Issue 41, 2022

Topology- and wavelength-governed CO2 reduction photocatalysis in molecular catalyst-metal–organic framework assemblies

Abstract

Optimising catalyst materials for visible light-driven fuel production requires understanding complex and intertwined processes including light absorption and catalyst stability, as well as mass, charge, and energy transport. These phenomena can be uniquely combined (and ideally controlled) in porous host–guest systems. Towards this goal we designed model systems consisting of molecular complexes as catalysts and porphyrin metal–organic frameworks (MOFs) as light-harvesting and hosting porous matrices. Two MOF-rhenium molecule hybrids with identical building units but differing topologies (PCN-222 and PCN-224) were prepared including photosensitiser-catalyst dyad-like systems integrated via self-assembled molecular recognition. This allowed us to investigate the impact of MOF topology on solar fuel production, with PCN-222 assemblies yielding a 9-fold turnover number enhancement for solar CO2-to-CO reduction over PCN-224 hybrids as well as a 10-fold increase compared to the homogeneous catalyst-porphyrin dyad. Catalytic, spectroscopic and computational investigations identified larger pores and efficient exciton hopping as performance boosters, and further unveiled a MOF-specific, wavelength-dependent catalytic behaviour. Accordingly, CO2 reduction product selectivity is governed by selective activation of two independent, circumscribed or delocalised, energy/electron transfer channels from the porphyrin excited state to either formate-producing MOF nodes or the CO-producing molecular catalysts.

Graphical abstract: Topology- and wavelength-governed CO2 reduction photocatalysis in molecular catalyst-metal–organic framework assemblies

Supplementary files

Article information

Article type
Edge Article
Submitted
02 6月 2022
Accepted
30 9月 2022
First published
03 10月 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 12164-12174

Topology- and wavelength-governed CO2 reduction photocatalysis in molecular catalyst-metal–organic framework assemblies

P. M. Stanley, K. Hemmer, M. Hegelmann, A. Schulz, M. Park, M. Elsner, M. Cokoja and J. Warnan, Chem. Sci., 2022, 13, 12164 DOI: 10.1039/D2SC03097G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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