Green Synthesis of Macrocyclic CO2 Conversion Catalysts

This project pioneers a sustainable synthetic approach that merges mechanochemistry and cryogenic control to revolutionize the preparation of macrocyclic catalysts for electrochemical CO2 conversion. Porphyrins and corroles are essential molecular frameworks in catalysis and energy conversion but remain difficult to synthesize efficiently using conventional, solvent-based routes. The project develops solvent-free, cryo-mechanochemical protocols for their formation—transforming mechanical energy into chemical reactivity while operating at sub-zero temperatures to stabilize reactive intermediates and improve macrocyclization selectivity.
Through systematic optimization of reaction parameters such as milling frequency, temperature, and catalytic additives, the research aims to achieve unprecedented yields and purities for porphyrinoid macrocycles. Subsequent metalation with transition metals (Fe, Mn, Co) will generate active complexes that serve as electrocatalysts for CO2 reduction, nitrogen fixation, and oxygen evolution reactions. Extending the methodology to polymeric and networked architectures will enable the design of 1D–3D conductive materials, bridging molecular catalysis and materials science.
By replacing hazardous solvents and minimizing energy input, this cryogenic mechanochemical approach establishes a paradigm shift in green synthesis. The resulting catalysts will be integrated into gas diffusion electrode systems, enhancing CO2 availability and selectivity toward valuable C1–C3 products such as formate, methanol, and acetate. Combining experimental studies with advanced DFT modeling, the project elucidates the mechanistic foundations of solid-state macrocyclization and electrocatalytic CO2 activation.
This interdisciplinary research links synthetic chemistry, electrocatalysis, and materials engineering, contributing to Austria’s leadership in sustainable molecular energy conversion. It sets the stage for next-generation CO2 utilization technologies, aligning with global decarbonization goals.