Electrodeposited zirconium-doped α-Fe2O3 thin film for photoelectrochemical water splitting

Nanostructured hematite thin films were doped with zirconium successfully using electrodeposition method for their implementation as photoanode in photoelectrochemical (PEC) cell for hydrogen generation. XRD, Raman, XPS, SEM and UV-visible spectroscopy techniques were used to characterize the thin films. Highest photocurrent density of 2.1 mA/cm² at 0.6 V/SCE was observed for 2.0 at.% Zr⁴⁺ doped α-Fe₂O₃ sample with solar to hydrogen conversion efficiency of 1.43%. Flatband potential (−0.74 V/SCE) and donor density (2.6 × 10²¹ cm⁻³) were found to be maximum for the same sample. These results suggest substantial potential of hematite thin films with controlled doping of zirconium in PEC water splitting applications.     

Nanostructured hematite photoelectrochemical electrodes prepared by the low temperature thermal oxidation of iron

We report on a facile low temperature method for the preparation of high surface area, nanostructured α-Fe₂O₃ (hematite) thin films and their application as photoelectrochemical (PEC) water splitting electrodes. The hematite films are fabricated by thermal oxidation in air of DC sputter deposited iron films at temperatures as low as 255 °C. This method results in films with a higher surface area than typically obtained by directly sputtering α-Fe₂O₃. It is shown that beyond a minimum iron thickness, α-Fe₂O₃ nanowires result upon thermal treatment in atmospheric conditions. Structural and optical characteristics of the resulting films are analyzed. The oxidation process is studied in detail and correlated to the photoelectrical properties. The Fe films oxidize in stages via Fe-oxide layers of increasing oxidation states. Resulting photoelectrochemical performance of fully oxidized films is a balance between optical absorption and charge collection, which varies with film thickness. The optimum film achieved a net photocurrent density of 0.18 mA/cm² in 1 M NaOH at 1.23 V vs. RHE under simulated AM1.5 sunlight, amongst the highest values reported for undoped hematite films produced at low temperature.     

Photoactivity of MWCNTs modified α-Fe2O3 photoelectrode towards efficient solar water splitting

MWCNTs (Multiwalled Carbon Nanotubes) modified α-Fe₂O₃ (hematite) photoelectrodes have been investigated for their possible application in hydrogen generation via photoelectrochemical (PEC) splitting of water. Enhanced photoresponse seen in comparison to the pristine α-Fe₂O₃ films is credited to the effective charge facilitation and charge separation provided by MWCNT conducting support. 0.2 wt% MWCNTs modified α-Fe₂O₃ thin film exhibited the maximum photocurrent density of 2.8 mA/cm² at 0.75 V/SCE. Measured values of flat band potential, donor density, resistance, Applied bias photon-to-current efficiency (ABPE) and Incident-photon-to current-conversion efficiency (IPCE) support the observed enhancement in photocurrent.     

Electrodeposited Cr-Doped α-Fe2O3 thin films active for photoelectrochemical water splitting

Polycrystalline hematite (α-Fe₂O₃) Chromium (Cr)-doped thin films were electrodeposited on fluorine-doped tin oxide-coated glass substrates. The electrodeposition bath comprised an aqueous solution containing FeCl₃·6H₂O, NaCl, and H₂O₂.Chromium was added to the electrolyte at such a proportion that the Cr/(Cr + Fe) ratio remained within the 2–8 at. % range. The as-deposited films were subsequently annealed in air at 650 °C for 2 h. The structure and morphological characteristics of the undoped and Cr-doped α-Fe₂O₃ thin films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV–Vis spectroscopy. Cr doping led the main XRD lines to shift to lower angles, which mostly resulted from substituting Fe³⁺ for Cr⁴⁺ ions that leads to α-Fe₂O₃ lattice contraction. The SEM observations showed that the roughness and aspect of surfaces changed with the Cr doping level. The photoelectrochemical (PEC) performance of the α-Fe₂O₃ films was examined by chronoamperometry and linear sweep voltammetry techniques. The Cr-doped films exhibited greater photoelectrochemical activity than the undoped α-Fe₂O₃ thin films. The highest photocurrent density was obtained for the 8% Cr-doped α-Fe₂O₃ films in 1 M NaOH electrolyte. All the samples achieved their best IPCE at 400 nm. The IPCE values for the 8 at.% Cr-doped hematite films were 20-fold higher than that of the undoped sample.This Cr-doped hematite films ‘excellent photoelectrochemical performance was mainly attributed to improved charge carrier properties. Such high photoactivity was attributed to the large active surface area and increased donor density caused by increasing the Cr doping in the α-Fe₂O₃ films.     

