Publisher: American Chemical Society (ACS)

Issue: 12

License: [{"start"=>{"date-parts"=>[[2022, 6, 8]], "date-time"=>"2022-06-08T00:00:00Z", "timestamp"=>1654646400000}, "content-version"=>"vor", "delay-in-days"=>0, "URL"=>"https://creativecommons.org/licenses/by/4.0/"}]

Publication date(s): 2022/06/28 (print) 2022/06/08 (online)

Pages: 5511-5521

Volume: 34 Issue: 12

Journal: Chemistry of Materials

Link: [{"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.2c00528", "content-type"=>"application/pdf", "content-version"=>"vor", "intended-application"=>"unspecified"}, {"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.2c00528", "content-type"=>"unspecified", "content-version"=>"vor", "intended-application"=>"similarity-checking"}]

Solar H₂O₂ produced by O₂ reduction provides a green, efficient, and ecological alternative to the industrial anthraquinone process and H₂/O₂ direct-synthesis. We report efficient photocatalytic H₂O₂ production at a rate of 73.4 mM h^–1 in the presence of a sacrificial donor on a structurally engineered catalyst, alkali metal-halide modulated poly(heptazine imide) (MX → PHI). The reported H₂O₂ 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 H₂O₂ 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 O₂ 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 H₂O₂ production rate. Spectroscopic data help us to rationalize the exceptional photochemical performance and structural characteristics of MX → PHI.