The pursuit of a low-cost, robust water oxidation catalyst is a pursuit for the generation of clean, renewable solar hydrogen. Inspired by nature's calcium-manganese water oxidation catalyst, manganese-based minerals have long been of interest as biologically inspired catalysts. Birnessite (layered AxMnO2, A = s-block metal ion) has long been studied for this catalysis, but generally thought to be among the poorer active Mn-based catalysts. We have shown that enrichment of the catalyst by MnIII, or the inclusion of CoII, FeII, NiII or CuII dopants significantly increases catalytic activity. Molecular dynamics simulation of interlayer water dynamics guides our understanding and design of better catalytic systems. Guided by Quantum calculations, we also have demonstrated that vertical distribution of such ions in adjacent stacks by controlled stacking of nanosheets gives improved catalysis, mediated by nearly isoenergetic positioning of conduction band maxiumum of one sheet with valence band minimum of an adjacent sheet. With these innovations, birnessite can be crafted into the best known manganese-oxide-based water-oxidation catalysts.

Experimental optimization of layered manganese oxide water-oxidation catalysts by nano-level organizational control guided by molecular dynamics and quantum calculation

ACS Spring Meeting 2021

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.