Tailoring porphyrinic MOF-545 performances for CO₂ photocatalytic reduction through linker chlorination
Abstract
The development of technologies for CO₂ sequestration and its conversion into value-added chemicals has received considerable and growing attention. However, achieving high conversion efficiency and product selectivity under mild conditions remains a major challenge. This study investigates the photocatalytic CO₂ reduction activity of Zr-based porphyrinic MOF-545 derivatives synthesized by varying the percentages of two porphyrin linkers: tetrakis(4-carboxyphenyl)porphyrin (TCPP) and its β-pyrrolic chlorinated analogue (TCPPCl8). A comprehensive set of spectroscopic and analytical techniques was employed to characterize the materials, revealing the impact of linker chlorination on the optical band gap, particle size and crystallinity. The incorporation of chlorine-substituted linkers significantly enhanced the photocatalytic activity. Notably, under visible light irradiation and using triethanolamine (TEOA) as a sacrificial electron donor, the MOF-545 derivative containing 50% TCPPCl8 achieved the highest formate production, with a rate 2.6 times greater than that of pristine MOF-545, with a production rate of 625 μmol g−1 h−1 after 2 h. Density Functional Theory (DFT) calculations were also performed to gain insight into the electronic properties of the chlorinated porphyrinic materials. These calculations showed the stabilization of both the HOMO and LUMO energy levels upon chlorination of the porphyrin linkers, with a more pronounced stabilisation of the LUMO, leading to a smaller band gap, in line with optical measurements. Additionally, the stabilisation of the HOMO level is expected to increase the oxidizing power of the photogenerated holes, thus facilitating TEOA oxidation and enhancing the overall photocatalytic activity, and this rationalizes the experimental observations.
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BibTeX
@article{robinson2026tailoring,
title = {{Tailoring porphyrinic MOF-545 performances for CO₂ photocatalytic reduction through linker chlorination}},
author = {Amanda Lyn Robinson and Sadiya Sadiya and Sandeep Kumar and Francesc Penas-Hidalgo and Khadija Talbi and Zakaria Halime and Mathieu Frégnaux and Damien Aureau and Maria Gomez-Mingot and Pierre Mialane and Albert Solé-Daura and Caroline Mellot-Draznieks and Anne Dolbecq},
journal = {Dalton Transactions},
year = {2026},
month = sep,
doi = {10.1039/d5dt02590g},
url = {https://hal.science/hal-05548544v1},
note = {CC BY-NC 4.0},
}
RIS
TY - JOUR
TI - Tailoring porphyrinic MOF-545 performances for CO₂ photocatalytic reduction through linker chlorination
AU - Amanda Lyn Robinson
AU - Sadiya Sadiya
AU - Sandeep Kumar
AU - Francesc Penas-Hidalgo
AU - Khadija Talbi
AU - Zakaria Halime
AU - Mathieu Frégnaux
AU - Damien Aureau
AU - Maria Gomez-Mingot
AU - Pierre Mialane
AU - Albert Solé-Daura
AU - Caroline Mellot-Draznieks
AU - Anne Dolbecq
PY - 2026
DA - 2026/09/30
JO - Dalton Transactions
DO - 10.1039/d5dt02590g
UR - https://hal.science/hal-05548544v1
AB - The development of technologies for CO₂ sequestration and its conversion into value-added chemicals has received considerable and growing attention. However, achieving high conversion efficiency and product selectivity under mild conditions remains a major challenge. This study investigates the photocatalytic CO₂ reduction activity of Zr-based porphyrinic MOF-545 derivatives synthesized by varying the percentages of two porphyrin linkers: tetrakis(4-carboxyphenyl)porphyrin (TCPP) and its β-pyrrolic chlorinated analogue (TCPPCl8). A comprehensive set of spectroscopic and analytical techniques was employed to characterize the materials, revealing the impact of linker chlorination on the optical band gap, particle size and crystallinity. The incorporation of chlorine-substituted linkers significantly enhanced the photocatalytic activity. Notably, under visible light irradiation and using triethanolamine (TEOA) as a sacrificial electron donor, the MOF-545 derivative containing 50% TCPPCl8 achieved the highest formate production, with a rate 2.6 times greater than that of pristine MOF-545, with a production rate of 625 μmol g−1 h−1 after 2 h. Density Functional Theory (DFT) calculations were also performed to gain insight into the electronic properties of the chlorinated porphyrinic materials. These calculations showed the stabilization of both the HOMO and LUMO energy levels upon chlorination of the porphyrin linkers, with a more pronounced stabilisation of the LUMO, leading to a smaller band gap, in line with optical measurements. Additionally, the stabilisation of the HOMO level is expected to increase the oxidizing power of the photogenerated holes, thus facilitating TEOA oxidation and enhancing the overall photocatalytic activity, and this rationalizes the experimental observations.
SN - 1477-9226
SN - 1477-9234
ER -