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Electrolyte Effects on Electrochemical CO2 Reduction Reaction at Sn Metallic Electrode

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Autor(es):
Rodrigues Pinto, Maria ; Vos, Rafael E. ; Nagao, Raphael ; Koper, Marc T. M.
Número total de Autores: 4
Tipo de documento: Artigo Científico
Fonte: Journal of Physical Chemistry C; v. 128, n. 50, p. 9-pg., 2024-12-05.
Resumo

Understanding the electrolyte factors governing the electrochemical CO2 reduction reaction (CO2RR) is fundamental for selecting the optimized electrolyte conditions for practical applications. While noble metals are frequently studied, the electrolyte effects on the CO2RR on Sn catalysts are not well explored. Here, we studied the electrolyte effect on Sn metallic electrodes, investigating the impact of electrolyte concentration, cation identity, and anion properties, and how it shapes the CO2RR activity and selectivity. The activity for formic acid and carbon monoxide increases with the cation concentration and size at mild acid conditions. In contrast, hydrogen production is not strongly influenced by the cathodic potential, electrolyte concentration, and cation size. Furthermore, we have compared the CO2RR performance at a constant cation concentration in K2SO4 (pH 4) and KHCO3 (pH 7), where we show that the reaction rate toward HCOOH and CO are minimally impacted by the anion identity on the SHE scale, while being affected by the cations in solution, which we attribute to the reaction being limited by cation-coupled electron transfer steps rather than by a proton-coupled electron transfer step. We propose that the HCOOH forms via adsorbed hydrides leading to *OCHO intermediate, while CO forms through an electron transfer step, producing *CO2 delta-. Cations facilitate both processes by stabilizing the negatively charged intermediates, and the difference in the extent of the promotion of HCOOH over CO formation would stem from the stronger cation effects on *H compared with *CO2 delta- species. Additionally, the presence of HCO3- at high concentrations (1.0 mol L-1) is shown to significantly enhance the production of H-2 at high overpotentials (>-1.0 V vs RHE) due to bicarbonate ions acting as protons donors, outcompeting water reduction. These findings underscore the significance of electrolyte engineering for enhanced formic acid synthesis, offering valuable insights for optimizing the CO2RR processes on Sn electrocatalysts. (AU)

Processo FAPESP: 19/08244-2 - Síntese de nanofios para aplicação na reação de redução de dióxido de carbono
Beneficiário:Maria Rodrigues Pinto
Modalidade de apoio: Bolsas no Brasil - Doutorado
Processo FAPESP: 21/08868-6 - Eletrodos dissipativos tandem aplicados na redução de dióxido de carbono para formação de produtos C2+
Beneficiário:Raphael Nagao de Sousa
Modalidade de apoio: Auxílio à Pesquisa - Programa BIOEN - Regular
Processo FAPESP: 22/03750-0 - Efeito do cátion em eletrodos de Sn e Bi durante a reação de redução de CO2 sob condições de transporte de massa bem definidas
Beneficiário:Maria Rodrigues Pinto
Modalidade de apoio: Bolsas no Exterior - Estágio de Pesquisa - Doutorado
Processo FAPESP: 17/11986-5 - Geração e Armazenamento de Novas Energias: trazendo desenvolvimento tecnológico para o país
Beneficiário:Ana Flávia Nogueira
Modalidade de apoio: Auxílio à Pesquisa - Programa Centros de Pesquisa em Engenharia