Electro-oxidation of alcohols on platinum: a multifaceted computational approach via electronic structure calculations and microkinetic modeling

• Grant number: 24/21412-0
• Support Opportunities: Scholarships in Brazil - Doctorate
• Start date: June 01, 2025
• End date: April 30, 2029
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Antonio Gustavo Sampaio de Oliveira Filho
• Grantee: Bruno Santana Sampaio
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
• Associated research grant: 21/00675-4 - Tying up materials for electrochemical energy storage and catalysis, AP.TEM

Abstract

The development of new sustainable energy generation strategies is a growing demand worldwide. Direct methanol and ethanol fuel cells are promising candidates for this purpose. The development of new catalysts and improvement of process efficiency require a deep understanding of the electro-oxidation mechanism. However, due to its complexity, purely experimental studies are subject to limitations. In this context, computational chemistry can be used to describe the thermodynamic and kinetic parameters of the elementary steps of chemical reactions, as well as the intermediates present and the influence of adsorbates on kinetics. This project aims to describe, based on density functional theory (DFT), the thermodynamic and kinetic parameters of the electro-oxidation mechanism of methanol and ethanol on platinum (111) and (100), using a microkinetic description of the elementary reaction steps. The DFT methodology used will be previously validated based on experimental data of adsorption energies of small molecules on metal surfaces and ab initio calculations. The results obtained will allow the description of the electro-oxidation reaction of both alcohols, from first principles, under different conditions, and a direct comparison with experimental observations from the literature to evaluate the quality of the developed model and the approximations used. Furthermore, this project will enable the development of a computational strategy for describing electrocatalytic reactions that can be used in the development of more efficient electrocatalysts. (AU)