Iron doped nanostructured TiO2 for photoelectrochemical generation of hydrogen

This paper describes the photoelectrochemical studies on nanostructured iron doped titanium dioxide (TiO₂) thin films prepared by sol-gel spin coating method. Thin films were characterized by X-ray diffraction, Raman spectroscopy, spectral absorbance, atomic force microscopy and photoelectrochemical (PEC) measurements. XRD study shows that the films were polycrystalline with the photoactive anatase phase of TiO₂. Doping of Fe in TiO₂ resulted in a shift of absorption edge towards the visible region of solar spectrum. The observed bandgap energy decreased from 3.3 to 2.89 eV on increasing the doping concentration upto 0.2 at.% Fe. 0.2 at.% Fe doped TiO₂ exhibited the highest photocurrent density, ∼0.92 mA/cm² at zero external bias. Flatband potential and donor density determined from the Mott–Schottky plots were found to vary with doping concentration from −0.54 to −0.92 V/SCE and 1.7 × 10¹⁹ to 4.3 × 10¹⁹ cm⁻³, respectively.     

Photoelectrochemical properties of hematite films grown by plasma enhanced chemical vapor deposition

Nanostructured α-Fe₂O₃ thin films were grown by plasma-enhanced chemical vapor deposition (PE-CVD) using iron pentacarbonyl (Fe(CO)₅) as precursor. Influence of the plasma parameters on photoelectrochemical (PEC) properties of the resulting hematite thin films toward solar oxidation of water was investigated under one sun illumination in a basic (1 M NaOH) electrolyte. PEC data analyzed in conjunction with the data obtained by scanning electron microscopy, X-ray diffraction and Mott–Schottky analysis showed 100 W plasma power to be an optimal RF-power value for achieving a high photocurrent density of ∼1098 μA/cm² at 0.9 V/SCE external applied potential. The donor density, flat band potential, grain size and porosity of the films were observed to be highly affected by RF-power, which in turn resulted in enhanced photoresponse.     

Photoelectrochemical water splitting at nanostructured α-Fe2O3 electrodes

In this study, nanostructured α-Fe₂O₃ thin films were deposited by simple electrodeposition for photoelectrochemical water splitting. Post-annealing temperature was found to have drastic effect on photoactivity of these films. SEM analysis illustrated that size of nanoparticles increases with annealing temperature. The current–potential characteristics showed that the water-splitting photocurrent strongly depends on post-annealing temperature. A maximum photocurrent density of 0.67 mA/cm² was observed at 1.23 V versus reversible hydrogen electrode (RHE) under standard illumination conditions (AM 1.5 G 100 mW/cm²), and the water-splitting current was over 1.0 mA/cm² before the dark current flow starts (at 1.55 V versus RHE). The electrode shows an onset potential as low as 0.8 V (versus RHE) for water photooxidation, which is one of the best results reported for hematite photoanodes. This high photoactivity of electrodes is attributed to the preferential growth of hematite nanostructures along the most conductive plane (001) and incorporation of Sn in film from the substrate at high annealing temperature. The best-performing electrode shows an incident photon conversion efficiency (IPCE) of 12% at 400 nm (in 1 M NaOH at 1.23 V versus RHE), which indicate the improved light-harvesting properties of these nanostructures.     

CdSe quantum dots sensitized nanoporous hematite for photoelectrochemical generation of hydrogen

A novel system of CdSe quantum dots (QDs) sensitized porous hematite (α-Fe₂O₃) films has been investigated as a potential photoelectrode for hydrogen generation via photoelectrochemical (PEC) splitting of water. Before sensitization, nanoporous hematite thin films were prepared by spray pyrolysis. Characterizations for crystalline phase formation, crystallite size, absorption spectra, and flatband potential were carried out to analyze PEC data. Loading time of sensitizer to hematite thin films was found to be crucial in affecting its PEC properties. Film having sensitizer loading time as 42 h exhibited best photocurrent density of 550 μA cm⁻² at 1.0 V versus SCE. Current study, for the first time, explores the possibility of using low band gap QDs sensitization on a low band gap film, hematite in PEC splitting of water.     

