Hydrogen chemistry as a potential basis for future hydrogen technology has recently experienced three important new challenges in research: development of metal-free and of non-precious metal hydrogenation chemistry and the hydrogenation of CO2/bicarbonate and CO. New hydrogenations with non-precious metal catalysts may pave the way to more efficiently produce chiral compounds and low carbon oxygenates. In addition to hydrogenation chemistry a new approach was created to store hydrogen chemically in MOFs introducing new functional units for its reversible binding. This project is therefore divided into three parts to establish efficient new ways of hydrogen catalyses and storage:
A) Enantioselective hydrogenations of prochiral olefins and hetero-olefins with non-precious metal catalysts
B) Development of catalysts for homogeneous CO2 /HCO3- and CO hydrogenations to low carbon oxygenates
C) Hydrogen storage in linker and metal center modified metalorganic frameworks (MOFs)
Parts A) and B) propose various new rhenium, tungsten and molybdenum based hydrogenation catalyses for olefins and hetero-olefins and for CO2/bicarbonate and CO reductions. Part A) is additionally directed toward chiral hydrogenations using bidentate chiral phosphines and nitrogen ligands. Part B) is thought to establish pathways to low molecular weight oxygenated low carbon materials, such as methanol, formoses ((CH2O)n) and ethylene glycol, which could principally be envisaged as chemical hydrogen storage materials. Part C) focuses on hydrogen storage in chemically modified porous metalorganic framework compounds (MOFs) constructed from 3d elements building up porous frameworks. The strategy pursues the accomplishment of a second generation of MOF frameworks incorporating chemical functionalities, thus providing additional hydrogen storage capacity on top of the given MOF type physical hydrogen storage potential. Special linker functions are developed enabling reversible chemical hydrogen storage and metal centers with free sites to allow binding of dihydrogen to them.