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.     

Self-oriented iron oxide nanorod array thin film for photoelectrochemical hydrogen production

In this work, iron films were deposited on fluorine-tin-oxide coated glass substrate using radio frequency sputtering. Self-oriented iron oxide nanorod array thin films were obtained by anodizing the sputtered films. Anodization was carried out in an ethylene glycol solution containing 0.1 M NH₄F and various content of water. We studied the mechanism of anodization of iron thin films, and investigated the effects of some parameters on the properties of the iron oxide thin films.     

Charge transfer in iron oxide photoanode modified with carbon nanotubes for photoelectrochemical water oxidation: An electrochemical impedance study

Iron oxide photoanode was modified with multi-wall carbon nanotubes (MWCNTs) to improve the charge transport property of iron oxide in the photoelectrochemical water oxidation under solar light. The MWCNT-modified Fe₂O₃ electrode exhibited markedly increased photocurrent generation (by 66%) relative to unmodified Fe₂O₃ electrode. Electrochemical impedance spectroscopy demonstrated that MWCNT modification dramatically decreased resistance over the entire electrode and increased capacitance at the interface between carbon nanotubes and conducting substrate. The Mott-Schottky analysis showed that the flat band potential of the Fe₂O₃ electrode shifted to a more positive potential in the MWCNT-modified anode, indicating the charge migration from Fe₂O₃ to MWCNT. Thus the role of the MWCNT as an expressway for electron transport has been clearly demonstrated, which would help charge separation and improve photoelectrochemical water oxidation efficiency of the poorly conducting Fe₂O₃ electrode.     

Elucidation the role of Co-MOF on hematite for boosting the photoelectrochemical performance toward water oxidation

Developing an efficient photoanode to convert solar energy into hydrogen fuel confronts big challenges owing to the sluggish water oxidation kinetics. Herein, we proposed a feasible method to coat Co-based metal-organic framework (Co-MOF) on Ti doped α-Fe₂O₃ and revealed its functions on the oxygen evolution reaction (OER) and photoelectrochemical (PEC) water oxidation. The Co-MOF/Ti–Fe₂O₃ showed a photocurrent density of 1.01 mA/cm² (1.23V_RHE) with a low turn-on voltage (V_on) of 0.80 V_RHE. The significant improvement of photocurrent density which was ca. 3 times higher than the pristine Fe₂O₃, was contributed by the improved charge separation efficiency on the surface rather than in the bulk. And this was validated by the increased trapping capacitance (C_trap) and reduced charge transport resistance (R_ct). Additionally, the low V_on was attributable to the compromise of introduced surface states and the catalytic effect of the Co-MOF. In this work, we discovered the Co-MOF not only offered catalysis sites for OER, but shed light on its influence on the overall PEC water oxidation, and led to an in-depth understanding of cocatalysts on the PEC water splitting.     

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.     

Nanostructured Zn-Fe2O3 thin film modified by Fe-TiO2 for photoelectrochemical generation of hydrogen

Nanostructured semiconductor thin films of Zn-Fe₂O₃ modified with underlying layer of Fe-TiO₂ have been synthesized and studied as photoelectrode in photoelectrochemical (PEC) cell for generation of hydrogen through water splitting. The Zn-Fe₂O₃ thin film photoelectrodes were designed for best performance by tailoring thickness of the Fe-TiO₂ film. A maximum photocurrent density of 748 μA/cm² at 0.95 V/SCE and solar to hydrogen conversion efficiency of 0.47% was observed for 0.89 μm thick modified photoelectrode in 1 M NaOH as electrolyte and under 1.5 AM solar simulator. To analyse the PEC results the films were characterized for various physical and semiconducting properties using XRD, SEM, EDX and UV–Visible spectrophotometer. Zn-Fe₂O₃ thin films modified with Fe-TiO₂ exhibited improved visible light absorption. A noticeable change in surface morphology of the modified Zn-Fe₂O₃ film was observed as compared to the pristine Zn-Fe₂O₃ film. Flatband potential values calculated from Mott–Schottky curves also supported the PEC response.     