Enhanced photocurrent by MOFs layer on Ti-doped α-Fe2O3 for PEC water oxidation

Low photocurrent density of hematite (α-Fe₂O₃) originating from the inherent defects usually hinders its application in photoelectrochemical (PEC) water oxidation. In this paper, the synergetic effect of increase of oxygen vacancies and in-situ constructing heterojunction by coating MOFs on the α-Fe₂O₃ nanoarrays gives rise to the boosted photocurrent of α-Fe₂O₃ from 0.25 mA/cm² to 2.1 mA/cm² at 1.23 V (vs. RHE). The results showed that the appropriate energy band structure engineered by the presence of MOFs layer not only facilitated the PEC water oxidation, but also enhanced the light absorption performance. With inducing oxygen vacancies in further, the intrinsic conductivity of photoanode can be well ameliorated. The value of carrier density is improved one order higher to promote charge transfer between the interfaces and raise the carrier separation efficiency as a result.     

Nanostructured Ti-doped hematite (α-Fe2O3) photoanodes for efficient photoelectrochemical water oxidation

We present a form of hematite (α-Fe₂O₃) nanostructured architecture suitable for photoelectrochemical water oxidation that is easily synthesized by a pulsed laser deposition (PLD) method. The architecture is a column-like porous nanostructure consisting of nanoparticles 30–50 nm in size with open channels of pores between the columns. This nanostructured film is generated by controlling the kinetic energy of the ablated species during the pulsed laser deposition process. In a comparison with the nanostructured film, hematite thin film was also synthesized by PLD. All of the developed films were successfully doped with 1.0 at% of titanium. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and UV–visible spectroscopy were used to characterize the films. To fabricate the photoelectrochemical (PEC) cell, Ti-doped hematite films were used as the working electrode, Ag/AgCl as the reference electrode, platinum wire as the counter electrode and an aqueous solution of 1 M NaOH as the electrolyte. The photovoltaic characteristics of all cells were investigated under AM 1.5G sunlight illumination of 100 mW/cm². The photocurrent density was enhanced by approximately 220% using nanostructured film at 0.7 V versus Ag/AgCl compared to hematite thin film, and the highest photocurrent density of 2.1 mA/cm² at 0.7 V/Ag/AgCl was obtained from the 1.0 at% Ti-doped hematite nanostructured film. The enhanced photocurrent density is attributed to its effective charge collection due to its unique column-like architecture with a large surface area.     

Enhanced photoelectrochemical performance of an α-Fe2O3 nanorods photoanode with embedded nanocavities formed by helium ions implantation

Hematite is a prospective semiconductor in photoelectrochemical (PEC) water oxidation field due to its suitable bandgap for the solar spectrum absorption. Nevertheless, the low transfer and separation efficiency of the charge carriers are restricted by its diffusion length of hole which is 2–4 nm and further reduce the PEC performance. Here, we report an innovative method, by introducing nanocavities into the α-Fe₂O₃ nanorod arrays photoanodes through helium ions implantation, to improve the charge carriers' transfer and separation efficiency and further to enhance water oxidation performance. The result indicates that, the photocurrent density of nanocavities embedded α-Fe₂O₃ photoanode (S2-A sample) reaches 1.270 mA/cm² at 1.6 V vs. RHE which is 1-fold higher than that of the pristine α-Fe₂O₃ (0.688 mA/cm²) and the photocurrent density of S2-A sample reaches 0.652 mA/cm² at 1.23 V vs. RHE. In this work, the ion implantation combined with post annealing method is found to be a valid method to improve the photoelectrochemical performance, and it also can be further used to modify the other semiconductor photoelectrodes materials.     

Microwave-assisted low temperature fabrication of nanostructured α-Fe2O3 electrodes for solar-driven hydrogen generation

