CAS: H-atom Uptake and Transfer at the Surface of Vanadium-alkoxide and -carboxylate Clusters

With the support from the Chemical Synthesis (SYN) program in the Division of Chemistry Professor Ellen Matson of the University of Rochester is studying the hydrogen atom uptake and transfer at the surface of polyoxovanadate complexes. The ability to control the activation and transfer of hydrogen is vital for the implementation of H2 use as a fuel and energy carrier, but also the broader effort to electrify chemical manufacturing. The research investigated in this proposal will achieve atomic-level insights into the transfer of H-atom equivalents on a series of model substrates for interfacial (de)hydrogenation chemistries. Results from this work will inform the design of novel materials for efficient and selective hydrogenation reactivity using protons and electrons as a source of hydrogen. The project will support the training of graduate and undergraduate students in the synthesis and characterization of air- and moisture-sensitive inorganic complexes, as well as mechanistic elucidation. The project will also support a regional meeting of inorganic chemists titled the “Western New York Inorganic Symposium” to foster networks and collaborations across local research and undergraduate institutions. The proposed research implements polyoxovandate-alkoxide and polyoxovanadate-carboxylate clusters for the purposes of elucidating structure-function relationships of H-atom uptake on the surface of reducible metal oxide nanomaterials. The project will leverage both self-assembly and post-synthetic modification of polyoxovanadate clusters to access novel structures that mimic surface reactivity of reduced metal oxides. During the project period, elements that modify the regioselectivity of H-atom uptake at the surface of the polyoxovanadate will be investigated (e.g., heterometal substituted assemblies, assemblies featuring bridging and terminal oxide ligands). The improved knowledge of proton-electron transfer reactions at vanadium oxide assemblies will be used in the context of improving product selectivity of stoichiometric O2 (i.e. H2O, H2O2) with broader implications for reducible metal oxide facilitated electrocatalysis. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.