Spatially Programmed Regioisomeric Conjugated Microporous Polymers Modulating Zinc Sites for Selective CO2 Photoreduction to CH4

Abstract

Conjugated microporous polymers show great potential for photocatalytic CO2 reduction into value-added products. However, their catalytic activity and selectivity remain significantly limited due to poor charge separation efficiency and the lack of suitable active sites. Herein, we propose a topology-driven dipole programming strategy that synergistically decouples atomic-level electronic configuration control from spatially resolved active site engineering. Crucially, the regioisomer-dependent π-topology governs light-harvesting ability, dipole polarization hierarchy, and directional charge transport networks. As a result, the designed Zn-TPA-BPy-1, featuring dipole polarization fields and extra-channel Zn-N₂O₂ sites, exhibits exceptional photocatalytic CO2 conversion activity, with a CH4 evolution rate of 753.18 μmol g-1 h-1 and a high selectivity of 89.7%. Experimental and theoretical results reveal that asymmetric dipole arrays lower the energy barrier for *COOH and *CO intermediates while stabilizing *CHO intermediates through dynamic charge compensation, which contributed to the high activity and selectivity. This finding offers new insights into designing polymer-photocatalysts by subtle structural modulation for CO2 conversion.

Supplementary files

Article information

Article type
Edge Article
Submitted
18 Apr 2025
Accepted
30 Jun 2025
First published
30 Jun 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2025, Accepted Manuscript

Spatially Programmed Regioisomeric Conjugated Microporous Polymers Modulating Zinc Sites for Selective CO2 Photoreduction to CH4

X. Lan, J. Wang, L. Chen, H. Xu, T. Zhang and Y. Chen, Chem. Sci., 2025, Accepted Manuscript , DOI: 10.1039/D5SC02835C

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