The role of single-atom Rh-dopants in the adsorption properties of OH and CO on stepped Ag(211) surfaces

Autor(es)

Neto, Marionir M. C. B. ; Verga, Lucas G. ; Da Silva, Juarez L. F. ; Galvao, Breno R. L.

• Tipo de documento: Artigo Científico
• Fonte: Physical Chemistry Chemical Physics; v. 25, n. 6, p. 11-pg., 2023-01-10.

Resumo

Several chemical reactions with commercial and environmental importance can benefit from the development of more active or selective heterogeneous catalysts. Particularly, those catalyzed by metallic surfaces are usually impacted by the presence of defects such as kinks and dopants. Here, we employed density functional theory calculations within van der Waals correction to investigate the effects of single-atom Rh-dopants in the adsorption properties of OH and CO on stepped Ag(211) surfaces. From our calculations and analyses, we found that the dopant is more energetically stable when replacing more coordinated (and less exposed to the vacuum) sites of the surface. However, in the presence of both molecules, this trend is inverted, and the dopant is more stable in the least coordinated site (step). While OH presents high adsorption energies on both doped and non-doped silver surfaces, CO binds weakly to the noble metal, and strongly on doped sites. The results are relevant for understanding single-atom catalysts on noble-metal surfaces, where the difference in selectivity and activity between the host metal and dopants is exploited. The charge redistribution caused by the dopant, and the appearance of a sharp peak in the density of states of the surface are used to rationalize the results and provide insights into the interactions involved in the adsorption of both molecules. (AU)

• Processo FAPESP: 19/05561-7 - Simulações Mutiescala Aplicadas à Redução do CO2 em Nanopartículas Metálicas: Efeitos de Tamanho das Nanopartículas e Concentração de Adsorvatos
• Beneficiário: Lucas Garcia Verga
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado
• Processo FAPESP: 18/21401-7 - EMU concedido no processo 2017/11631-2: cluster computacional de alto desempenho - ENIAC
• Beneficiário: Juarez Lopes Ferreira da Silva
• Modalidade de apoio: Auxílio à Pesquisa - Programa Equipamentos Multiusuários
• Processo FAPESP: 17/11631-2 - CINE: desenvolvimento computacional de materiais utilizando simulações atomísticas, meso-escala, multi-física e inteligência artificial para aplicações energéticas
• Beneficiário: Juarez Lopes Ferreira da Silva
• Modalidade de apoio: Auxílio à Pesquisa - Programa Centros de Pesquisa em Engenharia
• Processo FAPESP: 21/07129-5 - Redução de CO2 em superfícies intermetálicas de Cu-Au: efeitos do ordenamento atômico e concentração de adsorvatos
• Beneficiário: Lucas Garcia Verga
• Modalidade de apoio: Bolsas no Exterior - Estágio de Pesquisa - Pós-Doutorado