Novel metal-free holey BC4N nanostructure for enhanced photoelectrocatalytic nitrogen reduction: insight from grand-canonical density functional theory

The carbon-based metal-free catalysts with graphene-like structures have been demonstrated to be highly efficient in promoting both photocatalytic and electrocatalytic reactions. Here, in the framework of constant potential model (CPM), we computationally explore material and catalytic properties of...

Full description

Saved in:
Bibliographic Details
Published in:Science China materials 2024-04, Vol.67 (4), p.1192-1201
Main Authors: Li, Yunyi, An, Wei, Wang, Yibo, Liu, Mingming, Guo, Ruixian, Shi, Xugen, Dai, Enduo, Men, Yong
Format: Article
Language:English
Subjects:
Ammonia
Aqueous electrolytes
Chemical reduction
Chemistry and Materials Science
Chemistry/Food Science
Density functional theory
Electron transfer
Electrons
Graphene
Materials Science
Molecular dynamics
Photocathodes
Reaction intermediates
Ultraviolet radiation
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The carbon-based metal-free catalysts with graphene-like structures have been demonstrated to be highly efficient in promoting both photocatalytic and electrocatalytic reactions. Here, in the framework of constant potential model (CPM), we computationally explore material and catalytic properties of the proposed novel two-dimensional BC 4 N structure for promoting the photoelectrocatalytic (PEC) N 2 reduction reaction (NRR). The results reveal that BC 4 N as a photocathode exhibits high efficiency of harvesting visible light and ultraviolet light. The photogenerated electrons can deliver a potential of U e = −1.07 V, sufficient to overcome the potential-limiting step in PEC NRR in continuum aqueous electrolyte solution. Moreover, it is found that the co-adsorbed reaction intermediates play an important role in mediating/facilitating the NRR towards NH 3 formation. Ab-initio molecular dynamics simulations indicate that the proton-coupled electron transfer can interplay with the intermolecular hydrogen transfer, leaving NRR mechanism even complicated at the atomic scale. The underlying disparity in CPM and the popular constant charge model was also discussed. This study provides fundamental insight into working mechanism of metal-free semiconducting materials driving photo-assisted PEC NRR under quasi-realistic conditions.
ISSN:2095-8226
2199-4501
DOI:10.1007/s40843-023-2805-y