.e., transition metals anchored on N/O-codoped graphene, for nitrogen fixation via high-throughput screening combined with first-principles calculations. The catalytic performance can be effectively modulated by coordination engineering. Among 10 representative electrocatalysts (i.e., V–N4@Gra, Tc–N4@Gra, V–O1N3@Gra, V–O2N2α@Gra, V–O2N2β@Gra, V–O2N2γ@Gra, V–O3N1@Gra, Mo–O3N1@Gra, V–O4@Gra and Ru–O4@Gra), V–O2N2γ@Gra possesses the lowest ΔGmax of 0.38 eV. Molecular dynamics simulation results indicate that all the predicted TM–OxNy@Gra (x + y = 4) have high stabilities and can be used as electrocatalysts under practical reaction conditions. The more charge on the adsorbed N2, the longer the N–N bond length and the greater the activation of N2. Interestingly, the linear combination of adsorption energy of different intermediates, i.e., ΔEads[(*N2 − *N) + (*NNH − *N) + (*NH2 − *N)], can be used as a good descriptor to unveil the structure–property relations, and V–O2N2γ@Gra possessed moderate adsorption energy, so it exhibits the highest catalytic activity for the electrocatalytic nitrogen reduction reaction (eNRR) among all investigated materials. Overall, through coordination engineering, the coordination environment and electronic structure of the active centers can be modulated properly, thereby regulating the catalytic activity effectively. We expect that our work will provide new insights into the rational design of electrocatalysts and effective modulation of the catalytic performance via coordination engineering. The present study opens up an important route for the development of efficient catalysts for the eNRR, and will inspire the follow-up experimental and theoretical efforts in this direction.

Graphical abstract: Efficient modulation of the catalytic performance of electrocatalytic nitrogen reduction with transition metals anchored on N/O-codoped graphene by coordination engineering

Supplementary files

Article information

Article type
Paper
Submitted
14 Oct 2021
Accepted
01 Dec 2021
First published
02 Dec 2021

J. Mater. Chem. A, 2022,10, 1481-1496

Efficient modulation of the catalytic performance of electrocatalytic nitrogen reduction with transition metals anchored on N/O-codoped graphene by coordination engineering

X. Wang and L. Yang, J. Mater. Chem. A, 2022, 10, 1481 DOI: 10.1039/D1TA08877G

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