通过修饰的共价有机框架实现的增强相互作用提高一氧化碳光还原效率

Enhancing CO Photoreduction Efficiency Through Improved Interaction Enabled by a Decorated Covalent-Organic Framework.

作者信息

Zhao Wenling, Li Jiangnan, Li Ke, Jiao Jiapeng, Liu Shiqiang, Yang Jiahao, Frogley Mark D, Peng Yaguang, Wang Yiyong, Wang Hengan, Zhang Shipeng, Jing Lihong, Liu Chengcheng, Yang Sihai, Kang Xinchen, Han Buxing

机构信息

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, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.

School of Chemistry, University of Chinese Academy of Sciences, Beijing, 100049, China.

出版信息

Angew Chem Int Ed Engl. 2025 Sep 8;64(37):e202510550. doi: 10.1002/anie.202510550. Epub 2025 Jul 29.

DOI:10.1002/anie.202510550

PMID:40728115

Abstract

Photoreduction of CO 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 h and a high CO selectivity of 95.8% in 2 h for CO photoreduction at room temperature. The pore size of Co-PyPDA-COF is comparable to the diameter of CO, which allows simultaneous interaction of a single CO molecule with the two Co(II) sites. The enhanced interaction result in increased local CO pressure, limited CO diffusion after adsorption, shortened distance for photoelectron transfer, and reduced energy barrier for the rate-determining step in CO reduction, promoting CO activation and conversion. This work opens a new way to design efficient catalysts by optimizing the pore size of the host.

摘要

一氧化碳（CO）的光还原反应常常因其活化动力学缓慢而受到阻碍。优化主体-客体相互作用是克服这一障碍的有效策略。在此，我们报道了将活性Co(II)位点固定在具有一维（1D）链状结构的共价有机框架（COF）Co-PyPDA-COF中，该材料在室温下进行CO光还原反应时，展现出30.5 mmol g⁻¹ h⁻¹的显著CO生成速率以及在2小时内95.8%的高CO选择性。Co-PyPDA-COF的孔径与CO的直径相当，这使得单个CO分子能够同时与两个Co(II)位点相互作用。这种增强的相互作用导致局部CO压力增加、吸附后CO扩散受限、光电子转移距离缩短以及CO还原速率决定步骤的能垒降低，从而促进了CO的活化和转化。这项工作通过优化主体的孔径为设计高效催化剂开辟了一条新途径。