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Aromatic alcohols oxidation and hydrogen evolution over π-electron conjugated porous carbon nitride rods

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Abstract

Photocatalysis using polymeric carbon nitride (CN) materials is a constantly evolving field, where the variation of synthetic procedures allows the constant improvement of activity by tackling the intrinsic limitations of these materials (optical absorbance, specific surface area, charge migration, etc.). Amongst the possible photocatalytic reactions, the most popular application of CNs is the hydrogen evolution reaction (HER) from water. In this work, we design precisely-controlled carbon-doped porous CN rods with extended π-electron conjugation from supramolecular assemblies of melem and co-monomers, which partially substitute nitrogen for carbon atoms at the pyrimidine ring of the melem. Dense hydrogen bonds and good thermal stability of the melem-based supramolecular framework allow synthesizing a more ordered structure for improved charge migration; the control from the molecular level over the position of carbon-substituted nitrogen positions tailors the band alignment and photogenerated charge separation. The optimal photocatalyst shows an excellent HER rate (up to 10.16 mmol·h−1·g−1 under 100 W white light-emitting diode (LED) irradiation, with an apparent quantum efficiency of 20.0% at 405 nm, which is 23.2 times higher compared to a reference bulk CN). To fully harness the benefits of the developed metal-free CNs, selective oxidation reaction of aromatic alcohols is demonstrated with high conversion and selectivity.

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Acknowledgements

The authors are grateful for the financial support from the National Natural Science Foundation of China (Nos. 22078028 and 21978026), the Special Program for Introducing Foreign Talents of Changzhou (No. CQ20214032), the joint Israel Science Foundation-National Science Foundation of China (ISF-NSFC) (No. 2969/19 and the ISF No. 601/21). The authors thank Jonathan Tzadikov, Rotem Geva, Liel Abisdris, Junyi Li, and Ayelet Tashakory (Ben-Gurion University of the Negev) for technical support and Dr. Laurent Chabanne for fruitful discussion.

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Authors and Affiliations

  1. Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou University, Changzhou, 213164, China

    Jiawei Xia & Haiqun Chen

  2. Department of Chemistry and Ilse Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beer-Sheva, 8410501, Israel

    Jiawei Xia, Neeta Karjule, Gabriel Mark, Michael Volokh & Menny Shalom

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  1. Jiawei Xia
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  2. Neeta Karjule
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  3. Gabriel Mark
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Correspondence to Menny Shalom.

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Xia, J., Karjule, N., Mark, G. et al. Aromatic alcohols oxidation and hydrogen evolution over π-electron conjugated porous carbon nitride rods. Nano Res. 15, 10148–10157 (2022). https://doi.org/10.1007/s12274-022-4717-4

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