Atom-Precise Ag Clusters as Precursors for Selective Bimetallic AgPd Heterogeneous Catalysts

Kazeem O. Sulaiman, Andrew Bueckert, Ahmed Abdellah, Sudheesh Kumar Veeranmaril, Drew C. Higgins, Robert W.J. Scott*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations


Bimetallic clusters can have superior catalytic properties compared to those of monometallic clusters due to synergistic interactions between the constituent metals. Here we show that atom-precise Ag clusters can be used as templates for the design of AgPd bimetallic heterogeneous catalysts using a sequential deposition approach. Atom-precise 2,4-dimethylbenzenethiol-protected Ag25(SR)18clusters were used as precursors for sequential Pd deposition and the eventual structures of the AgPd bimetallic catalysts were revealed by X-ray absorption spectroscopy (XAS) studies. EXAFS data shows that Ag clusters on carbon supports can be thermally activated at low temperatures and then used as templates for the subsequent sequential reduction of Pd ions to form bimetallic clusters. In AgPd bimetallic catalysts with low Pd loadings, Ag atoms are predominately on the catalyst surface while Pd atoms occupy subsurface sites; however at higher Pd loadings most Pd atoms occupy surface sites. These structural changes play a significant role in the selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE). Bimetallic AgPd catalysts showed superior activity to monometallic Ag catalysts and higher Ag/Pd ratios led to better MBE selectivity. MBE selectivity of 96.6% was obtained for 12:1-Ag:Pd/carbon catalysts and the selectivity progressively reduced with increased Pd loadings, to 0% for 1:6-Ag:Pd/carbon catalysts, in which only the fully hydrogenated product was formed. This work demonstrates a significant structure-property relationship between the geometry and the catalytic performance of AgPd bimetallic clusters prepared via a sequential deposition strategy.

Original languageEnglish (US)
Pages (from-to)16117-16126
Number of pages10
Issue number38
StatePublished - Sep 29 2022

Bibliographical note

Funding Information:
The authors acknowledge financial assistance from the National Sciences and Engineering Research Council of Canada (NSERC). Randy W. Purves is acknowledged for his assistance with ESI-MS measurements. We also thank Roman Chernikov and Emilio Heredia at the BioXAS Beamline for their assistance with XAS experiments and Sarah Purdy for assistance with XPS sample acquisition. The Saskatchewan Structural Sciences Centre (SSSC) is acknowledged for providing XPS facilities to conduct this research. Funding from Canada Foundation for Innovation, Natural Sciences and Engineering Research Council of Canada and the University of Saskatchewan support research at the SSSC. XAS experiments were performed at the Canadian Light Source, a national research facility of the University of Saskatchewan, which is supported by the Canada Foundation for Innovation (CFI), the Natural Sciences and Engineering Research Council (NSERC), the National Research Council (NRC), the Canadian Institutes of Health Research (CIHR), the Government of Saskatchewan, and the University of Saskatchewan. STEM-EDX measurements were conducted at the Canadian Centre for Electron Microscopy (CCEM) at McMaster University.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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