It is demonstrated for the first time that significant enhancement of photoelectrochemical performance could be achieved by using microwave-assisted annealing for the fabrication of α-Fe₂O₃ thin films. The process can also lead to significant energy savings (>60% when compared with conventional methods). Different types of Fe thin films were oxidized using both microwave and conventional heating techniques. The photoelectrochemical performance of electrodeposited, undoped and Si-doped iron oxide samples showed that microwave-annealing resulted in superior structural and performance enhancements. The photocurrent densities obtained from microwave annealed samples are among the highest values reported for α-Fe₂O₃ photoelectrodes fabricated at low temperatures and short times; the highest photocurrent density at 0.55 V vs. V_Ag/AgCl, before the dark current onset, was 450 μA cm⁻² for the Si-doped films annealed at 270 °C for 15 min using microwave irradiation (and 180 μA cm⁻² at 0.23 V vs. V_Ag/AgCl) while conventional annealing at the same temperature resulted in samples with negligible (3 μA cm⁻²) photoactivity. In contrast, a 450 °C/15 min conventional heat treatment only resulted in a film with 25% lower photocurrent density than that of the microwave annealed sample. The improved performance is attributed to the lower processing temperatures and rapidity of the microwave method that help to retain the nanostructure of the thin films whilst restricting the grain growth to a minimum. The lower processing temperature requirements of the microwave process can also open up the possibility of fabricating hematite thin films on conducting, flexible, plastic electronic substrates.     

Plasma-chemical reduction of iron oxide photoanodes for efficient solar hydrogen production

We demonstrate the effect of hydrogen plasma treatment on hematite films as a simple and effective strategy for modifying the existing substrate to improve significantly the band edge positions and photoelectrochemical (PEC) performance. Plasma treated hematite films were consist of mixed phases (Fe₃O₄:α-Fe₂O₃) which was confirmed by XPS and Raman analysis, treated films also showed higher absorption cross-section and were found to be a promising photoelectrode material. The treated samples showed enhance photocurrent densities with maximum of 3.5 mA/cm² at 1.8 V/RHE and the photocurrent onset potentials were shifted from 1.68 V_RHE (untreated) to 1.28 V_RHE (treated). Hydrogen plasma treatment under non-equilibrium conditions induced a valence dynamics among Fe centers in the sub-surface region that was sustained by the incorporation of hydrogen in the hematite lattice as supported by the density functional theory calculations.     

Nanostructured hematite for photoelectrochemical generation of hydrogen

With the advent of nanotechnology there has been a resurge of interest in α$\alpha$-Fe₂O₃, as suitable candidate for photoelectrochemical (PEC) splitting of water to generate hydrogen. This paper describes the enhanced PEC behaviour of nanostructured α$\alpha$-Fe₂O₃ thin films modified by various techniques. Nanostructured thin film/pellets of α$\alpha$-Fe₂O₃ prepared by various techniques and various dopants were investigated for their photoelectrochemical response. Thin films prepared by spray pyrolysis having particle size of 20–30 nm exhibited better photoresponse as compared to the films prepared by sol–gel methods, which further improved on doping with Zn. These films were further modified by (i) depositing Zn dots on the surface of α$\alpha$-Fe₂O₃ films using thermal evaporation method and (ii) irradiating it with 170 MeV Au¹³⁺${\mathrm{Au}}^{13+}$ ions. When used as electrode in photoelectrochemical cell, a significant increase in the photoresponse of these modified films were observed, details of which are discussed.     

Photoelectrochemical water oxidation performance promoted by a cupric oxide-hematite heterojunction photoanode

Hematite is a promising material for photoelectrochemical (PEC) water oxidation due to its narrow bandgap and chemical stability in alkaline electrolytes. However, the PEC performance of hematite is known to be inhibited by a short carrier diffusion length and slow kinetics for the oxygen evolution process. The rational control of morphology, crystallinity, and interfacial charge transfer plays an important role in tuning the PEC performance of α-Fe₂O₃ photoelectrodes. In this study, different iron oxide nano/microstructures are synthesized by the sintering of iron sheets in air at different temperatures. The synergetic effect of the surface morphology and crystallinity on the photocurrent and onset potential of the photoanode is investigated. The coral-like structure with high index (104) facets prepared at a high temperature shows a decreased onset potential, suggesting a strong correlation between the onset potential and crystalline orientation. To further improve the photocurrent density of this hematite photoanode, cupric oxide-hematite heterostructures are explored. An obvious improvement in the photocurrent density is observed from 1.1 to 1.6 V. The resulting α-Fe₂O₃/CuO photoanode exhibits a photocurrent density of 1.5 mA cm⁻² at 1.6 V, 25% higher than that of the pristine hematite. The Mott-Schottky plot and EIS measurement indicate that the α-Fe₂O₃/CuO heterojunction facilitates the extraction of the accumulated holes in the hematite through a type-II band alignment and the CuO can serve as a catalyst for promoting the oxygen evolution reaction.     

