Supplementary Information for:

Preparation, Characterization and Catalytic Activity of MgO/SiO2supported Vanadium Oxide Based Catalysts

Eman Fahmy ABOELFETOHa and Rudolf PIETSCHNIGb)*

a) Chemistry Department, Faculty of Science, Tanta University, Tanta 31527, Egypt

b) Institute of Chemistry and Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel, Heinrich-Plett-Straße 40, 34132 Kassel, Germany

* Author for correspondance

E-mail:

Phone:+49 (0)561 804 4615

Fax:+49 (0)561 804 4649

I. Structural Characterization of Catalysts

Fig. S1: XRD patterns of impregnated (VOx/Florisil) catalysts with different vanadium loadings.

Fig. S2: FT-IR spectra of impregnated (VOx/Florisil) catalysts with different vanadium loading.

Fig. S3: DR-UV-Visible spectra of impregnated (VOx/Florisil) catalysts under inert conditions.

Fig. S4: DR-UV-Visible spectra of grafted (VOx/Florisil) catalysts under inert conditions.

Fig. S5: DR-UV-Visible spectra of grafted (VOx/Florisil) catalysts after 3 h of air exposure.

Fig. S6: EDX mapping of florisil showing the high dispersion of Mg on the silica surface.

Fig. S7: EDX mapping of Imp4F catalyst confirms the presence of aggregates of MgO (in blue color).

Fig. S8: SEM micrograph of Florisil at high magnification (A), SEM micrograph of Imp5F showing the presence of pyro-Mg2V2O7 (B), meta-MgV2O6 (C) and aggregates of V2O5 (D) at high magnification.

Fig. S9: TEM micrograph of Imp4F showing the presence of MgO particles (A), TEM micrograph of Imp5Fshowing the presence of pyro-Mg2V2O7(B), and needle-like crystals of V2O5 (C).

Table S1: Comparison of the edge energy values and the color of (VOx/Florisil) catalysts under inerta and hydratedb conditions.

Catalysts / Catalyst color (a) / Catalyst color (b) / Eg (eV)a /
Eg (eV)b
Imp1F / white / white / 3.56 / 3.56
Imp2F / white / white / 3.54 / 3.54
Imp3F / dirty white / yellowish white / 3.50 / 3.47
Imp4F / dirty white / yellowish white / 3.49 / 3.46
Imp5F / dark brown / dark brown / 3.21 / 3.20
Florisil diluted V2O5 / - / orange / - / 2.47
Ungrf1F / white / white / 3.44 / 3.43
Grf1F / white / white / 3.48 / 3.43
Grf2F / white / yellow / 3.41 / 3.22
Grf3F / white / yellow / 3.33 / 2.92

II. Catalytic Performance of Catalysts

Fig. S10: Variation of cyclohexane conversion and selectivity to cyclohexyl hydroperoxide with different VOx/Florisil catalysts at equal V conc. 11 mol.

Fig. S11: Variation of TON with different amounts of Grf1F catalyst.

Fig. S12:Variation of TON with different amounts of Imp1F catalyst.

Fig. S13: Variation of TON with the reaction time using Grf1F catalyst 0.77 mol V.

Fig. S14:Variation of cyclohexane conversion and selectivity to cyclohexylhydroperoxide with PCA conc., using Ungrf1F catalyst 11 mol V.

Table S2: Oxidation of cyclohexane using different amounts of Ungrf1F catalyst*.

V conc. (μ mol) / %Conv. / TON / %SCy-OH / %SCy=O / %SCy-OOH /
%(OS)
/
%By-products
00.00 / 00.18 / 50 / 45.90 / 54.10 / 00.00 / 100.00 / 0.00
00.21 / 17.67 / 23109 / 13.85 / 20.49 / 65.66 / 100.00 / 0.00
00.77 / 34.52 / 12020 / 12.66 / 16.92 / 68.93 / 98.51 / 0.51
01.52 / 64.92 / 11267 / 08.41 / 12.23 / 75.90 / 96.54 / 2.24
03.50 / 75.00 / 5649 / 04.69 / 8.85 / 82.00 / 95.54 / 3.34
11.00 / 58.40 / 1442 / 00.00 / 08.45 / 90.00 / 98.45 / 0.90
44.00 / 15.28 / 93 / 00.00 / 06.29 / 91.14 / 97.43 / 0.39
00.21(a) / 30.80 / 38165 / 15.65 / 21.73 / 57.35 / 94.30 / 1.75
00.77(b) / 69.86 / 22895 / 11.04 / 15.29 / 65.45 / 91.78 / 5.74

*Reaction conditions: Cyclohexane (1.06 M, 27.56 mmol), H2O2 (0.40 M, 10.5 mmol), PCA (1.70x10-3 M, 0.044 mmol), CH3CN (20 ml), 60 °C, 24 h. %; By-products1,4-cyclohexanedione, 1,3-cyclohexanediol, 4-hydroxy-cyclohexanone, 2-hydroxy-cyclohexanone, 2,4-dihydroxy-cyclohexanone.

(a) The same reaction conditions* except H2O2 (0.86 M, 22.36 mmol). (b) as (a) except the catalyst (Grf1F).

Fig. S15: Variation of conversion and selectivity to cyclohexyl hydroperoxide with different amounts of Grf1F catalyst.

Fig. S16: Variation of conversion and selectivity to cyclohexyl hydroperoxide with different amounts of Imp1F catalyst.