Electrooxidation of C-4 Polyols on Platinum Single-Crystals: A Computational and Electrochemical Study

Author(s)

Soffiati, Gabriela ^[1] ; Bott-Neto, Jose L. ^{[1, 2]} ; Yukuhiro, Victor Y. ^{[1, 2]} ; Pires, Cleo T. G. V. M. T. ^[1] ; Lima, Carlos C. ^[1] ; Zanata, Cinthia R. ^[3] ; Birdja, Yuvraj Y. ^[4] ; Koper, Marc T. M. ^[4] ; San-Miguel, Miguel A. ^[1] ; Fernandez, Pablo S. ^{[1, 2]}

Affiliation

^[1] Univ Estadual Campinas, Chem Inst, BR-13083970 Campinas, SP - Brazil

^[2] Univ Estadual Campinas, Ctr Innovat New Energies, BR-13083841 Campinas, SP - Brazil

^[3] Univ Fed Mato Grosso do Sul, Inst Chem, BR-79070900 Campo Grande, MS - Brazil

^[4] Leiden Univ, Leiden Inst Chem, NL-2300 Leiden - Netherlands

• Document type: Journal article
• Source: Journal of Physical Chemistry C; v. 124, n. 27, p. 14745-14751, JUL 9 2020.
• Web of Science Citations: 0

Abstract

Many polyols are abundant and cheap molecules highly spread in the biomass. These molecules have an enormous potential to be used in electrochemical devices to generate energy and/or value-added molecules. The electrooxidation of polyols can produce different substances of interest in the chemical industry concomitantly to high purity hydrogen in electrolyzers. The cost in the production of all these chemicals depends, among other factors, on the develop of more active and selective catalysts. However, in order to search for these materials using computational experiments, it is mandatory to have a better understanding of the fundamental aspect of the reactions, which permit to base the search on the adsorption energies of one or more key reaction intermediates. To contribute to this task, we performed (spectro)-electrochemical and computational experiments to study the electrooxidation of C-4 polyols. We show that the electrooxidation of polyols does not depend on the relative orientation of their OH groups. Besides, using Pt single crystals, we demonstrate that the trend for the oxidation of the primary carbon (relative to the secondary) increases in the order Pt(111) < Pt(100) < Pt(110) and that this result can be extended to polyols with longer carbon chains. Finally, computational experiments permit us to rationalize these trends looking at the relative stability of double dehydrogenated intermediates on the Pt basal planes. (AU)

• FAPESP's process: 16/23891-6 - Computer modeling of condensed matter
• Grantee: Alex Antonelli
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 13/07296-2 - CDMF - Center for the Development of Functional Materials
• Grantee: Elson Longo da Silva
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
• FAPESP's process: 18/20952-0 - Applied and fundamental studies of the electrochemical conversion of alcohols and CO2
• Grantee: Pablo Sebastián Fernández
• Support Opportunities: Program for Research on Bioenergy (BIOEN) - Regular Program Grants
• FAPESP's process: 19/07449-0 - Towards a general understanding of the effect of p-block adatoms on the electrooxidation of polyols on platinum in alkaline media
• Grantee: Pablo Sebastián Fernández
• Support Opportunities: Regular Research Grants