Enhancing CO <sub>2</sub> Photoreduction Efficiency Through Improved Interaction Enabled by a Decorated Covalent‐Organic Framework

W Wenling Zhao (Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry) J Jiangnan Li (College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences) K Ke Li J Jiapeng Jiao (Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering) S Shiqiang Liu (Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry) J Jiahao Yang (Xiamen University , , ,) M Mark D. Frogley (Diamond Light Source, Harwell Science Campus, Oxfordshire OX11 0DE, U.K.) Y Yaguang Peng (Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry) Y Yiyong Wang (Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry) H Hengan Wang (Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry) S Shipeng Zhang (Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry) L Lihong Jing (Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry) C Chengcheng Liu (Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering) S Sihai Yang (Peking University , , ,) X Xinchen Kang (Institute of Chemistry, Chinese Academy of Sciences , , ,) B Buxing Han (Institute of Chemistry, Chinese Academy of Sciences , , ,)

Abstract

Abstract Photoreduction of CO 2 is often hindered by the sluggish kinetics for its activation. Refinement of host–guest interactions is an effective strategy to overcome this barrier. Here, we report the immobilization of active Co(II) sites within a covalent‐organic framework (COF) with a one‐dimensional (1D) chain structure, Co‐PyPDA‐COF, which demonstrates a remarkable CO generation rate of 30.5 mmol g −1 h −1 and a high CO selectivity of 95.8% in 2 h for CO 2 photoreduction at room temperature. The pore size of Co‐PyPDA‐COF is comparable to the diameter of CO 2 , which allows simultaneous interaction of a single CO 2 molecule with the two Co(II) sites. The enhanced interaction result in increased local CO 2 pressure, limited CO 2 diffusion after adsorption, shortened distance for photoelectron transfer, and reduced energy barrier for the rate‐determining step in CO 2 reduction, promoting CO 2 activation and conversion. This work opens a new way to design efficient catalysts by optimizing the pore size of the host.

Article Details

Volume / Issue Vol. 64, Issue 37
Published September 08, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (16)

W

Wenling Zhao

Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry

J

Jiangnan Li

College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences

K

Ke Li

J

Jiapeng Jiao

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering

S

Shiqiang Liu

Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry

J

Jiahao Yang

Xiamen University , , ,

M

Mark D. Frogley

Diamond Light Source, Harwell Science Campus, Oxfordshire OX11 0DE, U.K.

Y

Yaguang Peng

Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry

Y

Yiyong Wang

Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry

H

Hengan Wang

Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry

S

Shipeng Zhang

Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry

L

Lihong Jing

Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry

C

Chengcheng Liu

Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering

S

Sihai Yang

Peking University , , ,

X

Xinchen Kang

Institute of Chemistry, Chinese Academy of Sciences , , ,

B

Buxing Han

Institute of Chemistry, Chinese Academy of Sciences , , ,