新加坡国立大学Bin Liu团队报道了拓扑控制BODIPY和CO₂基金属锆-有机框架的直接合成，用于高效光催化CO₂还原。相关研究成果于2025年1月1日发表于国际顶尖学术期刊《德国应用化学》。

基于硼二吡咯甲烷（BODIPY）的锆金属有机框架（Zr-MOFs）具有很强的集光能力，在不使用牺牲试剂的情况下具有巨大的人工光合作用潜力。然而，由于合成合适配体的挑战，它们的直接制备尚未实现。

该文中，研究人员报道了首次成功利用CO作为原料直接合成BODIPY基Zr-MOFs。通过控制合成条件，成功地获得了两种不同的Zr-MOFs。第一种是CO₂-Zr₆-DEPB，其表现出基于Zr₆(μ3-O)₄(μ3-OH)₄节点的面心立方（fcu）拓扑结构，而第二种是CO₃-Zr₁₂-DEPB，其特征是围绕Zr₁₂(μ3-O)₈(μ3-OH)₈(μ2-OH)₆节点的六方密堆积（hcp）拓扑结构。通过粉末X射线衍射和高分辨率透射电子显微镜分析证实，这两种MOFs都表现出优异的结晶度。

这些MOFs催化剂在没有助催化剂或有毒牺牲试剂的情况下，使用H₂O作为电子供体，显示出合适的光催化氧化还原电位，用于将CO₂还原为CO。在光照条件下，CO₂-Zr₁₂-DEPB和CO₂-Zr₆-DEPB的CO收率分别为16.72和13.91μmol·g^-1·h^-1，选择性接近100%。CO₂吸收和光电化学实验揭示了驱动两种MOFs不同催化活性的机制的关键见解。这些基于BODIPY和CO₂的光响应Zr-MOFs代表了开发高效光催化剂的有前景的平台。

附：英文原文

Title: Direct Synthesis of Topology-Controlled BODIPY and CO2-Based Zirconium Metal-Organic Frameworks for Efficient Photocatalytic CO2 Reduction

Author: Bo Song, Wentao Song, Yuhang Liang, Yong Liu, Bowen Li, He Li, Liang Zhang, Yanhang Ma, Ruquan Ye, Ben Zhong Tang, Dan Zhao, Yi Zhou, Bin Liu

Issue&Volume: 2025-01-01

Abstract: Boron dipyrromethene (BODIPY)-based zirconium metal-organic frameworks (Zr-MOFs) possess strong light-harvesting capabilities and great potential for artificial photosynthesis without the use of sacrificial reagents. However, their direct preparation has not yet been achieved due to challenges in synthesizing suitable ligands. Herein, we reported the first successful direct synthesis of BODIPY-based Zr-MOFs, utilizing CO as a feedstock. By controlling synthetic conditions, we successfully obtained two distinct Zr-MOFs. The first, CO2-Zr6-DEPB, exhibits a face-centered cubic (fcu) topology based on a Zr6(μ3-O)4(μ3-OH)4 node, while the second, CO2-Zr12-DEPB, features a hexagonal closed packed (hcp) topology, structured around a Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6 node. Both MOFs demonstrated excellent crystallinity, as verified through powder X-ray diffraction and high-resolution transmission electron microscopy analyses. These MOF catalysts displayed suitable photocatalytic redox potentials for the reduction of CO2 to CO using H2O as the electron donor in the absence of co-catalyst or toxic sacrificial reagent. Under light irradiation, CO2-Zr12-DEPB and CO2-Zr6-DEPB offered high CO yields of 16.72 and 13.91 μmol·g1·h1, respectively, with nearly 100% selectivity. CO2 uptake and photoelectrochemical experiments revealed key insights into the mechanisms driving the different catalytic activities of the two MOFs. These BODIPY and CO2-based, light-responsive Zr-MOFs represent a promising platform for the development of efficient photocatalysts.

DOI: 10.1002/anie.202421248

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202421248