Role of the OH-group in the adsorption properties of methanol, ethanol, and ethylene glycol on 15-atom 3d, 4d, and 5d transition-metal clusters

Autor(es)

Bezerra, Raquel C. ^[1] ; de Mendonca, Joao Paulo A. ^[2] ; Mendes, Paulo C. D. ^[2] ; Passos, Raimundo R. ^[1] ; Da Silva, Juarez L. F. ^[2]

Afiliação do(s) autor(es)

^[1] Univ Fed Amazonas, Dept Chem, Av Gen Rodrigo Octavio 6200, Coroado 1, BR-69080900 Manaus, AM - Brazil

^[2] Univ Sao Paulo, Sao Carlos Inst Chem, POB 780, BR-13560970 Sao Carlos, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Physical Chemistry Chemical Physics; v. 23, n. 32 JUL 2021.
• Citações Web of Science: 0

Resumo

The adsorption of alcohols on transition-metal (TM) substrates has received the attention of many researchers due to the applications of alcohols in several technological fields. However, our atomic-level understanding is still far from satisfactory, in particular for the interaction of alcohols with finite-size TM clusters, where new effects can arise due to the presence of quantum-size effects. In this work, we report a theoretical investigation of the adsorption properties of methanol, ethanol, and ethylene glycol on 12 different 3d, 4d, and 5d TM15 clusters based on density functional theory calculations within the semi-empirical D3 van der Waals corrections. From the correlation analysis of all the lowest- and high-energy configurations, we identified the adsorption modes of methanol, ethanol, and ethylene glycol on the TM15 clusters, in which the OH group binds to the cationic TM sites via the O-TM and H-TM interactions. Due to the relatively weak alcohol-TM15 interaction, the changes induced on the TM15 clusters are small, except for Au-15 and Ru-15, where the bare cluster changes its structure to a nearby minimum in the potential energy surface. The adsorption energy for the alcohol/TM15 systems is correlated to the combination of several parameters, in which the main contribution is connected with the O-TM interaction and the HOTM angles. Furthermore, the TM electronegativity is an important descriptor for the methanol and ethanol adsorption energies, while charge transfer is important for ethylene glycol. (AU)

• 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