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The synthesis and stabilization of Pd nanoclusters on a support, as well as simultaneously achieving optimal catalytic activity, remain challenging tasks. Functionalizing the support surface with specific ligands offers a promising solution, but it often requires carefully balancing trade-offs between reaction yield and catalyst stability. Here, we used two different ligands (propylamine and propylthiol) to functionalize the layered silicate’s interlayer surface for Pd nanocluster synthesis and stabilization. For dehydrogenating formic acid, Pd nanoclusters on aminopropyl groups achieved a catalytic activity ~27-fold higher than that
of thiopropyl groups at 70 °C. Our density functional calculations compared the adsorption energetics and bonding characteristics of single Pd atoms and Pd13 nanoclusters on aminoand thio-functionalized silicate surfaces. Pd‒N bonds were predicted to be weaker with minimal covalency, while Pd‒S bonds exhibit greater covalency due to higher 4d‒3p hybridization, resulting in better stability. However, Pd13 clusters undergo a severe structural deformation on thiol-functionalized surfaces, resulting in a smaller overall surface area and
diminished catalytic stability.

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• In Copyright
  This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials & Interfaces, copyright © 2024 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsami.4c13770.

Keyword: H2 generation, formic acid dehydrogenation, dehydrocoupling, Pd nanoclusters, single-atom catalyst, density functional calculations

Date published: 2024-11-27

Publisher: American Chemical Society (ACS)

Journal:

• ACS Applied Materials & Interfaces (ISSN: 19448244) vol. 16 issue. 47 p. 64736-64744

Funding:

• European Research Council PCI2023-143426
• Agencia Estatal de Investigaci?n PCI2022-135083-2
• T?rkiye Bilimsel ve Teknolojik Arastirma Kurumu 123N224
• Japan Science and Technology Corporation 2023-MLALH

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.5096

First published URL: https://doi.org/10.1021/acsami.4c13770

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Updated at: 2025-11-18 08:30:21 +0900

Published on MDR: 2025-11-18 08:22:57 +0900