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

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Autor(es):
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.
Número total de Autores: 10
Tipo de documento: Artigo Científico
Fonte: ChemPhysChem; v. N/A, p. 9-pg., 2025-07-03.
Resumo

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: approximate to 40 at% Pd/Au for 2.6 nm, approximate to 20 at% Pd/Au for 6.4 nm, and approximate to 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. (AU)

Processo FAPESP: 18/26253-6 - Catálise cooperativa: uma alternativa para o desenvolvimento de catalisadores a base de ouro e metais de transição abundantes
Beneficiário:Liane Marcia Rossi
Modalidade de apoio: Auxílio à Pesquisa - Regular
Processo FAPESP: 14/50279-4 - Brasil Research Centre for Gas Innovation
Beneficiário:Julio Romano Meneghini
Modalidade de apoio: Auxílio à Pesquisa - Programa Centros de Pesquisa Aplicada
Processo FAPESP: 20/15230-5 - Centro de Pesquisa e Inovação de Gases de Efeito Estufa - RCG2I
Beneficiário:Julio Romano Meneghini
Modalidade de apoio: Auxílio à Pesquisa - Programa Centros de Pesquisa Aplicada
Processo FAPESP: 21/00675-4 - Arquitetura de materiais para armazenamento de energia eletroquímica e catálise
Beneficiário:Roberto Manuel Torresi
Modalidade de apoio: Auxílio à Pesquisa - Temático