Under topological guidance, the self-assembly process based on a tetratopic porphyrin synthon results in a hydrogen-bonded organic framework (HOF) with the predicted square layers topology (sql) but unsatisfied stability. Strikingly, simply introducing a transition metal in the porphyrin center does not change the network topology but drastically causes noticeable change on noncovalent interaction, orbital overlap, and molecular geometry, therefore ultimately giving rise to a series of metalloporphyrinic HOFs with high surface area, and excellent stability (intact after being soaked in boiling water, concentrated HCl, and heated to 270 °C). On integrating both photosensitizers and catalytic sites into robust backbones, this series of HOFs can effectively catalyze the photoreduction of CO2 to CO, and their catalytic performances greatly depend on the chelated metal species in the porphyrin centers. This work enriches the library of stable functional HOFs and expands their applications in photocatalytic CO2 reduction.

Metallization-Prompted Robust Porphyrin-Based Hydrogen-Bonded Organic Frameworks for Photocatalytic CO2 Reduction / Q. Yin, E.V. Alexandrov, D.-. Si, Q.-. Huang, Z.-. Fang, Y. Zhang, A.-. Zhang, W.-. Qin, Y.-. Li, T.-. Liu, D.M. Proserpio. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 61:6(2022 Feb 01), pp. e202115854.1-e202115854.8. [10.1002/anie.202115854]

Metallization-Prompted Robust Porphyrin-Based Hydrogen-Bonded Organic Frameworks for Photocatalytic CO2 Reduction

D.M. Proserpio
Ultimo
2022

Abstract

Under topological guidance, the self-assembly process based on a tetratopic porphyrin synthon results in a hydrogen-bonded organic framework (HOF) with the predicted square layers topology (sql) but unsatisfied stability. Strikingly, simply introducing a transition metal in the porphyrin center does not change the network topology but drastically causes noticeable change on noncovalent interaction, orbital overlap, and molecular geometry, therefore ultimately giving rise to a series of metalloporphyrinic HOFs with high surface area, and excellent stability (intact after being soaked in boiling water, concentrated HCl, and heated to 270 °C). On integrating both photosensitizers and catalytic sites into robust backbones, this series of HOFs can effectively catalyze the photoreduction of CO2 to CO, and their catalytic performances greatly depend on the chelated metal species in the porphyrin centers. This work enriches the library of stable functional HOFs and expands their applications in photocatalytic CO2 reduction.
Hydrogen-bonded organic frameworks; Metallization; Photocatalytic CO2 reduction; Porphyrin; Structural stability
Settore CHIM/03 - Chimica Generale e Inorganica
1-feb-2022
21-dic-2021
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/911551
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