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  • Review Article
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Confining isolated atoms and clusters in crystalline porous materials for catalysis

Nature Reviews Materials volume 6, pages 244–263 (2021)Cite this article

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Abstract

Structure–reactivity relationships for nanoparticle-based catalysts have been greatly influenced by the study of catalytic materials with either supported isolated metal atoms or metal clusters comprising a few atoms. The stability of these metal species is a key challenge because they can sinter into large nanoparticles under harsh reaction conditions. However, stability can be achieved by confining the nanoparticles in crystalline porous materials (such as zeolites and metal–organic frameworks). More importantly, the interaction between the metal species and the porous framework may modulate the geometric and electronic structures of the subnanometric metal species, especially for metal clusters. This confinement effect can induce shape-selective catalysis or different chemoselectivity from that of metal atoms supported on open-structure solid carriers. In this Review, we discuss the structural features, synthesis methodologies, characterization techniques and catalytic applications of subnanometric species confined in zeolites and metal–organic frameworks. We make a critical comparison between confined and non-confined isolated atoms and metal clusters, and provide future perspectives for the field.

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Fig. 1: Isolated atoms and subnanometric metal clusters on different supports.
Fig. 2: Different methods for the introduction of metal catalysts into zeolite crystallites.
Fig. 3: Catalytic performance of Pt–zeolite materials for propane dehydrogenation.
Fig. 4: Influence of the density of Cu species in CHA zeolites on the activity for selective catalytic reduction of NOx.
Fig. 5: Photocatalysis and electrocatalysis using subnanometric metal species in MOFs.

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Acknowledgements

We are grateful for financial support from the European Research Council (grant ERC-AdG-2014-671093, SynCatMatch) and the Spanish Government through the Severo Ochoa Program (SEV-2016-0683).

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  1. Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas (UPV–CSIC), Av. de los Naranjos s/n, Valencia, Spain

    Lichen Liu & Avelino Corma

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  1. Lichen Liu
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  2. Avelino Corma
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A.C. conceived the structure of this Review. L.L. and A.C. wrote this Review together.

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Correspondence to Avelino Corma.

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Liu, L., Corma, A. Confining isolated atoms and clusters in crystalline porous materials for catalysis. Nat Rev Mater 6, 244–263 (2021). https://doi.org/10.1038/s41578-020-00250-3

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