期刊
INORGANIC CHEMISTRY
卷 60, 期 24, 页码 18957-18963出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c02769
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资金
- Max-Planck Society
A novel bottom-up preparation route for heptazine-based polymers (melon) was presented, showing the growth characteristics of isolated 1D melon strings in microporous templates. The study demonstrated the advantages and limitations of the bottom-up approach using microporous templates with different pore sizes, and clarified how the molecular size of heptazine units influenced the formation of melon in micropores of varying widths. The self-assembly of isolated 1D melon to stacked 3D structures offered a new experimental perspective to the controversial debate on the polymerization degree in 2D sheets of graphitic carbon nitride.
Herein, we present a novel bottom-up preparation route for heptazine-based polymers (melon), also known as graphitic carbon nitride. The growth characteristics of isolated 1D melon strings in microporous templates are presented and studied in detail. Removal of the microporous silicate template via etching is accompanied by the self-assembly of a 1D melon to stacked 3D structures. The advantages and limitations of the bottom-up approach are shown by using microporous templates with different pore sizes (ETS-10, ZSM-S, and zeolite Y). In accordance with the molecular size of the heptazine units (0.67 nm), a 1D melon can be deposited in ETS-10 with a pore width of about 0.78 nm, whereas its formation in the smaller 0.47 nm pores of ZSM-S is sterically impeded. The self-assembly of isolated 1D melon to stacked 3D structures offers a novel experimental perspective to the controversial debate on the polymerization degree in 2D sheets of graphitic carbon nitride as micropore sizes below 1 nm confine the condensation degree of heptazine to isolated 1D strands at a molecular level. The growth characteristics and structural features were investigated by X-ray diffraction, N-2 physisorption, scanning transmission electron microscopy/energy-dispersive X-ray analysis, C-13 CP-NMR spectroscopy, and attenuated total reflection- infrared spectroscopy.
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