富电子大环金属有机骨架光催化CO2高效还原
近日，吉林大学陈龙团队实现了富电子大环金属有机骨架光催化CO2高效还原。2025年9月8日出版的《美国化学会志》发表了这项成果。
金属有机框架（MOF）以其结构多样性、可调谐的电子特性和在各种应用中的卓越性能而闻名。值得注意的是，配体的给电子能力显著增强了这些框架内配体到金属的电荷转移（LMCT）过程，从而促进了有效的电荷迁移。
研究组开发了两种富电子的大环配体，它们来自于吩噻嗪和吩嗪功能化的杯[3]芳烃，以及它们相应的钴配位MOF。值得注意的是，以给电子能力更强的杯状[3]吩噻嗪配体（C[3]PTZ-COOH）为主题构建的Co-C[3]PTZ-MOF，具有优越的光响应和增强的电荷输运特性。该材料的CO2光还原初始效率为17800 μmol g-1 h-1， CO选择性为81%。优异的光催化性能源于杯状[3]芳烃配体的强给电子性质，这有利于高效的LMCT过程。该研究为通过大环配体的合理工程设计高性能光催化剂提供了有价值的见解。
附：英文原文
Title: Electron-Rich Macrocycle-Based Metal–Organic Frameworks for Efficient Photocatalytic CO2 Reduction
Author: Zhaohui Zhang, Qiang Xu, Weiran Li, Yunhai Zhu, Jun-Sheng Qin, Yingkui Yang, Heng Rao, Long Chen
Issue&Volume: September 8, 2025
Abstract: Metal–organic frameworks (MOFs) are distinguished by their structural diversity, tunable electronic properties, and exceptional performance in various applications. Notably, the electron-donating ability of ligands significantly enhances the ligand-to-metal charge transfer (LMCT) processes within these frameworks, thereby promoting efficient charge migration. Herein, we developed two electron-rich macrocyclic ligands derived from phenothiazine- and phenoxazine-functionalized calix[3]arenes, alongside their corresponding cobalt-coordinated MOFs. Remarkably, the MOF designated as Co-C[3]PTZ-MOF─constructed using the more electron-donating calix[3]phenothiazine ligand (C[3]PTZ-COOH)─exhibited superior photoresponse and enhanced charge-transport characteristics. This optimized material achieved an exceptional CO2 photoreduction initial efficiency of 17,800 μmol g–1 h–1 with 81% CO selectivity. The outstanding photocatalytic performance originates from the strong electron-donating nature of the calix[3]arene-based ligands, which facilitated efficient LMCT processes. This study provides valuable insights for designing high-performance photocatalysts through rational engineering of macrocyclic ligands.
DOI: 10.1021/jacs.5c09419