Volcano‐like Activity Trends in Au@Pd Catalysts: The Role of Pd Loading and Nanoparticle Size

Braga, Adriano H.; Fiorio, Jhonatan L.; Yang, Ofelia; Silva, Karla L. C.; Silva, Tiago A.; Hoffman, Adam S.; Bare, Simon R.; Bettini, Jefferson; Mogili, Naga Vishnu V.; Rossi, Liane M.

doi:10.1002/cphc.202500164

Volcano‐like Activity Trends in Au@Pd Catalysts: The Role of Pd Loading and Nanoparticle Size

Journal Article · Thu Jul 03 00:00:00 EDT 2025 · ChemPhysChem

DOI:https://doi.org/10.1002/cphc.202500164· OSTI ID:2583426

Braga, Adriano H. ^[1]; Fiorio, Jhonatan L. ^[1]; Yang, Ofelia ^[1]; Silva, Karla L. C. ^[1]; Silva, Tiago A. ^[1]; Hoffman, Adam S. ^[2]; ^[2]; Bettini, Jefferson ^[3]; Mogili, Naga Vishnu V. ^[4]; ^[1]

Univ. of Sao Paulo (Brazil)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Brazilian Center for Research in Energy and Materials (CNPEM), Sao Paulo (Brazil). Brazilian Nanotechnology National Laboratory (LNNano); Univ. of Campinas (UNICAMP), Sao Paulo (Brazil)
Brazilian Center for Research in Energy and Materials (CNPEM), Sao Paulo (Brazil). Brazilian Nanotechnology National Laboratory (LNNano)

The addition of palladium (Pd) to preformed gold nanoparticles (Au NPs) enables the formation of core‐shell structures with enhanced catalytic performance in oxidation reactions. However, predicting the precise palladium content required to achieve maximum catalytic activity remains difficult based on current understanding. Herein, Pd was systematically introduced onto titania‐supported Au NPs (2, 6, and 10 nm) to evaluate their performance in benzyl alcohol oxidation. A volcano‐like trend in catalytic activity was observed, where activity increased with Pd addition, peaked, and then declined. The Pd loading required for maximum activity depended on Au NP size: ≈40 at% Pd/Au for 2.6 nm, ≈20 at% Pd/Au for 6.4 nm, and ≈12.5 at% Pd/Au for 10.6 nm. For Au NPs > 6 nm, peak activity aligned with monolayer Pd coverage, while for smaller NPs (2–3 nm), optimal Pd content was below monolayer predictions. X‐ray absorption spectroscopy revealed a core‐shell structure at low Pd content, but higher Pd loadings led to Pd diffusion into the Au core. This structural transformation likely caused activity decline, indicating that AuPd alloying negatively impacts catalysis. These results highlight that core‐shell Au@Pd catalysts outperform AuPd alloys and provide crucial insights for designing highly active bimetallic catalysts.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2583426

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 16 Vol. 26; ISSN 1439-4235; ISSN 1439-7641

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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