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Sol–gel synthesis of NiFe2O4 with PVA matrices and their catalytic activities for one-step hydroxylation of benzene into phenol

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Abstract

Nickel ferrite (NiFe2O4) was synthesized using citric acid (CA) as a chelating agent and varying amounts of polyvinyl alcohol (PVA) as powder binder via a combustion process. The influence of PVA/NiFe2O4 blend composition on the phase, crystal structure, and morphology has been investigated by X-ray diffraction (XRD), scanning electron microscopy, and Fourier transform infrared spectroscopy, respectively. The probable assignments of the thermal degradation products of PVA/NiFe2O4 were studied by complementary thermogravimetric analysis and differential thermal analysis. The PVA/NiFe2O4 crystals preferentially oriented along the (311) plane as revealed by XRD, owing to diffusion of α-Fe2O3 particles into the lattice matrix where the rate of diffusion increased significantly with the PVA concentration increase from 0.1 to 0.3 mol%. A vibrational doublet at 1,644 and 1,609 cm−1 for the ≡Fe–O–COOH complex was emitted in the spectra of PVA-impregnated NiFe2O4 to assure the attachment of Fe(III) to the chelating agents CA/PVA. Thermal kinetic consideration based on Coats–Redfern and Horowitz–Metzger equations at subsequent decomposition steps of CA/PVA/NiFe2O4 illustrated that the values of activation free energy ΔG* increase significantly, indicating the non-spontaneous behavior. The one-step direct hydroxylation of benzene toward phenol has been extensively investigated using hydrogen peroxide as an oxidant.

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Abbreviations

PVA:

Polyvinyl alcohol

CA:

Citric acid

XRD:

X-ray diffraction analysis

FT-IR:

Fourier transform infrared

E :

Activation energy (kJ mol−1)

ΔG*:

Activation Gibbs free energy change (kJ mol−1)

ΔH*:

Activation enthalpy change (kJ mol−1)

ΔS*:

Entropy change (kJ mol−1)

A :

Arrhenius factor (S−1)

T :

Kelvin temperature (K)

CR:

Coats–Redfern

HM:

Horowitz–Metzger

W f :

Mass loss at the completion of the reaction

W :

Mass loss

TG:

Thermogravimetric analysis

DTA:

Differential thermal analysis

SEM:

Scanning electron micrographs

R :

Universal gas constant

k :

Boltzmann constants

h :

Planck constants

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  1. Department of Chemistry, Faculty of Science, Al-Azhar University, Nasr City, 11884, Cairo, Egypt

    Ibraheem Othman Ali

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Ali, I.O. Sol–gel synthesis of NiFe2O4 with PVA matrices and their catalytic activities for one-step hydroxylation of benzene into phenol. J Therm Anal Calorim 116, 805–816 (2014). https://doi.org/10.1007/s10973-013-3584-3

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