Determination of Site Occupancy in the M-Pd-Zn (M = Cu, Ag, and Au) γ-Brass Phase by CALculation of PHAse Diagrams Modeling and Rietveld Refinement

Rushi Gong, Anish Dasgupta, Shun Li Shang, Haoran He, Melanie Kirkham, Eric K. Zimmerer, Griffin A. Canning, Michael J. Janik, Robert M. Rioux, Zi Kui Liu

Research output: Contribution to journalArticlepeer-review

Abstract

The Pd-Zn γ-brass phase provides exciting opportunities for synthesizing site-isolated catalysts with precisely controlled Pd active site ensembles. Introducing a third metallic element into the γ-brass lattice further perturbs the catalytic active site ensembles. Here, we introduce coinage metallic elements M (M = Cu, Ag, and Au) into the Pd-Zn γ-brass phase and investigate the site occupation factors of each element in the γ-brass lattice. The CALculation of PHAse Diagrams (CALPHAD) modeling approach supported by energetics predicted by the density functional theory and X-ray and neutron diffraction with Rietveld refinement were used to identify the SOF on each Wyckoff site for various M amounts alloyed into the Pd-Zn γ-brass phase. The present analysis unveils the strong preference for Pd occupying the outer tetrahedral (OT) site in the γ-brass lattice, while the coinage metallic elements tend to substitute for Zn on the octahedral (OH) site. The determination of site occupancy in the bulk M-Pd-Zn γ-brass phase provides opportunities to investigate and tailor potential catalytically active site ensembles in the γ-brass phase materials.

Original languageEnglish
JournalInorganic Chemistry
DOIs
StateAccepted/In press - 2025
Externally publishedYes

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