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Title: Hydrazone-Linked Heptazine Polymeric Carbon Nitrides for Synergistic Visible-Light-Driven Catalysis

Abstract

Heptazine-based conjugated polymeric carbon nitrides (PCNs) are promising metal-free photocatalysts, yet their synthesis is challenging due to the electron-deficiency and insolubility of heptazine units. Indeed, heptazine-containing polymers have only been prepared through nucleophilic substitution with amines by using toxic cyameluric chloride as the starting material. Herein, we report the novel and environmentally friendly method for preparing heptazine-based mesoporous PCNs with hydrazone links formed through a simple Schiff base condensation of melem-NH2 and aldehydes. Unlike cyameluric chloride, melem-NH2 is non-toxic, stable, and can be readily obtained from melem and hydrazine in solution. We demonstrate that the hydrazone linkages and the heptazine units synergistically enhance the photocatalytic activity of PCNs in visible-light-driven aerobic oxidation of benzyl alcohol to benzaldehyde. In particular, the polymer constructed from melem-NH2 and p-phthalaldehyde shows 17 times more activity than graphitic carbon nitride (g-C3N4).

Authors:
 [1];  [2];  [3];  [2]; ORCiD logo [2];  [2];  [4]; ORCiD logo [4]
  1. Fuzhou Univ. (China). College of Materials Science and Engineering; Univ. of Amsterdam (Netherlands). Van't Hoff Inst. for Molecular Sciences (HIMS)
  2. Fuzhou Univ. (China). College of Materials Science and Engineering
  3. Ames Lab., Ames, IA (United States)
  4. Ames Lab., and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1632322
Alternate Identifier(s):
OSTI ID: 1631509
Report Number(s):
IS-J-10,237
Journal ID: ISSN 0947-6539
Grant/Contract Number:  
51703031; 201506140058; AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 26; Journal Issue: 33; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heptazines; hydrazone linkages; porous polymers; synergistic effects; visible light

Citation Formats

Zhang, Wei, Xu, Congying, Kobayashi, Takeshi, Zhong, Yun, Guo, Zhiyong, Zhan, Hongbing, Pruski, Marek, and Huang, Wenyu. Hydrazone-Linked Heptazine Polymeric Carbon Nitrides for Synergistic Visible-Light-Driven Catalysis. United States: N. p., 2020. Web. doi:10.1002/chem.202000934.
Zhang, Wei, Xu, Congying, Kobayashi, Takeshi, Zhong, Yun, Guo, Zhiyong, Zhan, Hongbing, Pruski, Marek, & Huang, Wenyu. Hydrazone-Linked Heptazine Polymeric Carbon Nitrides for Synergistic Visible-Light-Driven Catalysis. United States. doi:https://doi.org/10.1002/chem.202000934
Zhang, Wei, Xu, Congying, Kobayashi, Takeshi, Zhong, Yun, Guo, Zhiyong, Zhan, Hongbing, Pruski, Marek, and Huang, Wenyu. Tue . "Hydrazone-Linked Heptazine Polymeric Carbon Nitrides for Synergistic Visible-Light-Driven Catalysis". United States. doi:https://doi.org/10.1002/chem.202000934.
@article{osti_1632322,
title = {Hydrazone-Linked Heptazine Polymeric Carbon Nitrides for Synergistic Visible-Light-Driven Catalysis},
author = {Zhang, Wei and Xu, Congying and Kobayashi, Takeshi and Zhong, Yun and Guo, Zhiyong and Zhan, Hongbing and Pruski, Marek and Huang, Wenyu},
abstractNote = {Heptazine-based conjugated polymeric carbon nitrides (PCNs) are promising metal-free photocatalysts, yet their synthesis is challenging due to the electron-deficiency and insolubility of heptazine units. Indeed, heptazine-containing polymers have only been prepared through nucleophilic substitution with amines by using toxic cyameluric chloride as the starting material. Herein, we report the novel and environmentally friendly method for preparing heptazine-based mesoporous PCNs with hydrazone links formed through a simple Schiff base condensation of melem-NH2 and aldehydes. Unlike cyameluric chloride, melem-NH2 is non-toxic, stable, and can be readily obtained from melem and hydrazine in solution. We demonstrate that the hydrazone linkages and the heptazine units synergistically enhance the photocatalytic activity of PCNs in visible-light-driven aerobic oxidation of benzyl alcohol to benzaldehyde. In particular, the polymer constructed from melem-NH2 and p-phthalaldehyde shows 17 times more activity than graphitic carbon nitride (g-C3N4).},
doi = {10.1002/chem.202000934},
journal = {Chemistry - A European Journal},
number = 33,
volume = 26,
place = {United States},
year = {2020},
month = {6}
}

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