Superior Performance of Metal–Organic Frameworks over Zeolites as Solid Acid Catalysts in the Prins Reaction: Green Synthesis of Nopol

Authors

  • Dr. Maksym Opanasenko,

    1. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of Czech Republic, v.v.i. Dolejškova 3, 182 23 Prague 8 (Czech Republic)
    2. L. V. Pisarzhevskiy Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 pr. Nauky, Kyiv 03028 (Ukraine)
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  • Dr. Amarajothi Dhakshinamoorthy,

    1. Instituto Universitario de Tecnología Química CSIC-UPV and Departamento de Química, Universidad Politécnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia (Spain)
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  • Dr. Young Kyu Hwang,

    1. Research Group for Nanocatalyst, Korea Research Institute of Chemical Technology (KRICT), 107, Yuseong, Daejeon 305-600 (South Korea)
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  • Dr. Jong-San Chang,

    1. Research Group for Nanocatalyst, Korea Research Institute of Chemical Technology (KRICT), 107, Yuseong, Daejeon 305-600 (South Korea)
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  • Prof. Hermenegildo Garcia,

    1. Instituto Universitario de Tecnología Química CSIC-UPV and Departamento de Química, Universidad Politécnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia (Spain)
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  • Prof. Jiří Čejka

    Corresponding author
    1. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of Czech Republic, v.v.i. Dolejškova 3, 182 23 Prague 8 (Czech Republic)
    • J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of Czech Republic, v.v.i. Dolejškova 3, 182 23 Prague 8 (Czech Republic)
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Abstract

The catalytic performance of a set of metal–organic frameworks [CuBTC, FeBTC, MIL-100(Fe), MIL-100(Cr), ZIF-8, MIL-53(Al)] was investigated in the Prins condensation of β-pinene with formaldehyde and compared with the catalytic behavior of conventional aluminosilicate zeolites BEA and FAU and titanosilicate zeolite MFI (TS-1). The activity of the investigated metal–organic frameworks (MOFs) increased with the increasing concentration of accessible Lewis acid sites in the order ZIF-8<MIL-53(Al)<FeBTC<MIL-100(Cr)<MIL-100(Fe). Unwanted β-pinene-like isomerization takes place on the strong Brønsted acid sites of zeolites BEA and FAU, which showed significantly lower selectivity to the target nopol than the MOFs. Its high activity, the preservation of its structure and active sites, and the possibility to use it in at least three catalytic cycles without loss of activity make MIL-100 (Fe) the best performing catalyst of the series for the Prins condensation of β-pinene and paraformaldehyde. Our report exemplifies the advantages of MOFs over zeolites as solid catalysts in liquid-phase reactions for the production of fine chemicals.

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