Water oxidation, a crucial half of water splitting, has slow kinetics since it involves a multi-electron transfer process. The benchmark noble IrO2 and RuO2 catalysts are discouraging due to their unsustainability. CoFe Prussian blue analogues (CoFe-PBA) are highly ranked as one of the alternatives for the noble catalyst due to their facile synthesis approach, easily tuned metals sites, outstanding stability, and fast electron transfer from Fe to catalytic Co sites through the short cyanide bridge. Several methods have been reported to tune the activity of Co-Fe PBA; however, almost all the methods reported to directly tune the catalytic cobalt site usually lead to a destruction in the cyanide environment and transformation into its corresponding oxides, sulfides, and phosphides. Herein, with the understanding of the catalytic coordination environment in PBA, we designed the catalytic cobalt sites of CoFe-PBA with bidentate pyridyl ligands. A series of characterization techniques confirms the preservation of the cyanide coordination environment. Finally, we investigated and compared their activity using experimental photocatalytic studies and computational electronic structure calculations.

Solar-driven water oxidation with ligand-engineered Prussian blue analogues

ACS Spring 2022

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