Synthetic Photoelectrochemistry: An Innovative Strategy for Sustainable Synthesis

• Grant number: 25/02336-3
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Start date: August 01, 2025
• End date: July 31, 2027
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Júlio Cezar Pastre
• Grantee: Rodrigo Costa e Silva
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated research grant: 21/06661-5 - Enabling technologies for the sustainable chemical synthesis of platform molecules, new chemicals and bioactive compounds, AP.BIOEN.JP2

Abstract

The environmental impact resulting from the rampant use of fossil fuels has driven the advancement of more sustainable technologies and processes, in line with the recommendations of the United Nations (UN) as expressed in the Sustainable Development Goals (SDGs). In this context, this research project proposes a study on photoelectrochemical organic synthesis, an area still little explored in Brazil. The study will be carried out along two main axes: Metal-Photoelectrochemistry and Continuous Flow Photoelectrochemistry. In Axis 1, Metal-Photoelectrochemistry, the combination of photoelectrochemistry with metal catalysis will be explored, focusing on coupling reactions catalyzed by palladium via the activation of the C-H bond in deactivated aryl derivatives. The strategy is based on accessing high oxidative potentials provided by photoelectrochemical catalysis and the careful selection of the photoelectrocatalyst, allowing the selective oxidation of the aryl derivatives in the presence of palladium(0) without compromising its catalytic properties. Subsequently, in Axis 2, Continuous Flow Photoelectrochemistry, the goal is to develop photoelectrochemical reactions under continuous flow conditions. In particular, the regeneration system of benzophenone by anodic oxidation in photochemical hydrogen atom transfer (HAT) reactions will be investigated. Although benzophenone is effective in promoting various HAT reactions in continuous flow, its use in stoichiometric amounts is necessary due to the formation of benzopinacol as a byproduct. To overcome this limitation, it is proposed to regenerate benzophenone by the anodic oxidation of benzopinacol-a process known as recycling e-PRC. This approach will enable the catalytic use of benzophenone, making the process more accessible and efficient for the studied photochemical reactions. (AU)