Chemical Research in Chinese Universities ›› 2017, Vol. 33 ›› Issue (2): 231-238.doi: 10.1007/s40242-017-6420-7

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Synthesis, Post-modification and Catalytic Properties of Metal-organic Framework NH2-MIL-53(Al)

LIU Lili, TAI Xishi, ZHOU Xiaojing, LIU Lijuan   

  1. School of Chemistry & Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, P. R. China
  • Received:2016-10-11 Revised:2016-10-28 Online:2017-04-01 Published:2016-11-28
  • Contact: LIU Lili,E-mail:liulili122@126.com;TAI Xishi,E-mail:taixs@wfu.edu.cn E-mail:liulili122@126.com;taixs@wfu.edu.cn
  • Supported by:

    Supported by the Promotive Research Fund for Young and Middle-aged Scientists of Shandong Province, China(No. BS2014CL021), the Project of Shandong Provincical Higher Educational Science and Technology Program, China(No.J14LC01) and the Technology Research and Development Program of Weifang, China(No.2014GX030).

Abstract:

A postsynthetic modification method was used to prepare salicylaldehyde functionalized metal-organic frameworks through the nucleophilic addition of salicylaldehyde with the amine group present in the frameworks of NH2-MIL-53(Al). Hydroxyl groups were successfully grafted onto NH2-MIL-53(Al), and imine groups were formed. Importantly, these hydroxyl and imine groups of the resulting NH2-MIL-53(Al)-SA can be used as the anchoring group to stabilise Au3+ ions and Au0 nanoparticles(NPs). By doing this, Au3+ ions and Au0 NPs were successfully encapsulated in the cages of NH2-MIL-53(Al) by a simple impregnation method. The resulting gold functionalized NH2-MIL-53(Al) showed good catalytic activities in the one-pot synthesis of structurally divergent propargylamines by three-component coupling reactions of aldehydes, amines and alkynes. Various aromatic/aliphatic aldehydes, aromatic alkynes, and piperidine were able to undergo three-component coupling on NH2-MIL-53(Al)-Au. In addition, the catalyst NH2-MIL-53(Al)-Au was recovered easily by centrifugation and reused up to four times. Thus, it can be used for the environmentally friendly synthesis of propargylamines.

Key words: Metal-organic framework, Postmodification, NH2-MIL-53(Al), Three-component coupling, Propargylamine