Bioelectrocatalysis: Investigation of Redox Enzymes, Biomimetics, and Single-Entity Electron Transfer

• Grant number: 24/22202-9
• Support Opportunities: Regular Research Grants
• Start date: September 01, 2025
• End date: August 31, 2028
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Frank Nelson Crespilho
• Grantee: Frank Nelson Crespilho
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil

Abstract

Contemporary bioelectrochemistry faces critical challenges in understanding and optimizing complex electron transfer processes in biological and bioinspired systems, limiting the efficient use of biocatalysts in sustainable energy conversion platforms. In this context, we propose an in-depth exploration of bioelectrocatalytic dynamics within redox systems to maximize catalytic efficiency and stability under demanding operational conditions. The primary focus centers on redox enzymes and biomimetic complexes involved in water oxidation, hydrogen generation, and CO¿ reduction, leveraging advanced spectroscopic and electrochemical analyses to elucidate underlying electron transport mechanisms and their interactions within the catalytic microenvironment. In a second focus, we will examine sugar bioelectrocatalysis mediated by Saccharomyces cerevisiae, emphasizing the regulatory role of EPS (extracellular polymeric substance) as a conductive matrix modulating redox dynamics within bioelectrochemical processes. Finally, we will apply single-entity probing, STM, STS, and quantum conductance to map redox channels and characterize electronic conductance in natural and synthetic enzymatic systems, aiming to elucidate conduction mechanisms in bioinspired structures and develop platforms with high selectivity and efficiency. This study seeks to push the theoretical and applied boundaries of bioelectrochemistry, opening new avenues for biohybrid energy conversion systems. (AU)