Executive Summary : | Global warming and environmental issues are the major challenges in the current world and we are looking for sustainable renewable energies which are directly related to net zero emission and carbon neutral processes. Several technologies are developing worldwide including Indian Government which set a major target of net zero carbon emission by 2070 in the Paris Agreement. The harvesting of green hydrogen is one of the fundamental steps to avoid grey hydrogen which is synthesized from non-renewable sources and is currently used in industrial processes. Green hydrogen is mainly produced by the electrochemical water-splitting process where many limitations and challenges still exist (like the efficiency of the electrode, direct use of solar energy, electrode lifetime, etc.). The alternative source of renewable hydrogen is biomass which is considered the ultimate renewable source. Biomass is generated from the natural photosynthesis process in living trees where the solar energy is stored as chemical energy. Cellulose and hemicellulose are the major component in biomass which is considered hydrogen-rich substrates. Some techniques are developed for hydrogen production from biomass although they are based on thermal techniques or heterogeneous-based catalytic process which generally works at high temperature and drastic reaction conditions. The development of a homogeneous catalyst is extremely important at the current time which will be functional for the synthesis of the bio-hydrogen at moderate reaction conditions and follow the green chemistry protocols. To do so, the new generation of sustainable catalyst designing is our prime target in this project which will be based on the bifunctional cooperative molecular catalyst. The molecular catalyst with an accurate ligand architecture is required to activate the cellulose derivatives. In this project, the synthesis of metal-coordinated bis-(2-hydroxy pyridine) complexes is proposed which should show the dual nature or bifunctionality during the catalysis process. The catalysts will follow the basic principle of metal-ligand cooperativity for the acceptorless alcohol dehydrogenation of substrates. The basic structure of the cellulose derivatives contains the hydroxy moieties in the adjacent carbon chain which afford a strong hydrogen bonding network. The decomposition of polymeric cellulose or hemicellulose to monosaccharide and followed by the alcohol dehydrogenation will generate hydrogen in presence of an active catalyst under appropriate reaction conditions. So, the hydrogen bonding properties in the catalyst also play a crucial role during the catalysis process. The maximum TON and TOF for the hydrogen generation will be our main goal in this process and followed by the details mechanistic studies will allow us to modify our catalyst system for further development. The details of the metal-ligand cooperativity and the role of the ligand in the outer-sphere substrate activation will be studied. |