Conversion of Sewage Water into H 2 Gas Fuel Using Hexagonal Nanosheets of the Polyaniline-Assisted Deposition of PbI 2 as a Nanocomposite Photocathode with the Theoretical Qualitative Ab-Initio Calculation of the H 2 O Splitting.

This study is very promising for providing a renewable enrgy (H₂ gas fuel) under the elctrochemical splitting of the wastwater (sewage water). This study has double benefits: hydrogen generation and contaminations removel. This study is carried out on sewage water, third stage treated, from Beni-Suef city, Egypt. Antimony tin oxide (ATO)/polyaniline (PANI)/PbI₂ photoelectrode is prepared through the in situ oxidative polymerization of PANI on ATO, then PANI is used as an assistant for PbI₂ deposition using the ionic adsorption deposition method. The chemical structural, morphological, electrical, and optical properties of the composite are confirmed using different analytical tools such as X-ray diffreaction (XRD), scanning electron microscope (SEM), transmision electron microscope (TEM), Fourier-transform infrared spectroscopy (FTIR), and UV-Vis spectroscopy. The prepared PbI₂ inside the composite has a crystal size of 33 nm (according to the peak at 12.8°) through the XRD analyses device. SEM and TEM confirm the hexagonal PbI₂ sheets embedded on the PANI nanopores surface. Moreover, the bandgap values are enhanced very much after the composite formation, in which the bandgap values for PANI and PANI/PbI₂ are 3 and 2.51 eV, respectively. The application of ATO/PANI/PbI₂ nanocomposite electrode for sewage splitting and H₂ generation is carried out through a three-electrode cell. The measurements carreid out using the electrocehical worksattion under th Xenon lamp (100 mW.cm⁻²). The produced current density (J_ph) is 0.095 mA.cm⁻² at 100 mW.cm⁻² light illumination. The photoelectrode has high reproducibility and stability, in which and the number of H₂ moles is 6 µmole.h⁻¹.cm⁻¹. The photoelectrode response to different monochromatic light, in which the produced J_ph decreases from 0.077 to 0.072 mA.cm⁻² with decreasing of the wavelengths from 390 to 636 nm, respectively. These values confirms the high response of the ATO/PANI/PbI₂ nanocomposite electrode for the light illuminaton and hydrogen genration under broad light region. The thermodynamic parameters: activation energy (Ea), enthalpy (ΔH*), and entropy (ΔS*) values are 7.33 kJ/mol, −4.7 kJ/mol, and 203.3 J/mol.K, respectively. The small values of ΔS* relted to the high sesnivity of the prepared elctrode for the water splitting and then the hydrogen gneration. Finally, a theoretical study was mentioned for calculation geometry, electrochemical, and thermochemistry properties of the polyaniline/PbI₂ nanocomposite as compared with that for the polyaniline. [ABSTRACT FROM AUTHOR]