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Developing efficient catalysts for selective hydrogenation of molecules bearing multiple reducible functional groups remains a major challenge. Palladium (Pd) nanoclusters are promising candidates owing to their strong H2 activation ability, broad substrate compatibility, and unique surface properties. However, the controlled synthesis of small Pd nanoclusters with accessible, coordinatively unsaturated active sites remains difficult as they are prone to aggregation. In this study, we present a strategy to fabricate surface-exposed Pd nanoclusters confined within a ring-shaped polyoxometalate (POM) via a mild solid-state reduction process (1 atm H2, ~25 °C). The resulting Pd nanocluster exhibits exceptional chemoselectivity in the hydrogenation of multifunctional substrates by preferentially adsorbing C=C and C≡C bonds on its discrete, exposed Pd surface with a well-defined coordination environment. Importantly, the rigid POM framework considerably stabilizes Pd nanocluster, enabling excellent reusability over multiple catalytic cycles. This study demonstrates a molecular templating approach for constructing robust and chemoselective metal nanocluster catalysts, offering new opportunities in the design of hydrogenation systems.

Rights:

• Creative Commons BY Attribution 4.0 International
  

Keyword: heterogeneous catalysis, palladium nanoclusters, polyoxometalates, selective hydrogenations

Date published: 2025-07-28

Publisher: Wiley

Journal:

• Advanced Science (ISSN: 21983844) vol. 12 issue. 38 e09418

Funding:

• Japan Society for the Promotion of Science JP24K01448
• Japan Society for the Promotion of Science JP24H02210
• Japan Society for the Promotion of Science JP24H02217
• Japan Society for the Promotion of Science JP24K01279
• Japan Society for the Promotion of Science JP23K13812
• Japan Society for the Promotion of Science JP22H04971
• Core Research for Evolutional Science and Technology JPMJCR20B2
• Fusion Oriented REsearch for disruptive Science and Technology JPMJFR213

Manuscript type: Publisher's version (Version of record)

MDR DOI:

First published URL: https://doi.org/10.1002/advs.202509418

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Updated at: 2025-10-21 16:06:30 +0900

Published on MDR: 2025-10-21 15:43:36 +0900