中国科学院上海高等研究院Qing Xu课题组的研究发现，在三组分共价有机框架中精细调节中间体的结合强度可用于CO₂还原反应。2024年2月26日，国际知名学术期刊《德国应用化学》发表了这一成果。

电催化CO₂还原反应(CO₂RR)的催化性能取决于反应物和中间体的结合强度。已有研究采用共价有机框架(COFs)催化CO₂RR，并通过构建供体-受体(DA)体系来调节其结合能力。然而，大多数DA COFs具有单一的供体和受体单元，这使得它们在调节中间体结合强度方面的准确性不足。构建高效催化剂需要对催化剂与中间体的相互作用进行更精细的调控。

在该研究中，研究人员首先通过引入富电子的二芳胺单元和缺电子的苯并噻唑和钴卟啉单元，构建了供体-受体-受体单元的三组分COF。与双组分COFs相比，所设计的COF具有更高的电子导电性、更强的还原性、高效率的电荷转移，进一步提高了CO₂RR的电催化性能，在-0.8 V时的法拉第效率为97.2%，在-1.0 V时电流在27.85 mA cm^-2，超过其他双组分COFs。理论计算表明，三组分COF的催化位点对中间体具有合适的结合能力，有利于*COOH的形成和*CO的解吸。这项工作为多组分COFs的发展提供了有价值的见解，使调制电荷转移能够提高CO2RR活性。

附：英文原文

Title: Elaborate Modulating Binding Strength of Intermediates via Three-component Covalent Organic Frameworks for CO2 Reduction Reaction

Author: Minghao Liu, Cheng-Xing Cui, Shuai Yang, Xiubei Yang, Xuewen Li, Jun He, Qing Xu, Gaofeng Zeng

Issue&Volume: 2024-02-26

Abstract: The catalytic performance for electrocatalytic CO2 reduction reaction (CO2RR) depends on the binding strength of the reactants and intermediates. Covalent organic frameworks (COFs) have been adopted to catalyze CO2RR, and their binding ability were tuned via constructing donor-acceptor (DA) systems. However, most DA COFs had single donor and acceptor units, which caused wide-range but lacking accuracy in modulating the binding strength of intermediates. More elaborate regulation of the interactions with intermediates are necessary and challenge to construct high-efficiency catalysts. Herein, the three-component COF with donor-acceptor-acceptor units was first constructed by introducing electron-rich diarylamine unit and electron-deficient benzothiazole and Co-porphyrin units. Compared with two-component COFs, the designed COF exhibit elevated electronic conductivity, enhanced reducibility, high efficiency charge transfer, further improving the electrocatalytic CO2RR performance with the faradic efficiency of 97.2% at 0.8 V and high activity with the partial current density of 27.85 mA cm2 at 1.0 V which exceed other two-component COFs. Theoretical calculations demonstrate that catalytic sites in three-component COF had suitable binding ability of the intermediates, which were benefit for formation of *COOH and desorption of *CO. This work offers valuable insights for the advancement of multi-component COFs, enabling modulated charge transfer to improve the CO2RR activity.

DOI: 10.1002/anie.202401750

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202401750