New Insights into the Role of Amines in the Synthesis of Molecular Sieves in Ionic Liquids

Authors

  • Renshun Xu,

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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  • Weiping Zhang Prof. Dr.,

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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  • Jing Guan,

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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  • Yunpeng Xu Dr.,

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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  • Lei Wang Dr.,

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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  • Huaijun Ma Dr.,

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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  • Zhijian Tian Prof. Dr.,

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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  • Xiuwen Han Prof.,

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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  • Liwu Lin Prof.,

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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  • Xinhe Bao Prof. Dr.

    1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China), Fax: (+86) 411-8469-4447
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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.

original image

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.

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