Integrating Ultrasmall Pd NPs into Core–Shell Imidazolate Frameworks for Photocatalytic Hydrogen and MeOH Production
The construction of photoactive units in the proximity of a stable framework support is one of the promising strategies for uplifting photocatalysis. In this work, the ultrasmall Pd NPs implanted onto core–shell (CS) metal organic frameworks (MOFs), i.e., CS@Pd nanoarchitectures with tailored electr...
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Veröffentlicht in: | Inorganic chemistry 2023-05, Vol.62 (19), p.7235-7249 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | The construction of photoactive units in the proximity of a stable framework support is one of the promising strategies for uplifting photocatalysis. In this work, the ultrasmall Pd NPs implanted onto core–shell (CS) metal organic frameworks (MOFs), i.e., CS@Pd nanoarchitectures with tailored electronic and structural properties are reported. The all-in-one heterogeneous catalyst CS@Pd3 improves the surface functionalities and exhibits an outstanding hydrogen evolution reaction (HER) activity rate of 12.7 mmol g–1 h–1, which is 10-folds higher than the pristine frameworks with an apparent quantum efficiency (AQE) of 9.02%. The bifunctional CS@Pd shows intriguing results when subjected to photocatalytic CO2 reduction with an impressive rate of 71 μmol g–1 h–1 of MeOH under visible-light irradiation at ambient conditions. Spectroscopic data reveal efficient charge migrations and an extended lifetime of 2.4 ns, favoring efficient photocatalysis. The microscopic study affirms the formation of well-ordered CS morphology with precise decoration of Pd NPs over the CS networks. The significance of active Pd and Co sites is addressed by congruent charge-transfer kinetics and computational density functional theory calculations of CS@Pd, which validate the experimental findings with their synergistic involvement in improved photocatalytic activity. This present work provides a facile and competent avenue for the systematic construction of MOF-based CS heterostructures with active Pd NPs. |
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ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/acs.inorgchem.2c04524 |