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

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

doi:10.1002/anie.202421248

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

Angew Chem Int Ed Engl. 2025 Jan 1:e202421248. doi: 10.1002/anie.202421248. Online ahead of print.

Authors

Bo Song¹, Wentao Song¹, Yuhang Liang², Yong Liu³, Bowen Li¹, He Li¹, Liang Zhang⁴, Yanhang Ma², Ruquan Ye³, Ben Zhong Tang⁴, Dan Zhao¹, Yi Zhou², Bin Liu⁵

Affiliations

¹ National University of Singapore, Chemical and Biomolecular Engineering, SINGAPORE.
² ShanghaiTech University, Physical Science and Technology, CHINA.
³ City University of Hong Kong, Chemistry, HONG KONG.
⁴ The Hong Kong University of Science and Technology, Chemistry, HONG KONG.
⁵ National University of Singapore, Department of Chemical and Biomolecular Engineering, 4 Engineering Drive 4, National University of Singapore, 117585, Singapore, SINGAPORE.

PMID: 39742452
DOI: 10.1002/anie.202421248

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 CO₂ 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·g-1·h-1, 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.

Keywords: BODIPY; CO2-based metal-organic frameworks; high-resolution and scanning transmission electron microscopy; photocatalytic CO2 reduction; topology-control.