Journal
INORGANIC CHEMISTRY
Volume 58, Issue 23, Pages 15880-15888Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.9b02287
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Funding
- Research Grants Council of Hong Kong [17212015, C7044-14G, T21-771/16R]
- National Natural Science Foundation of China [41701560, 51708143]
- Guangzhou Science and Technology Foundation of China [201804010197, 201804010366]
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Graphitic carbon nitride (g-C3N4)-based materials have attracted interdisciplinary attention from many fields. However, their crystal structures have not yet been described well. Poly(triazine imide)/LiCl (PTI/LiCl) of good crystallinity synthesized from salt melts enables a confident structural solution for a better understanding of g-C3N4-based materials. In this study, we synthesize PTI/LiCl of high crystallinity in air without byproducts and confirm the orthorhombic feature, which is not observed in powder X-ray diffraction (PXRD) patterns at room temperature, by employing low-temperature synchrotron PXRD. Together with spectroscopic techniques (X-ray photoelectron spectroscopy, solid-state nuclear magnetic resonance, and Fourier-transform infrared/Raman), the orthorhombic structure (space group Cmc2(1), No. 36) was determined and found to be a superstructure of the previously reported hexagonal structure, as confirmed by electron diffraction. The temperature-dependent synchrotron PXRD data also reveal a highly anisotropic expansion. This work also shows the much higher activity of PTI/LiCl than of g-C3N4 for the photocatalytic degradation of methyl orange under ultraviolet irradiation, especially so for PTI/LiCl with a densely packed (001) plane. This study demonstrates the structural complexity of the g-C3N4 class of materials and illustrates how their temperature-dependent anisotropies facilitate the discovery of the structural features in resolving the structure of g-C3N4-related materials and their structure-property relationship.
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