Biodiesel photoelectrocatalytic synthesis employing α-Fe2O3 film decorated with Pt nanoparticles as photoanode

Abstract

In this work, photoelectrochemical route for biodiesel production using an electrochemical cell configured with platinum and α-Fe₂O₃ modified with Pt nanoparticles as electrodes was investigated. XRD patterns registered for film prepared by modified hydrothermal method revealed a trigonal structure of the hematite (α-Fe₂O₃) phase. The α-Fe₂O₃ film surface was decorated by metallic Pt nanoparticles (Pt^NP) in order to reduce the charge recombination and improve the photocatalytic efficiency. The band gap energy (E_BG) of the α-Fe₂O₃ and Pt^NP/α-Fe₂O₃ films was estimated by UV-Vis spectroscopy at approximately 2.1 eV. Electrochemical measurements showed that the oxide is an n-type semiconductor adequate to be used as a photoanode in biodiesel synthesis. Under polarization conditions, the electrochemical cell changed the pH from 7 to 14 when the system was polarized at 5.0 V. In the synthesis of biodiesel by esterification reaction, oleic acid, 300 µL of 0.1 mol L⁻¹ aqueous KCl solution and methanol were used as precursor reagents. The reaction was carried out free of strong base, such as KOH or NaOH, as a supporting electrolyte. In this route, the reduction of the water molecule occurred on the cathode, with the formation of hydroxyl (OH^-) species, methoxy, and consequently fatty acid methyl esters (FAMEs). Thermogravimetric analysis (TGA) and Gas chromatography coupled to mass spectrometry (CG-MS) were performed to evaluate the catalysis products. GC-MS analyzes show that the reaction has a yield of about 7 % with the formation of FAMEs, such as methyl 9-octadecenoate, methyl hexadecanoate and methyl hexadecanoate.