Enhanced HO Production via Photocatalytic O Reduction over Structurally-Modified Poly(heptazine imide).

Solar HO produced by O reduction provides a green, efficient, and ecological alternative to the industrial anthraquinone process and H/O direct-synthesis. We report efficient photocatalytic HO production at a rate of 73.4 mM h in the presence of a sacrificial donor on a structurally engineered catalyst, alkali metal-halide modulated poly(heptazine imide) (MX → PHI). The reported HO production is nearly 150 and >4250 times higher than triazine structured pristine carbon nitride under UV-visible and visible light (≥400 nm) irradiation, respectively. Furthermore, the solar HO production rate on MX → PHI is higher than most of the previously reported carbon nitride (triazine, tri-s-triazine), metal oxides, metal sulfides, and other metal-organic photocatalysts. A record high AQY of 96% at 365 nm and 21% at 450 nm was observed. We find that structural modulation by alkali metal-halides results in a highly photoactive MX → PHI catalyst which has a broader light absorption range, enhanced light absorption ability, tailored bandgap, and a tunable band edge position. Moreover, this material has a different polymeric structure, high O trapping ability, interlayer intercalation, as well as surface decoration of alkali metals. The specific C≡N groups and surface defects, generated by intercalated MX, were also considered as potential contributors to the separation of photoinduced electron-hole pairs, leading to enhanced photocatalytic activity. A synergy of all these factors contributes to a higher HO production rate. Spectroscopic data help us to rationalize the exceptional photochemical performance and structural characteristics of MX → PHI.