Band edge modulation via a hydrogen-bond-free cation in hybrid bismuth iodine for overall photocatalytic CO2 reduction

Overall photocatalytic CO2 reduction (PCR) which transforms CO2 with H2O into value-added products without sacrificial reagents has attracted tremendous interest but is hindered by the large overpotential of the H2O oxidation half-reaction. We propose organic cation engineering by employing a “hydro...

Full description

Saved in:
Bibliographic Details
Published in:Inorganic chemistry frontiers 2024-07, Vol.11 (14), p.4364-4373
Main Authors: Liu, Guang-Ning, Cheng-Cheng, Gao, Fangzheng Qi, Wen-Tong, Chen, Ning-Ning, Zhang, Sun, Yiqiang, Zhao, Huaiqing, Chen, Guozhu, Li, Cuncheng
Format: Article
Language:English
Subjects:
Bismuth halides
Carbon dioxide
Cations
Halides
Hydrogen
Hydrogen bonds
Iodine
Methylation
Molecular orbitals
Oxidation
Photocatalysis
Reagents
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Overall photocatalytic CO2 reduction (PCR) which transforms CO2 with H2O into value-added products without sacrificial reagents has attracted tremendous interest but is hindered by the large overpotential of the H2O oxidation half-reaction. We propose organic cation engineering by employing a “hydrogen-bond-free” cation instead of a “hydrogen bond” cation to optimize the band edges and PCR performance of hybrid bismuth halides. (H2biz)BiI4·H2O (Hbiz = benzimidazole, 1) and (Me2biz)BiI4 (2) were designed. The methylation modification on Hbiz affords a “hydrogen-bond-free” cation (Me2biz)+ in 2 with a greatly increased VB edge of 1.31 eV (0.53 eV larger than that of 1), which activates the H2O oxidation half-reaction thermodynamically. Theoretical calculations disclose that the methylation modification greatly increases the highest occupied molecular orbital energy of the cation, thereby increasing the VB edge of 2. This study on 2 represents the first report of a hybrid bismuth-based photocatalyst for an overall PCR reaction in pure water.
ISSN:2052-1545
2052-1553
DOI:10.1039/d4qi01139b