Ultrafine Cobalt Catalysts on Covalent Carbon Nitride Frameworks for Oxygenic Photosynthesis.

The rational cooperation of sustainable catalysts with suitable light-harvesting semiconductors to fabricate photosynthetic device/machinery has been regarded as an ideal technique to alleviate the current worldwide energy and environmental issues. Cobalt based species (e.g., Co-Pi, Co3O4, and Co-cubene) have attracted particular attentions because they are earth-abundant, cost-acceptable, and more importantly, it shows comparable water oxidation activities to the noble metal based catalysts (e.g., RuO2, IrO2). In this contribution, we compared two general cocatalysts modification strategies, based on the surface depositing and bulk doping of ultrafine cobalt species into the sustainable graphitic carbon nitride (g-C3N4) polymer networks for oxygenic photosynthesis by splitting water into oxygen, electrons, and protons. The chemical backbone of g-C3N4 does not alter after both engineering modifications; however, in comparison with the bulk doping, the optical and electronic properties of the surface depositing samples are efficiently promoted, and the photocatalytic water oxidation activities are increased owing to much more exposed active sites, reduced overpotential for oxygen evolution and the accelerated interface charge mobility. This paper underlines the advantage of surface engineering to establish efficient advanced polymeric composites for water oxidation, and it opens new insights into the architectural design of binary hybrid photocatalysts with high reactivity and further utilizations in the fields of energy and environment.