Issue 34, 2024

Mechanistic study of the competition between carbon dioxide reduction and hydrogen evolution reaction and selectivity tuning via loading single-atom catalysts on graphitic carbon nitride

Abstract

In the context of catalytic CO2 reduction (CO2RR), the interference of the inherent hydrogen evolution reaction (HER) and the possible selectivity towards CO have posed a significant challenge to the generation of formic acid. To address this hurdle, in this work, we have investigated the impact of different single-atom metal catalysts on tuning selectivity by employing density functional theory (DFT) calculations to scrutinize the reaction pathways. Single-atom catalysts supported on carbon-based systems have proven to be pivotal in altering both the activity and selectivity of the CO2RR. In this study, a series of single-atom-metal-loaded g-C3N4 monolayers (MCN, M = Ni, Cu, Zn, Ga, Cd, In, Sn, Pb, Ag, Au, Bi, Pd and Pt) were systematically examined. Through detailed DFT calculations, we explored their influence on reaction selectivity between the *COOH and *OCHO intermediates. Notably, NiCN favors the reaction via the *OCHO route, with a significantly lower rate-determining potential of 0.36 eV, which is approximately 73.5% lower than that of the CN system (1.36 eV). Most importantly, the Ni single-atom catalyst with lower coordination significantly enhances CO2 adsorption, promoting CO2RR over HER. Overall, this study, guided by DFT calculations, provides a theoretical prediction of how the selection of single-atom metal catalysts can effectively modulate the reaction pathway, thereby offering a potential solution for achieving high product selectivity in CO2RR.

Graphical abstract: Mechanistic study of the competition between carbon dioxide reduction and hydrogen evolution reaction and selectivity tuning via loading single-atom catalysts on graphitic carbon nitride

Supplementary files

Article information

Article type
Paper
Submitted
04 may 2024
Accepted
01 iyl 2024
First published
01 iyl 2024

Nanoscale, 2024,16, 16015-16025

Mechanistic study of the competition between carbon dioxide reduction and hydrogen evolution reaction and selectivity tuning via loading single-atom catalysts on graphitic carbon nitride

J. J. Foo, S. Ng, M. Xiong and W. Ong, Nanoscale, 2024, 16, 16015 DOI: 10.1039/D4NR01932F

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