Formaldehyde Total Oxidation on Manganese-Doped Hydroxyapatite: The Effect of Mn Content

Abstract

An aqueous impregnation method using manganese (II) nitrate precursor, followed by calcination at 400 °C, was carried out for the preparation of manganese doped hydroxyapatite catalysts (MnxHap; x = Mn wt.%: 2.5, 5.0, 10, 20, and 30 based on MnO2). Methods of characterization including inductively coupled plasma spectroscopy (ICP), N2 physisorption, X-ray Diffraction (XRD), Fourier-Transform Transmission Infrared (FT-IR), Raman, and Thermal gravimetric analysis (TGA/MS) analysis were used for the identification of Mn species and its surrounding environment. Raman spectroscopy indicated the presence of the ε-MnO2 phase for Mn20Hap and Mn30Hap in agreement with the XRD results and the presence of β-MnOOH species for Mn5Hap and Mn10Hap. The formaldehyde total oxidation was investigated on these catalysts and it was shown that Mn5Hap was the most active catalyst, achieving a normalized rate of formaldehyde (HCHO) conversion into CO2 per mole of Mn of 0.042 h−1 at a temperature of 145 °C. The well dispersed oxidized manganese species on Hap with a medium Mn AOS (average oxidation state) were mainly responsible for this performance. Since HCHO was retained on the surface of all catalysts during the catalytic test, the combined Diffuse Reflectance Infrared Fourier Transform spectroscopy (DRIFT) experiment at room temperature and thermodesorption (TD)-FTIR identified formate species as their oxidation consumed surface OH groups. A stability test and moisture effect study showed that the presence of water vapor has a beneficial effect on the performances of the catalyst.