Engineering the Surface of a Polymeric Photocatalyst for Stable Solar‐to‐Chemical Fuel Conversion from Seawater

The design of an efficient and highly selective organic polymeric semiconductor photocatalyst consisting of Earth-abundant elements for solar fuel generation using seawater, and also deionized water, as a proton source is reported. The mesoporous g-C3 N4 synthesized using a conventional precursor (urea) shows significant H2 generation (ca. 33 000 μmol h-1 g-1 ) and drives the photoreduction of CO2 to CH4 , along with trace amount of methanol. However, when the chosen precursor cyanamide is used, drastic improvement in H2 generation (ca. 41 600 μmol h-1 g-1 ) and CO2 photoreduction is observed. The introduction of a surface nitrogen deficiency and modification of the surface with Cu0 further enhances solar H2 generation (ca. 50 000 μmol h-1 g-1 ) and CO2 photoreduction (3.12 μmol h-1 g-1 ) activity, respectively, owing to improvement in light harvesting and charge separation, as revealed by a shorter average lifetime of 3.52 ns and higher Stern-Volmer quenching constant value of approximately 11.2 m-1 . In addition, improved selectivity in CO2 photoreduction to only CH4 is also observed. The designed photocatalytic system is stable, with the solar H2 generation rate increasing even after 20 h under continuous illumination with a turnover number of 6500. When seawater used instead of deionized water, the overall solar fuel generation efficiencies of all photocatalysts marginally decreased owing to a decrease in the photogenerated charge-carrier separation efficacy.