Host-guest engineering in a two-dimensional anionic porphyrinic metal-organic framework via cationic bodipy encapsulation for boosting photocatalytic H₂ evolution.

Authors

Li-Lei Zhang, Xing-Yu Liu, Yu-Lan Wang, Ying Li, Xiao-Ge Zhu, Rong-Hui Cao, Hui-Ju Zhang, Xi-Yan Dong, Jian-Hua Qin

Published in

Journal of colloid and interface science. Volume 724. Issue Pt 1. Pages 141035. Jun 26, 2026. Epub Jun 26, 2026.

Abstract

The development of efficient and stable photocatalysts for solar-driven hydrogen production remains a significant challenge, primarily limited by inadequate light harvesting and rapid charge recombination. This work addresses these issues through the rational design of a host-guest system within a metal-organic framework (MOF). We report a novel two-dimensional anionic porphyrinic MOF (1) synthesized using 1-butyl-3-methylimidazolium (BMI) as a structure-directing agent, and replaced the inert BMI guests with photoactive 4,4-Difluoro-8-(1-methylpyridin-4-ium-4-yl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (Bodipy)-based cations by cationic exchange strategy, yielding the composite Bodipy@1. The Bodipy units act as complementary antennas, broadening the visible-light absorption range, while the favorable energy-level alignment between the porphyrinic host (donor) and the Bodipy guest (acceptor) establishes an efficient intramolecular charge-transfer pathway. Density functional theory calculations and spectroscopic studies confirm a spatial separation of frontier orbitals, with the highest occupied crystal orbital localized on the porphyrin linker and the lowest unoccupied crystal orbital on the Bodipy cation, which effectively suppresses charge-carrier recombination. Consequently, Bodipy@1 exhibits a remarkable enhancement in photocatalytic hydrogen evolution activity (∼2.5 mmol·g^-1·h^-1), outperforming the pristine MOF 1. This work highlights a potent strategy of energy-level engineering via host-guest assembly, demonstrating that precise post-synthetic modification of anionic MOFs with functional cations is a powerful avenue for designing advanced, stable photocatalysts for solar fuel production.

PMID:
42372337
Bibliographic data and abstract were imported from PubMed on 30 Jun 2026.

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