Tuning charge carrier transport in isostructural covalent organic frameworks for enhanced photocatalytic CO2 reduction

Abstract

Covalent organic frameworks (COFs) have demonstrated photocatalytic potential for CO2 reduction, yet their structure-property correlations, particularly concerning charge-carrier dynamics, remain poorly understood. Herein, we constructed a series of isostructural porphyrin-bicarbazole COFs (BCz-Por(M)-COF (M = H2, Co, and Ni)) through strategic integration of dual electron-donating moieties, achieving localized charge confinement within porphyrin units. Benefiting from the structural advantages, BCz-Por(Co)-COF showed an excellent CO production rate of 15411.8 μmol g-1 h-1, surpassing its BCz-Por(Ni)-COF and BCz-Por(H2)-COF counterparts by 4.2-fold and 68.2-fold, respectively, in photocatalytic CO₂-to-CO conversion. Both experimental and theoretical results reveal that the synergy of Co and porphyrin-bicarbazole COF establishes dual-channel charge-transport pathways, which simultaneously facilitates efficient in-plane charge separation and enables anisotropic out-of-plane charge migration. The efficient charge separation can activate and stabilize the key intermediates, thereby boosting its photocatalytic efficiency. This work highlights the potential of regulating charge-carrier dynamics in improving the photocatalytic performance of COFs-based photocatalysts.

Supplementary files

Article information

Article type
Paper
Accepted
23 May 2025
First published
26 May 2025

Green Chem., 2025, Accepted Manuscript

Tuning charge carrier transport in isostructural covalent organic frameworks for enhanced photocatalytic CO2 reduction

Y. Zhang, H. Xu, H. Li, J. Jiao, X. Wen, Q. Meng and X. Lan, Green Chem., 2025, Accepted Manuscript , DOI: 10.1039/D5GC02267C

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