title: New insights into the role of amines in the synthesis of molecular sieves in ionic liquids.
abstract: 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.
authors.affiliation: State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
authors.forename: Renshun
authors.initials: R
authors.lastname: Xu
authors.forename: Weiping
authors.initials: W
authors.lastname: Zhang
authors.forename: Jing
authors.initials: J
authors.lastname: Guan
authors.forename: Yunpeng
authors.initials: Y
authors.lastname: Xu
authors.forename: Lei
authors.initials: L
authors.lastname: Wang
authors.forename: Huaijun
authors.initials: H
authors.lastname: Ma
authors.forename: Zhijian
authors.initials: Z
authors.lastname: Tian
authors.forename: Xiuwen
authors.initials: X
authors.lastname: Han
authors.forename: Liwu
authors.initials: L
authors.lastname: Lin
authors.forename: Xinhe
authors.initials: X
authors.lastname: Bao