Issue 8, 2020

Nitrogen electroreduction performance of transition metal dimers embedded into N-doped graphene: a theoretical prediction

Abstract

The electrocatalytic nitrogen reduction reaction (eNRR) under ambient conditions using sustainable energy sources is a fascinating approach for ammonia (NH3) production to replace the industrial Haber–Bosch process with enormous energy input and continuous CO2 emissions. However, the eNRR process remains a coveted goal due to the poor product selectivity, low activity, and stability of traditional catalysts. Inspired by recent experimental advances in dual-atom catalysts, herein, by means of comprehensive spin-polarized density functional theory (DFT) computations, the catalytic performance of various binary transition metals dispersed in nitrogen-doped porous graphene (NPG) for the eNRR was systematically evaluated. Our results revealed that the N atoms around vacancies in the substrate can strongly stabilize the metal dimers by forming metal–N bonds. Among FeFe, FeCo, FeNi, FeCu, FeRh, FeRu, FePd, MoFe, MoCo, MoCu, MoRu, and MoMo, the binary FeRh embedded in NPG was identified as the best catalyst due to its lowest limiting potential (−0.22 V) and high selectivity towards the eNRR. Our results further suggested that the good eNRR catalytic activity of the dispersed FeRh mainly originates from its optimal eNRR intermediates’ adsorption/desorption features, obvious suppressing effects on the hydrogen evolution reaction, and great promise for synthesis. Our work not only opens a new door to advance sustainable NH3 production by tailoring the electronic structures of binuclear metal atoms, but also provides deeper insight into the structure–performance relationships of dual sites for eNRR electrocatalysts.

Graphical abstract: Nitrogen electroreduction performance of transition metal dimers embedded into N-doped graphene: a theoretical prediction

Supplementary files

Article information

Article type
Paper
Submitted
12 Dec 2019
Accepted
29 Jan 2020
First published
30 Jan 2020

J. Mater. Chem. A, 2020,8, 4533-4543

Nitrogen electroreduction performance of transition metal dimers embedded into N-doped graphene: a theoretical prediction

H. Li, Z. Zhao, Q. Cai, L. Yin and J. Zhao, J. Mater. Chem. A, 2020, 8, 4533 DOI: 10.1039/C9TA13599E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements