Ab initio study for late steps of CO₂ and CO electroreduction: from CHCO* toward C₂ products on Cu and CuZn nanoclusters

Autor(es)

Ocampo-Restrepo, Vivianne K. ; Verga, Lucas G. ; Da Silva, Juarez L. F.

• Tipo de documento: Artigo Científico
• Fonte: Physical Chemistry Chemical Physics; v. 25, n. 48, p. 8-pg., 2023-11-22.

Resumo

Electroreduction of CO2 to C-2 products such as ethanol is motivated by its potential application to satisfy global energy demand in a more sustainable and renewable way. Cooper-based catalysts have exhibited highlighted performance in obtaining C-2 products, but large overpotentials and poor selectivity are still challenging. Herein, we employed density functional theory calculations and the computational hydrogen electrode model to study the impact of CuZn alloys on the mechanism and selectivity of CO2 and CO electroreduction to C-2 products. On both clusters, the preferred pathway to ethanol and ethylene shares a common intermediate: CH2CHO*. On Cu-55, ethanol formation would occur at lower electrode potential than the formation of ethylene, which agrees with experimental studies. Since Cu42Zn13 increases the Gibbs free energy change between CH2CHO* and adsorbed acetaldehyde, the alloy exhibited lower selectivity toward ethanol than Cu-55 cluster. The role of Zn is mainly related to the stronger adsorption of the intermediates on Cu42Zn13 than in the Cu-55 group. Our results suggested that the d states of Zn are involved in the adsorption of intermediates, strengthening the interaction. (AU)

• 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: 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: 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