4.7 Article

Encapsulating spinel nancrystals in Laponite cages and applications in molecular oxidation of cyclohexane

Journal

APPLIED CLAY SCIENCE
Volume 181, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.clay.2019.105226

Keywords

Spinel nanocatalyst; ZIF-67; Laponite cage; Molecular oxygen; Cyclohexane oxidation

Funding

  1. National Natural Science Foundation of China [51874145, U1607122]
  2. Qinghai Basic Program [2017-ZJ-705]
  3. Open Foundation of State Key Laboratory of Mineral Processing [BGRIMM-KJSKL-2019-07]
  4. China Ocean Mineral Resources R&D Association (COMRA) Special Foundation [DY135-46, DY135-R2-1-01]
  5. Jilin University [SXGJSF2017-3]

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The Co-based spinel nanocrystals were fabricated by thermal decomposition of clay cages comprised with Laponite (LP) that were assembled on ZIF-67 frameworks (LP@ZIF-67). Spinel phases included Co3O4, FeCo2O4 and MgCo2O4 were produced and encapsulated within the Laponite cages (LP@spinel). The prepared materials were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), transmission electron microscopy (TEM), N-2 adsorption-desorption, Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analyses (TGA). It was indicated that the porous structure of Laponite and ZIF-67 was preserved after annealing at the temperature of similar to 400 degrees C. The XPS showed the binding energy of Co-2P in sample of LP@spinel shifted to lower values compared to the Co3O4 which was obtained by annealing the pure phase of ZIF-67, and this demonstrates the catalytically active Co-centers were (220) facetexposed in spinel nanocrystals. The material LP@spinel shares mesoporous structure with surface area of 135 m(2).g(-1). The LP@spinel was found to exhibit brilliant performance on aerobic oxidation of cyclohexane to get cyclohexanone and cyclohexanol (KA oil). At a preset O-2 pressure of 2.0 MPa, the catalysis showed an outstanding conversion at 17.2% and the selectivity was found to reach 95.3% of KA oil for a typical reaction t = 5.0 h at T = 150 degrees C.

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