[Electrocatalytic proton and CO2 reduction: Metal based fused diporphyrins with proton relays for efficient catalysis]

The project deals with the design and development of catalysts for sustainable hydrogen production on a laboratory scale. The rapid growth of the world’s population, increasing industrialization and the loss of green cover have led to extensive utilization of fossil fuels over time. In addition, the greenhouse gases produced by burning these fuels have raised environmental concerns that have propelled the development of sustainable and renewable energy sources. Hydrogen as an energy carrier is one of the most promising alternatives to conventional fossil fuels, as it generates water as a byproduct of combustion in addition to its high energy density. Therefore, the development of sustainable production of hydrogen is one of the challenges of our time. Electrolysis of water is one of the most convenient carbon-free techniques to produce hydrogen from renewable energy sources. Therefore, considerable efforts and resources have been devoted to the search for materials or catalysts that can effectively catalyze the reduction of protons or water to hydrogen. In this context, metalloporphyrin catalysts, which are also prevalent in natural systems such as chlorophyll or haemoglobin, can be effectively used to facilitate electrochemical HER.

Consistent with the above discussions, it is imperative that the catalytic systems based on bimetallic triply fused porphyrins developed in the project will contribute greatly to the ongoing research work in this field. Considering the lack of literature reports on electrochemical small molecule activations with these ligand scaffolds, the results obtained in this project can be used as a knowledge base for future projects, especially in terms of sustainability. Although, most of the work in this project and the results are limited to small scale laboratory application and the expansion of the literature database, there is a possibility of transferring them to industrial scale.

 i. Synthesis of a series of first row transition metal complexes of bimetallic triply fused and monomeric metalloporphyrin. Optimization of reaction conditions to address low yields of the bimetallic fused porphyrins.

ii. Judicious choice of functional groups on the backbone of the fused porphyrin ligands to deal with solubility problems of the extended framework.

iii.Investigation of the electronic structures of all the synthesized complexes to determine the ground state structure using various spectroscopic methods and crystallographic techniques.

iv.Electrochemical investigation of the fused metalloporphyrin and drawing a parallel with the corresponding monometallic complexes.

v.Analysis of the catalytic activity of the triply fused metalloporphyrin towards electrochemical HER and comparison of their activity with respective monomeric complexes.

vi.Quantification of electrocatalytic efficiency, and elucidation of catalytic reaction mechanism to develop structure-activity correlations.