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New Insights into the Role of Amines in the Synthesis of Molecular Sieves in Ionic Liquids
Author(s) -
Xu Renshun,
Zhang Weiping,
Guan Jing,
Xu Yunpeng,
Wang Lei,
Ma Huaijun,
Tian Zhijian,
Han Xiuwen,
Lin Liwu,
Bao Xinhe
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200802590
Subject(s) - molecular sieve , ionic liquid , crystallization , morpholine , ionic bonding , chemistry , nuclear magnetic resonance spectroscopy , hydrogen bond , thermogravimetric analysis , raman spectroscopy , spectroscopy , nucleation , zeolite , chemical engineering , inorganic chemistry , molecule , organic chemistry , ion , catalysis , adsorption , physics , quantum mechanics , optics , engineering
Abstract In a new direction : In situ NMR spectroscopy and DFT calculation studies demonstrate that the hybrid of imidazolium ionic liquids with morpholine can be formed by means of hydrogen bonds during the crystallization of molecular sieves (see graphic; T=Al or P), which drastically alters the structure‐directing property.A combination of state‐of‐the art in situ one‐ and two‐dimensional NMR spectroscopy and density functional theory (DFT) calculations have been employed for the first time to investigate the role of amines in the synthesis of aluminophosphate molecular sieves in ionic liquids (ILs). In situ rotating‐frame nuclear Overhauser effect spectroscopy (ROESY) was used to demonstrate that the hybrid of imidazolium ionic liquids with organic amines, such as morpholine, connected through a hydrogen bond can be formed in the gel during the crystallization of molecular sieves. By combining the characterizations of the final solid products obtained by using XRD analyses, solid‐state NMR spectroscopy, thermogravimetric analysis, and DFT calculation results, it was verified that the hybrid between morpholine and the imidazolium cation in the initial preparation stage can act as the structure‐directing agent (SDA) for the synthesis of AFI‐structured aluminophosphate molecular sieves. Our findings may suggest a synthesis mechanism of molecular sieves in ionic liquids in which the IL–organic amine hybrid is required in the nucleation step, whereas the crystal growth occurs through the occlusion of ionic liquids in the zeolite channels.