Executive Summary : | Natural system is indeed so beautiful to carry out various chemical reactions with high specificity and selectivity. It is a great lesson to learn from nature including natural photosynthesis and to mimic such natural process through clean, green and sustainable pathway for the development of environment friendly, low cost, easy to synthesize and recyclable bioinspired photo-catalytic energy nanomaterials. In this regard, water splitting reaction to produce proton and successive reduction of proton to produce molecular hydrogen is one of the important chemical transformations for solar fuel generation through green and sustainable pathway in order to address the energy crisis issue all over the world. Hydrogen (H2) has both the properties including a chemical reductant as well as carbon-free fuel and thus the reduction of protons to generate solar fuel is a reaction of high interest in the field of current research. Moreover, the investigation of the mechanistic studies of the photo catalytic hydrogen evolution reaction (HER) are really helpful to understand more complex reactions involving proton transfers. In this regard, perylenemonoimide/bisimide (PMI/PBI) appended peptide conjugated Co(III)-metallopeptide could be one of the smart functional supramolecular nanomaterials for water splitting and successive proton reduction to produce molecular hydrogen as judicious placement of suitably substituted phenylalanine (N,N-dimethyl-p-aminophenylalanine) within the peptide sidechain which will allow sacrificial electron transfer to perylene monoimide/bisimide. Interestingly, perylene is attached to the lysine side chain of the peptide and that is why perylene is a good source of electrons in this design to sensitize the photochemical reaction. Moreover, metallopeptide is chosen for very good water oxidation catalyst and the overall peptide backbone for promoting self-assembly for the construction of novel bioinspired supramolecular energy nanomaterials. These peptides will be synthesized with various different natural and unnatural amino acids side chains for stable metallopeptide formation, self-assembly and hydrogelation. These supramolecular materials will be further used for water oxidation and successive proton reduction to produce molecular hydrogen in aqueous medium (Scheme 1) at neutral pH by using photochemical and photo(electro)chemical techniques. |