Ultrathin Ti-doped hematite photoanode by pyrolysis of ferrocene

Ultrathin Ti-doped α-Fe₂O₃ photoanode was prepared by a facile atmospheric pressure chemical vapor deposition method through pyrolysis of ferrocene at 450 °C on Ti foil. The as prepared ultrathin hematite thin film has a surface feature size of 70 × 30 nm and a thickness of 50 nm. The photocurrent of this ultrathin hematite photoanode prepared at 450 °C in 1 M NaOH reaches 900 μA/cm² at 0.6 V_SCE under AM 1.5G illumination. The superior performance to the thin films prepared on FTO glass was ascribed to the diffusion and doping of Ti⁴⁺ from the metal substrate during pyrolysis deposition of hematite on Ti substrate.     

Electrostatic spray deposition of porous Fe2O3 thin films as anode material with improved electrochemical performance for lithium-ion batteries

Iron oxide materials are attractive anode materials for lithium-ion batteries for their high capacity and low cost compared with graphite and most of other transition metal oxides. Porous carbon-free α-Fe₂O₃ films with two types of pore size distribution were prepared by electrostatic spray deposition, and they were characterized by X-ray diffraction, scanning electron microscopy and X-ray absorption near-edge spectroscopy. The 200 °C-deposited thin film exhibits a high reversible capacity of up to 1080 mAh g⁻¹, while the initial capacity loss is at a remarkable low level (19.8%). Besides, the energy efficiency and energy specific average potential (E_av) of the Fe₂O₃ films during charge/discharge process were also investigated. The results indicate that the porous α-Fe₂O₃ films have significantly higher energy density than Li₄Ti₅O₁₂ while it has a similar E_av of about 1.5 V. Due to the porous structure that can buffer the volume changes during lithium intercalation/de-intercalation, the films exhibit stable cycling performance. As a potential anode material for high performance lithium-ion batteries that can be applied on electric vehicle and energy storage, rate capability and electrochemical performance under high-low temperatures were also investigated.     

Ultrathin hematite films deposited layer-by-layer on a TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe₂O₃) film deposited on a TiO₂ underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO₂ underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm⁻² at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm⁻²) illumination. The TiO₂ underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe₂O₃. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.     

Influence of sputter oxygen partial pressure on photoelectrochemical performance of tungsten oxide films

Polycrystalline tungsten oxide films of 1–1.2μm thickness were prepared by reactive sputtering at elevated substrate temperature (270 °C) and under different oxygen partial pressures in the range from 0.8 to 2.1 mTorr. At the lowest partial pressure the films were substoichiometric, showed increased disorder, and exhibited photocurrents of 0.6 mA/cm² at 1.8 V vs SCE in 0.33 M H₃PO₄. At partial pressures of 1.4 mTorr and greater, stoichiometric WO₃ films were produced which exhibited photocurrents of 2.4 mA/cm² at 1.8 V vs SCE. It has been determined that the photoelectrochemical performance of slightly substoichiometric films is adversely affected by changes in optical properties, while the photocurrents of severely substoichiometric films suffer additionally from poor carrier collection.     

Preparation and photocatalytic H2-production on α-Fe2O3 prepared by sol-gel

In this work, the hematite α-Fe₂O₃ was synthesized by sol-gel method and characterized by X-ray diffraction and optical properties. The XRD patterns realized at different temperatures, show that pure hematite is obtained above 500 °C. The diffuse reflectance gives respectively direct and indirect optical transitions at 2.17 and 2.04 eV, in agreement with the red color. The capacitance measurement of α-Fe₂O₃ indicates p type behavior with a conduction band (?1.14 V vs. SCE), more cathodic than the H₂ evolution (～?0.8 V vs. SCE). The oxide was successfully tested for the hydrogen production under visible irradiation (29 mW cm^?2). α-Fe₂O₃ is photo-electrochemically stable in alkaline medium by hole consumption reactions involving X^2? (= SO₃^2? and S₂O₃^2?) as hole scavengers. The best photocatalytic activity for H₂ production was obtained on α-Fe₂O₃, calcined at 500 °C, in (Na₂S₂O₃ 0.025 M, pH ～ 13), with an average evolution rate of 0.015 cm³ h^?1 (mg catalyst)^?1 and a quantum efficiency of 0.26%. The system shows a tendency toward saturation, due to the competitive reduction of end products with the water reduction and the cathodic shift of the H₂ potential.