Supramolecular Porous Assemblies of Atomically Precise Catalytically Active Cerium-Based Clusters

Cite this: Chem. Mater. 2020, 32, 19, 8522–8529
Publication Date (Web):September 16, 2020
https://doi.org/10.1021/acs.chemmater.0c02740
Copyright © 2020 American Chemical Society
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Abstract

Atomically precise metallic clusters offer total structural information lacking in metal oxide and nanoparticle catalysts. However, their use as heterogeneous catalysts requires accessible and robust catalytic sites, yet directing clusters into ordered and porous assemblies through functional control remains elusive. Herein, we report a supramolecular strategy to induce permanent porosity within assemblies of two cerium oxide clusters through the capping ligands used. Single-crystal X-ray crystallography and density functional theory calculations revealed cluster assemblies with accessible channels, while adsorption isotherms showed permanent porosity. The clusters exhibited a bulk modulus >5 GPa in variable pressure diffraction studies. X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and Raman spectroscopy demonstrated mixed valency (Ce3+/Ce4+) and oxygen vacancies in the clusters. We benchmarked catalytic activities through the photooxidation of 2-propanol.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.0c02740.

  • Synthesis and characterization data, including crystallographic refinement, computational details, PXRD patterns, pore size distributions, 1H NMR, XPS, EPR, in situ PXRD experiments, Le Bail refinements, and kinetic data (PDF)

  • Crystallographic data of Ce38-BA (CIF)

  • Crystallographic data of Ce38-NA (CIF)

  • Optimized structure of Ce38-BA (CIF)

  • Optimized structure of Ce38-NA (CIF)

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This article is cited by 6 publications.

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