Yang Zhao,Zhaoqi Ye,Lei Wang,Hongbin Zhang,Fangqi Xue,Songhai Xie,Xiao-Ming Cao,Yahong Zhang,Yi Tang
Constructing superstructured crystalline materials by crystal engineering is an attractive objective for miscellaneous fields of researchers spanning biomimetics to catalytic materials. Zeolite is a kind of important crystalline catalyst, and superstructured zeolite has great potential for widespread applications. However, the ambiguous crystallization mechanisms hamper the effective and scientific fabrication of superstructured zeolite with exceptional properties. Herein, a fractal superstructured MTW zeolite with mesocrystal side branches is prepared via a nanoparticle-based nonclassical pathway with twinning-plane induced crystallization, which is distinct from the formation of general mesocrystal via crystal–crystal oriented attachment. Deformed atomic connection at a specific crystallographic plane contributes to the production of side branches. Moreover, this intriguing morphology could be regulated merely via adjusting the crystallization kinetics based on the unequivocal nonclassical crystallization mechanism. It will open a new avenue for design and synthesis of targeted crystals with superstructure and extraordinary properties.
A series of diquaternary pyrazolium-derived organic templates (N,N′-dimethyl-N,N′-1,6-dihexylidenedipyrazolium, N,N′-diethyl-N,N′-1,6-dihexylidenedipyrazolium, N,N′-dipropyl-N,N′-1,6-dihexylidenedipyrazolium, denoted as 6C-DMP, 6C-DEP, 6C-DPP, respectively) with methyl, ethyl and propyl groups substituted on the N atom of pyrazole ring at both terminals have been used in the synthesis of high silica MTW and MFI zeolites. Through combining the characterization results, including XRD, NMR, elemental analysis, TG, XRF, FE-SEM, N2 sorption and FE-TEM, with molecular mechanics simulations to explore the location, orientation and the interaction energies of the three templates, we confirmed the state of templates in zeolite framework, carefully characterized their morphology/structure properties, and finally investigated their different spatial effects for the zeolite formation. The study found that 6C-DMP and 6C-DEP are able to produce MTW, while 6C-DPP is able to produce MFI. 6C-DMP, owing to a good match with the MTW framework and can be used to synthesize regular MTW zeolite with few defects. The MTW zeolite prepared by using 6C-DEP as a template presents more defects and irregular macromorphology due to a relatively poor match to the MTW framework. 6C-DPP can get MFI other than MTW due to a larger spatial hindrance, and it is located in the MFI framework with a special spatial orientation.
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