2-Isopropyl-1,3-dimethylimidazolium as a versatile structure-directing agent in the synthesis of zeolites

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 52; no. 43; pp. 15697 - 15711
• Main Authors: Yu, Huajian, Rojas, Alex, Gao, Zihao Rei, Gómez-Hortigüela, Luis, Villaescusa, Luis A, Li, Jian, Paillaud, Jean-Louis, Camblor, Miguel A
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 07.11.2023
• Subjects: Cations; Chemical composition; Chemical Sciences; Chemical synthesis; Crystallization; Diffraction patterns; Germanium; Impurities; NMR; Nuclear magnetic resonance; Silicon dioxide; Topology; X ray powder diffraction; Zeolites
• DOI: 10.1039/d3dt02414h
• ISSN: 1477-9226

An organic cation lacking specificity in its structure-directing action offers the possibility, through the screening of other structure-directing parameters, to synthesize a variety of zeolites. In this work we show that the organic structure-directing agent 2-isopropyl-1,3-dimethylimidazolium (2iPr13DMI) can produce up to seven different zeolite phases depending on water concentration, the presence of inorganic impurities, crystallization temperature and time, and germanium molar fraction. The obtained phases are very different in terms of pore system, connectivity of the zeolite structure and structural units. At the pure SiO 2 side, ZSM-12 and SSZ-35 dominate, with ZSM-12 being favored by the presence of potassium impurities and by less concentrated conditions. The introduction of Ge at low levels favors SSZ-35 over ZSM-12 and as the Ge fraction increases it successively affords CSV , -CLO and two distinct UOS zeolites, HPM-11 and HPM-6. These two zeolites have the same topology but distinct chemical compositions and display powder X-ray diffraction patterns that are much different from each other and from that of as-synthesized IM-16 ( UOS reference material). They also show different symmetry at 96 K. Rietveld refinements of the three as-made UOS materials mentioned are provided. HPM-6 and HPM-11 are produced in distinct, non-adjacent crystallization fields. The frequent cocrystallization of the chiral STW zeolite, however, did not afford its synthesis as a pure phase. Molecular mechanics simulations of the location of the organic cation and host-guest interactions fail to explain the observed trends, but also considering the intrinsic stability of the zeolites and the effect of germanium help to rationalize the results. The study is completed by DFT calculations of the NMR chemical shifts of 13 C in UOS (helping to understand splittings in the spectrum) and 19 F in CSV (supporting the location of fluoride inside the new [4 4 5 2 ], which is an incomplete double 4-ring). Organic structure directing agents with low specificity offer opportunities for zeolite discovery by tweaking other structure-directing factors.