Studying the structure–property relationship in Zr-BDI MOF for noble-metal-free selective photocatalytic CO2 conversion to CO
4 affiliations
- 1Department of Chemistry, Birla Institute of Technology and Science Hyderabad Campus Hyderabad 500078 India [email protected].
- 2Materials Centre for Sustainable Energy & Environment (McSEE), Birla Institute of Technology and Science Hyderabad Campus Hyderabad 500078 India.
- 3School of Science, RMIT University GPO Box 2476 Melbourne Victoria 3000 Australia.
- 4College of Chemical Sciences and Engineering (CCSE), Applied Chemistry and Engineering Research Centre of Excellence (ACER CoE), Mohammed VI Polytechnic University (UM6P) Ben Guerir 43150 Morocco.
Abstract
Photocatalytic conversion of CO₂ to value-added products by metal-organic framework (MOF)-based catalysts often requires the introduction of secondary metal sites or the anchoring of noble-metal-based photosensitizers, leading to complex designs and increased costs. In this work, we focus on the structure-property relationship of MOFs, emphasizing the band gap and conduction band position of the MOF catalyst. Here, we use a light-sensitive linker [N,N'-di(3,5-dicarboxyphenyl)benzene tetracarboxylic diimide] to design a robust, intrinsically photo-redox-active zirconium MOF. This Zr-MOF with scu topology has a band gap of 2.84 eV and a conduction band position of -0.64 V vs. NHE, which is well positioned for the conversion of CO₂ to CO without the addition of noble metal atoms or photosensitizers. Interestingly, anion radical generation by the linker under light irradiation supports linker-to-cluster charge transfer and simultaneously enables excellent conversion of CO₂ to CO and formate, with yields of 1083.2 µmol g⁻¹ and 265.62 µmol g⁻¹, respectively, and a CO selectivity of 72.12%, surpassing most noble-metal-free Zr-MOF benchmarks. Operando Raman spectroscopy has been used to identify key intermediates, including *CO₂ ⁻, *COOH, *CO, formyl, and O-bound methoxy species. DFT studies corroborate the experimental findings, showing that the free energy profile indicates a lower barrier for *CO than for formyl formation. This linker-first strategy offers an easy, cost-effective, and interesting approach in which judicious choice of the photo-redox linker can modulate the band-edge alignment and microenvironment of the MOF, enabling selective CO₂ to CO photocatalysis without precious metals.
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BibTeX
@article{chandran2026studying,
title = {{Studying the structure–property relationship in Zr-BDI MOF for noble-metal-free selective photocatalytic CO2 conversion to CO}},
author = {Akhil Chandran P and Tushar S Verma and Shreya Sarkar and Ankur Chanda and Ayalew H Assen and Amit Nag and Ravichandar Babarao and Sounak Roy and Himanshu Aggarwal},
journal = {RSC advances},
year = {2026},
month = nov,
doi = {10.1039/d6ra07959h},
url = {https://europepmc.org/article/PMC/PMC13725856},
note = {CC BY},
}
RIS
TY - JOUR
TI - Studying the structure–property relationship in Zr-BDI MOF for noble-metal-free selective photocatalytic CO2 conversion to CO
AU - Akhil Chandran P
AU - Tushar S Verma
AU - Shreya Sarkar
AU - Ankur Chanda
AU - Ayalew H Assen
AU - Amit Nag
AU - Ravichandar Babarao
AU - Sounak Roy
AU - Himanshu Aggarwal
PY - 2026
DA - 2026/11/02
JO - RSC advances
DO - 10.1039/d6ra07959h
UR - https://europepmc.org/article/PMC/PMC13725856
AB - Photocatalytic conversion of CO₂ to value-added products by metal-organic framework (MOF)-based catalysts often requires the introduction of secondary metal sites or the anchoring of noble-metal-based photosensitizers, leading to complex designs and increased costs. In this work, we focus on the structure-property relationship of MOFs, emphasizing the band gap and conduction band position of the MOF catalyst. Here, we use a light-sensitive linker [N,N'-di(3,5-dicarboxyphenyl)benzene tetracarboxylic diimide] to design a robust, intrinsically photo-redox-active zirconium MOF. This Zr-MOF with scu topology has a band gap of 2.84 eV and a conduction band position of -0.64 V vs. NHE, which is well positioned for the conversion of CO₂ to CO without the addition of noble metal atoms or photosensitizers. Interestingly, anion radical generation by the linker under light irradiation supports linker-to-cluster charge transfer and simultaneously enables excellent conversion of CO₂ to CO and formate, with yields of 1083.2 µmol g⁻¹ and 265.62 µmol g⁻¹, respectively, and a CO selectivity of 72.12%, surpassing most noble-metal-free Zr-MOF benchmarks. Operando Raman spectroscopy has been used to identify key intermediates, including *CO₂ ⁻, *COOH, *CO, formyl, and O-bound methoxy species. DFT studies corroborate the experimental findings, showing that the free energy profile indicates a lower barrier for *CO than for formyl formation. This linker-first strategy offers an easy, cost-effective, and interesting approach in which judicious choice of the photo-redox linker can modulate the band-edge alignment and microenvironment of the MOF, enabling selective CO₂ to CO photocatalysis without precious metals.
SN - 2046-2069
ER -