Engineering Covalent Organic Frameworks for Photocatalytic CO2 Reduction: From Exciton Dissociation to Product Selectivity
4 affiliations
- 1Nanjing Institute of Environmental Sciences, Ministry of Ecology and Environment, Nanjing 210042, China
- 2East China Regional Technology Center of Hazardous Waste Environmental Risk Prevention and Control, Nanjing 210042, China
- 3Shandong Haipuou Environmental Protection Equipment Technology Co., Ltd., Zhucheng 262200, China
- 4College of Mechanical Engineering, Ningbo University of Finance and Economics, Ningbo 315175, China
Abstract
Solar-driven CO2 reduction requires a photocatalyst to integrate light harvesting, exciton dissociation, long-range charge transport, CO2 adsorption and activation, and multielectron proton-coupled electron transfer within a single structural platform. Covalent organic frameworks (COFs) are attractive in this context because their π-conjugated backbones, periodic pores, linkage chemistry, stacking modes, and catalytic sites can be programmed with molecular precision. Nevertheless, the literature remains dominated by phenomenological correlations between optical response and product yield, while the causal relationships among exciton binding energy (Eb), free-carrier generation, interfacial charge transfer, intermediate adsorption, and product selectivity remain insufficiently resolved. This review develops a unified structure–activity framework in which intrinsic π-conjugation and donor–acceptor polarization regulate Eb and exciton diffusion; morphology and heterojunctions control the competition between interfacial transfer and recombination; and active-site coordination and pore microenvironments determine local electron density, proton delivery, and the adsorption energies of *COOH, *OCHO, *CO, *CHO, and *OCCO intermediates. Representative performance is benchmarked only when 13CO2 isotope tracing and appropriate blank controls are available, with external homogeneous photosensitizer systems treated separately. Among the entries retained in the condition-aware benchmark, reported CO production rates span 17.75–20,110 μmol g−1 h−1 and wavelength-specific AQYs span 0.058–5.1%; these values are not directly comparable without the associated photon flux, reactor configuration, catalyst loading, and auxiliary components. Finally, operando spectroscopy, density functional theory, microkinetic modelling, stability analysis, standardized reporting, machine-learning-assisted discovery, and device-oriented scale-up are discussed as routes toward predictive and reproducible COF photocatalyst engineering.
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BibTeX
@article{xue2026engineering,
title = {{Engineering Covalent Organic Frameworks for Photocatalytic CO2 Reduction: From Exciton Dissociation to Product Selectivity}},
author = {Dingming Xue and Bing Ma and Xiuzhen Fan and Lei Jiang and Ning Su and Xiaodong Li and Changchun Yan and Hao Zhou},
journal = {Catalysts},
year = {2026},
month = oct,
doi = {10.3390/catal16100909},
url = {https://www.mdpi.com/2073-4344/16/10/909},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Engineering Covalent Organic Frameworks for Photocatalytic CO2 Reduction: From Exciton Dissociation to Product Selectivity
AU - Dingming Xue
AU - Bing Ma
AU - Xiuzhen Fan
AU - Lei Jiang
AU - Ning Su
AU - Xiaodong Li
AU - Changchun Yan
AU - Hao Zhou
PY - 2026
DA - 2026/10/14
JO - Catalysts
DO - 10.3390/catal16100909
UR - https://www.mdpi.com/2073-4344/16/10/909
AB - Solar-driven CO2 reduction requires a photocatalyst to integrate light harvesting, exciton dissociation, long-range charge transport, CO2 adsorption and activation, and multielectron proton-coupled electron transfer within a single structural platform. Covalent organic frameworks (COFs) are attractive in this context because their π-conjugated backbones, periodic pores, linkage chemistry, stacking modes, and catalytic sites can be programmed with molecular precision. Nevertheless, the literature remains dominated by phenomenological correlations between optical response and product yield, while the causal relationships among exciton binding energy (Eb), free-carrier generation, interfacial charge transfer, intermediate adsorption, and product selectivity remain insufficiently resolved. This review develops a unified structure–activity framework in which intrinsic π-conjugation and donor–acceptor polarization regulate Eb and exciton diffusion; morphology and heterojunctions control the competition between interfacial transfer and recombination; and active-site coordination and pore microenvironments determine local electron density, proton delivery, and the adsorption energies of *COOH, *OCHO, *CO, *CHO, and *OCCO intermediates. Representative performance is benchmarked only when 13CO2 isotope tracing and appropriate blank controls are available, with external homogeneous photosensitizer systems treated separately. Among the entries retained in the condition-aware benchmark, reported CO production rates span 17.75–20,110 μmol g−1 h−1 and wavelength-specific AQYs span 0.058–5.1%; these values are not directly comparable without the associated photon flux, reactor configuration, catalyst loading, and auxiliary components. Finally, operando spectroscopy, density functional theory, microkinetic modelling, stability analysis, standardized reporting, machine-learning-assisted discovery, and device-oriented scale-up are discussed as routes toward predictive and reproducible COF photocatalyst engineering.
SN - 2073-4344
ER -