The recent momentum in energy research has simplified converting solar to electrical energy through photoelectrochemical (PEC) cells. There are numerous benefits to these PEC cells, such as the inexpensive fabrication of thin film, reduction in absorption loss (due to transparent electrolyte), and a substantial increase in the energy conversion efficiency. Alpha-hematite ([U+F061]-Fe2O3) has received considerable attention as a photoanode for water-splitting applications in photoelectrochemical (PEC) devices. The alpha-hematite ([U+F061]-Fe2O3) nanomaterial is attractive due to its bandgap of 2.1eV allowing it to absorb visible light. Other benefits of [U+F061]-Fe2O3 include low cost, chemical stability and availability in nature, and excellent photoelectrochemical (PEC) properties to split water into hydrogen and oxygen. However, [U+F061]-Fe2O3 suffers from low conductivity, slow surface kinetics, and low carrier diffusion that causes degradation of PEC device performance. The low carrier diffusion of [U+F061]-hematite is related to higher resistivity, slow surface kinetics, low electron mobility, and higher electro-hole combinations. All the drawbacks of [U+F061]-Fe2O3, such as low carrier mobility and electronic diffusion properties, can be enhanced by doping, which forms the nanocomposite and nanostructure films.
In this study, all nanomaterials were synthesized utilizing the sol-gel technique and investigated using Scanning Electron Microscopy (SEM), X-ray Diffractometer (XRD), UV-Visible Spectrophotometer (UV-Vis), Fourier Transform Infrared Spectroscopy (FTIR), Raman techniques, Particle Analyzer, Cyclic Voltammetry (CV), and Chronoamperometry, respectively. The surface morphology is studied by SEM. X-Ray diffractometer (XRD) is used to identify the crystalline phase and to estimate the crystalline size. FTIR is used to identify the chemical bonds as well as functional groups in the compound. A UV-Vis absorption spectral study may assist in understanding electronic structure of the optical band gap of the material. Cyclic voltammetry and chronoamperometry were used to estimate the diffusion coefficient and study electrochemical activities at the electrode/electrolyte interface.
In this investigation, the [U+F061]-Fe2O3 was doped with various materials such as metal oxide (aluminum, Al), dichalcogenide (molybdenum disulfide, MoS2), and co-catalyst (titanium dioxide, TiO2). By doping or composite formation with different percentage ratios (0.5, 10, 20, 30) of aluminum (Al) containing [U+F061]-Fe2O3, the mobility and carrier diffusion properties of [U+F061]-hematite ([U+F061]-Fe2O3) can be enhanced. The new composite, Al-[U+F061]-Fe2O3, improved charge transport properties through strain introduction in the lattice structure, thus increasing light absorption. The increase of Al contents in [U+F061]-Fe2O3 shows clustering due to the denser formation of the Al-[U+F061]-Fe2O3 particle. The presence of aluminum causes the change in structural and optical and morphological properties of Al-[U+F061]-Fe2O3 more than the properties of the [U+F061]-Fe2O3 photocatalyst. There is a marked variation in the bandgap from 2.1 to 2.4 eV. The structure of the composite formation Al-[U+F061]-Fe2O3, due to a high percentage of Al, shows a rhombohedra structure. The photocurrent (35 A/cm2) clearly distinguishes the enhanced hydrogen production of the Al-[U+F061]-Fe2O3 based photocatalyst.
This work has been conducted with several percentages (0.1, 0.2, 0.5, 1, 2, 5) of molybdenum disulfide (MoS2) that has shown enhanced photocatalytic activity due to its bonding, chemical composition, and nanoparticle growth on the graphene films. The MoS2 material has a bandgap of 1.8 eV that works in visible light, responding as a photocatalyst. The photocurrent and electrode/electrolyte interface of MoS2-[U+F061]-Fe2O3 nanocomposite films were investigated using electrochemical techniques. The MoS2 material could help to play a central role in charge transfer with its slow recombination of electron-hole pairs created due to photo-energy with the charge transfer rate between surface and electrons. The bandgap of the MoS2 doped [U+F061]-Fe2O3 nanocomposite has been estimated to be vary from 1.94 to 2.17 eV. The nanocomposite MoS2-[U+F061]-Fe2O3 films confirmed to be rhombohedral structure with a lower band gap than Al-[U+F061]-Fe2O3 nanomaterial. The nanocomposite MoS2-[U+F061]-Fe2O3 films revealed a more enhanced photocurrent (180 μA/cm2) than pristine [U+F061]-Fe2O3 and other transition metal doped Al-[U+F061]-Fe2O3 nanostructured films.
The p-n configuration has been used because MoS2 can remove the holes from the n-type semiconductor by making a p-n configuration. The photoelectrochemical properties of the p-n configuration of MoS2-α-Fe2O3 as the n-type and ND-RRPHTh as the p-type deposited on both n-type silicon and FTO-coated glass plates. The p-n photoelectrochemical cell is stable and allows for eliminating the photo-corrosion process. Nanomaterial-based electrodes [U+F061]-Fe2O3-MoS2 and ND-RRPHTh have shown an improved hydrogen release compared to [U+F061]-Fe2O3, Al-[U+F061]-Fe2O3 and MoS2-[U+F061]-Fe2O3 nanostructured films in PEC cells. By using p-n configuration, the chronoamperometry results showed that 1% MoS2 in MoS2-[U+F061]-Fe2O3 nanocomposite can be a suitable structure to obtain a higher photocurrent density. The photoelectrochemical properties of the p-n configuration of MoS2-α-Fe2O3 as n-type and ND-RRPHTh as p-type showed 3-4 times higher (450 A/cm2) in current density and energy conversion efficiencies than parent electrode materials in an electrolyte of 1M of NaOH in PEC cells.
Titanium dioxide (TiO2) is known as one of the most explored electrode materials due to its physical and chemical stability in aqueous materials and its non-toxicity. TiO2 has been investigated because of the low cost for the fabrication of photoelectrochemical stability and inexpensive material. Incorporation of various percentages (2.5, 5, 16, 25, 50) of TiO2 in Fe2O3 could achieve better efficiencies as the photoanode by enhancing the electron concentration and low combination rate, and both materials can have a wide range of wavelength which could absorb light in both UV and visible spectrum ranges. TiO2 doped with [U+F061]-Fe2O3 film was shown as increasing contacting area with the electrolyte, reducing e-h recombination and shift light absorption along with visible region. The [U+F061]-Fe2O3-TiO2 nanomaterial has shown a more enhanced photocurrent (800 μA/cm2) than metal doped [U+F061]-Fe2O3 photoelectrochemical devices.
| Identifer | oai:union.ndltd.org:USF/oai:scholarcommons.usf.edu:etd-8858 |
| Date | 05 July 2018 |
| Creators | Alrobei, Hussein |
| Publisher | Scholar Commons |
| Source Sets | University of South Flordia |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | Graduate Theses and Dissertations |
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