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Merging molecular catalysts and metal–organic frameworks for photocatalytic fuel production

Abstract

In the effort to generate sustainable clean energy from abundant resources such as water and carbon dioxide, solar fuel production—the combination of solar-light harvesting and the generation of efficient chemical energy carriers—by artificial molecular photosystems is very attractive. Molecular constituents that display attractive features for chemical energy conversion (such as high product selectivity and atom economy) have been developed, and their interfacing with host materials has enabled recyclability, controlled site positioning, as well as access to fundamental insights into the catalytic mechanism and environment-governed selectivity. Among the wide variety of supports, metal–organic frameworks (MOFs) possess valuable characteristics (such as their porosity and versatility) that can influence the reaction environment and material architecture in a unique fashion. Here we highlight the various existing synthetic strategies to graft molecular complexes such as catalysts and photosensitizers onto MOFs for solar fuel production. The opportunities and limitations of one-pot and stepwise approaches are critically assessed, and the resulting materials are discussed based on their photocatalytic performances and the practical applicability of selected examples.

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Fig. 1: Combining molecular catalysis and MOFs.
Fig. 2: Mechanism of integration of molecular complexes with MOFs using the one-pot engineered linker strategy.
Fig. 3: Bottle-around-the-ship strategy to interface molecular catalysts and MOFs.
Fig. 4: Stepwise node-docking approach, allowing for controllable and high molecular loadings.
Fig. 5: Linker-docking strategy as a stepwise assembly method in which molecular loading occurs at linkers bearing anchoring sites in an assembled MOF via chelation, nucleophile substitution or hydrogen-bond interactions.
Fig. 6: Stepwise ship-in-a-bottle design with self-assembly of a molecular complex from flexible precursors within MOF pores, capitalizing on MOF cavity sizes to assemble and trap one catalyst molecule per cage, assuming maximum loading.

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Acknowledgements

P.M.S. thanks the Chemical Industry Fonds (FCI) for a PhD fellowship. J.H. and N.B.S. thank the TUM Institute for Advanced Study (IAS) for funding. This work was supported by the German Research Foundation (DFG) Priority Program 1928 ‘Coordination Networks: Building Blocks for Functional Systems’, the research project MOFMOX (grant no. FI 502/43-1) and the Excellence Cluster 2089 ‘e-conversion’ (Fundamentals of Energy Conversion Processes).

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P.M.S., J.H. and J.W. conceived the idea and outline for this Review and wrote the manuscript with contributions from N.B.S. and R.A.F. All authors have approved the final version of this manuscript.

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Correspondence to J. Warnan.

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Stanley, P.M., Haimerl, J., Shustova, N.B. et al. Merging molecular catalysts and metal–organic frameworks for photocatalytic fuel production. Nat. Chem. 14, 1342–1356 (2022). https://doi.org/10.1038/s41557-022-01093-x

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