Sharma, Pankaj  ORCID: https://orcid.org/0000-0003-2319-260X, Slater, Thomas J. A. ORCID: https://orcid.org/0000-0003-0372-1551, Sharma, Monika, Bowker, Michael ORCID: https://orcid.org/0000-0001-5075-1089 and Catlow, C. Richard A. ORCID: https://orcid.org/0000-0002-1341-1541
2022.
Enhanced H2O2 production via photocatalytic O2 reduction over structurally-modified poly(heptazine imide).
Chemistry of Materials
34
(12)
, pp. 5511-5521.
10.1021/acs.chemmater.2c00528
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Abstract
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.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Professional Services > Advanced Research Computing @ Cardiff (ARCCA) Research Institutes & Centres > Cardiff Catalysis Institute (CCI) Schools > Chemistry |
| Additional Information: | CC-BY |
| Publisher: | American Chemical Society |
| ISSN: | 0897-4756 |
| Funders: | European Union�s Horizon 2020 Research and Innovation Programme, EPSRC |
| Date of First Compliant Deposit: | 15 June 2022 |
| Date of Acceptance: | 19 May 2022 |
| Last Modified: | 02 Aug 2024 09:13 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/150524 |
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