- The overall work of the MSCA project was performed according to the individual work packages: a) WP1 involved the development of synthetic methods for various precursor materials and transition metal (Cu, Ni, Co and Fe) complexes of metalloporphyrin monomers in appreciable yield and their characterization; b) WP2 included the design and modification of the effective synthetic strategies for the binuclear triply fused metalloporphyrins. The incorporation of selective functional groups through a comprehensive structure-activity analysis to improve solubility and low yields. Simplified purification techniques to minimize the loss of complexes during post-synthetic workup. A wide range of instrumental and theoretical techniques were employed to successfully determine the electronic structure of the complexes; c) WP3 comprised the study of the catalytic activity of the dinuclear and mononuclear metalloporphyrins in electrochemical proton and CO2 reduction reactions. Collaborative networks were established with colleagues from the Institute of Physical Chemistry to perform various experiments to substantiate and determine the electronic structures of these frameworks. The data obtained from the measurements showed a significant increase in catalytic activity and reduction in overpotential for the dinuclear complexes compared to the mononuclear complexes; d) WP4 encompassed evaluation of the catalytic parameters and the elucidation of the mechanistic pathway for the comparison of the catalytic activity between mono- and dinuclear metalloporphyrins. In addition, together with colleagues from the host research group, the candidate was involved in setting up a gas chromatography, bulk electrolysis and designing new cells for in situ EPR. Theoretical insights into the mechanism were gained via active collaboration with the institute’s theoretical research group. Evaluation of the catalytic parameters revealed a significant enhancement in the turnover numbers and Faradaic efficiency of the expanded metalloporphyrins. In addition, various strategies were successfully employed to address the problems associated with these moieties, such as insolubility and low product yield to a considerable extent. In addition, we have also used the setup to successfully demonstrate electrochemical CO2 reduction using a Ru-based molecular catalyst.
- Part of the project has already been published in three international peer-reviewed journals (Chem. Eur. J., 2022, 28, e202104550, ChemSusChem, 2023, 16, e202201146 and Chem. Eur. J., 2023, e202300405), while the remaining results will also soon be published. In addition, the results of the projects were presented at three international conferences (ICPP-2022, Madrid, ICOMC-2022, Prague and 55th DCHEMA-2022, Weimar) either in the form of poster or a talk. While, various aspects of the project were also discussed at the Open Science Day of the University of Stuttgart for various high-school and bachelor students.
