Bioelectrosynthesis of value-added compounds from atmospheric nitrogen and carbon dioxide

• Grant number: 20/15098-0
• Support Opportunities: Scholarships in Brazil - Doctorate
• Start date: May 01, 2021
• End date: April 30, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Frank Nelson Crespilho
• Grantee: Jessica Crivelaro Pacheco
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
• Associated research grant: 18/22214-6 - Towards a convergence of technologies: from sensing and biosensing to information visualization and machine learning for data analysis in clinical diagnosis, AP.TEM
• Associated scholarship(s): 23/04158-0 - Bioelectrosynthesis of value-added compounds: enzyme-displayed microbial cell surfaces and biomimetics metal-polypeptides complex, BE.EP.DR

Abstract

The use of enzymes to reduce CO2 and N2 for the bioelectrosynthesis of value-added products is a promising alternative to replace high-cost synthetic catalysts. For this purpose, interesting results have been obtained with the use of EcFDH-H and Mo-Fe nitrogenase enzymes immobilized on electrode surfaces. However, the bioelectrocatalytic and charge transfer mechanisms of these enzymes have not been fully elucidated yet. Detailed studies of these mechanisms are essential to understand biocatalysts in greater depth, aiming bioelectrosynthesis processes with high stability and catalytic efficiency. In this context, the present research project aims to elucidate the mechanisms by the use of spectroscopic techniques (FTIR: Fourier-Transform Infrared spectroscopy; Raman spectroscopy; XAS: X-ray absorption spectroscopy and DEMS: Differential Electrochemical Mass Spectrometry) in situ/operando, as they provide electrochemical control to modulate the bioelectrocatalytic activity, while structural and electronic changes of active sites are monitoraed, as well as the generation of products and intermediaries. Therefore, this project seeks to contribute to the advance of the bioelectrosynthesis technology, elucidating bioelectrocatalytic mechanisms for the production of value-added compounds, such as formate and ammonia, and in the further development of efficient three-dimensional catalysts inspired by the catalytic mechanism of enzymes with higher specificity activity. (AU)

Scientific publications

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

SEDENHO, GRAZIELA C.; NECKEL, ITAMAR T.; COLOMBO, RAFAEL N. P.; PACHECO, JESSICA C.; BERTAGLIA, THIAGO; CRESPILHO, FRANK N.. Investigation of Water Splitting Reaction by a Multicopper Oxidase through X-ray Absorption Nanospectroelectrochemistry. ADVANCED ENERGY MATERIALS, v. 12, n. 47, p. 6-pg., 2022-10-17. (19/15333-1, 20/04796-8, 18/22214-6, 21/05665-7, 20/03681-2, 19/12053-8, 20/15098-0)

ALI, MIAN A.; SEDENHO, GRAZIELA C.; PACHECO, JESSICA C.; IOST, RODRIGO M.; RAHMAN, ASMA; HASSAN, AYAZ; CARDOSO, DANIEL R.; GOMES, ROBERTO S.; CRESPILHO, FRANK N.. Metal-free, low-cost, and high-performance membraneless ethanol fuel cell. Journal of Power Sources, v. 551, p. 9-pg., 2022-10-08. (20/15098-0, 18/24485-7, 20/04796-8, 18/22214-6, 19/12053-8, 19/15333-1)

IOST, RODRIGO M.; VENKATKARTHICK, RADHAKRISHNAN; NASCIMENTO, STEFFANE Q.; LIMA, FABIO H. B.; CRESPILHO, FRANK N.. Hydrogen bioelectrogeneration with pH-resilient and oxygen-tolerant cobalt apoenzyme-saccharide. CHEMICAL COMMUNICATIONS, v. 60, n. 18, p. 3-pg., 2024-02-01. (22/09164-5, 23/10667-4, 21/05665-7, 18/22214-6, 23/01529-7, 20/15098-0)