南京大学朱嘉团队近日研究了混合连接金属-有机框架光敏化的多元调节，以有效减少二氧化碳。相关论文发表在2025年5月5日出版的《美国化学会杂志》上。

光敏化是一种通过改善光吸收、能量转移和电荷分离来提高光催化剂性能的有力方法。然而，实现高效率需要精确控制光敏剂、催化中心及其相互作用，这在非均相系统中仍然具有挑战性。研究组开发了具有混合连接体和可调缺陷的多元锆金属有机框架（MOF），可以对光敏剂、催化中心及其比例进行前所未有的控制，为二氧化碳减排创造了一个有效的平台。这些MOF整合了三苯胺、吩恶嗪或吩噻嗪基连接体作为光敏剂，以及金属卟啉连接体（金属=Fe、Co、Ni和Zn）作为CO₂还原催化中心。 

此外，坚固的Zr₆节点的缺陷容限允许通过引入缺失的接头缺陷来系统地改变接头比率。通过微调光敏剂、催化金属中心及其比例，研究组实现了CO₂与CO还原率为247.8 μmol g_cat.^-1 h^-1的优化光催化剂，比同质类似物提高了17倍。瞬态光谱和密度泛函理论计算揭示了框架结构在促进有效的网状内能量转移和电荷分离方面的关键作用。该研究强调了MOF平台在光催化剂多元调节方面的独特优势，为先进的人工光合系统铺平了道路。

附：英文原文

Title: Multivariate Tuning of Photosensitization in Mixed-Linker Metal–Organic Frameworks for Efficient CO2 Reduction

Author: Ya Yin, Shijia Feng, Xinyu Xu, Yifan Liu, Youcong Li, Lei Gao, Xiaocheng Zhou, Jiahao Dong, Yulun Wu, Jian Su, Jing-Lin Zuo, Shuai Yuan, Jia Zhu

Issue&Volume: May 5, 2025

Abstract: Photosensitization is a powerful approach for enhancing the photocatalyst performance by improving light absorption, energy transfer, and charge separation. However, achieving high efficiency requires precise control over photosensitizers, catalytic centers, and their interactions, which remain challenging in heterogeneous systems. Herein, we develop multivariate zirconium metal–organic frameworks (MOFs) with mixing linkers and tunable defects that enable unprecedented control over photosensitizers, catalytic centers, and their ratios, creating an efficient platform for CO2 reduction. These MOFs integrate triphenylamine, phenoxazine, or phenothiazine-based linkers as photosensitizers and metal porphyrin linkers (metal = Fe, Co, Ni, and Zn) as CO2 reduction catalytic centers. Furthermore, the defect tolerance of robust Zr6 nodes allows for a systematic variation in linker ratios by introducing missing linker defects. By fine-tuning the photosensitizers, catalytic metal centers, and their ratios, we achieved an optimized photocatalyst with CO2-to-CO reduction rates of 247.8 μmol gcat.–1 h–1, representing a 17-fold enhancement over homogeneous analogues. Transient spectra and density functional theory calculations reveal the critical role of the framework structure in promoting efficient intrareticular energy transfer and charge separation. This study highlights the unique advantage of MOF platforms in the multivariate tuning of photocatalysts, paving the way for advanced artificial photosynthetic systems.

DOI: 10.1021/jacs.5c02940

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c02940