Nanostructured hematite thin films produced by spin-coating deposition solution: Application in water splitting

Doped and undoped hematite films for photoelectrochemical hydrogen production were prepared by spin-coating deposition solution (SCDS). To understand the influence of the Si-doping and identify the critical parameters of the proposed SCDS method an extensive characterization was conducted. The Si-doped hematite exhibited higher photocurrent response when compared with undoped films. We have shown that the crystallographic orientation degree of the films appears to be a dominant factor affecting the photocurrent. The performance of our hematite electrodes is well below the maximum theoretical efficiency and the conceivable explanation could be given by the high value of recombination phenomena (electron/hole pair).     

Spray pyrolytically deposited nanoporous Ti doped hematite thin films for efficient photoelectrochemical splitting of water

Nanoporous hematite (α-Fe₂O₃) thin films doped with Ti⁴⁺ deposited by spray-pyrolysis were successfully used in photoelectrochemical splitting of water for solar hydrogen production. X-ray diffraction, field emission scanning electron microscopy, UV–visible absorption and photoelectrochemical studies have been performed on the undoped and Ti⁴⁺ doped hematite thin films. Morphology of α-Fe₂O₃ thin films was observed to be nanoporous, with increased porosity (pore size ∼12 to 20 nm) on increasing doping concentration. A significant decrease in the bandgap energy from 1.95 to 1.27 eV was found due to doping. α-Fe₂O₃ film doped with 0.02 M Ti⁴⁺ ions exhibited best solar to hydrogen conversion efficiency (photoconversion efficiency) of 1.38% at 0.5 V/SCE. Highest photocurrent densities of 0.34 mA/cm² at zero bias and 1.98 mA/cm² at 0.5 V/SCE were obtained by incorporating 0.02 M Ti⁴⁺ in α-Fe₂O₃, which are significantly larger than earlier reported values. Donor density (30.8 × 10²⁰ cm⁻³) and flatband potential (−1.01 V/SCE) obtained were also maximum for this sample. Hydrogen collected in 1 hr at Pt electrode with the best photoelectrode was 2.44 mL with 150 mW/cm² visible light source.     

Production of hydrogen by partial oxidation with thermal plasma

The purpose of this paper is to investigate the characteristics and optimum operating conditions of the plasmatron-assisted CH₄ reforming reaction for the hydrogen-rich gas production. In order to increase the hydrogen production and the methane conversion rate, parametric screening study was conducted at various CH₄ flow ratio and steam flow ratio and with and without adding catalyst in the reactor. High-temperature plasma flame was made with air and arc discharge, and the air flow rate and the input power were set to 5.1  L/min and 6.4 kW, respectively.When the steam flow ratio was 30.2%, the hydrogen production was maximized and the optimal methane conversion rate was 99.7%. Under these optimal conditions, the following syngas concentrations were determined: H₂, 50.4%; CO, 5.7%; CO₂, 13.8%; and C₂H₂, 1.1%. H₂/CO ratio was 9.7 and the hydrogen yield was 93.7%.     

Influence of electrolyte temperature on the synthesis of iron oxide nanostructures by electrochemical anodization for water splitting

Iron oxide nanostructures are an attractive option for being used as photocatalyst in photoelectrochemical applications such as water splitting for hydrogen production. Nanostructures can be obtained by different techniques, and electrochemical anodization is one of the simplest methods which allows high control of the obtained morphology by controlling its different operational parameters. In the present study, the influence of the electrolyte temperature during electrochemical anodization under stagnant and hydrodynamic conditions was evaluated. Temperature considerably affected the morphology of the obtained nanostructures and their photoelectrochemical behavior. Several techniques were used in order to characterize the obtained nanostructures, such as Field Emission Scanning Electron Microscopy (before and after the annealing treatment in order to evaluate the changes in morphology), Raman spectroscopy, photocurrent vs. potential measurements and Mott-Schottky analysis. Results revealed that the nanostructures synthesized at an electrolyte temperature of 25 °C and 1000 rpm are the most suitable for being used as photocatalysts for water splitting.     

Creation of oxygen vacancies to activate Fe2O3 photoanode by simple solvothermal method for highly efficient photoelectrochemical water oxidation

Photoelectric chemical (PEC) decomposition of water is regarded as one of the most promising ways to convert solar energy into hydrogen energy, which has attracted extensive attention from researchers at home and abroad. Among the numerous photoanode materials, α-Fe₂O₃ is considered to be one of the most promising photocatalytic materials. However, due to the poor conductivity, short photogenerated charge life and high overpotential of water oxidation reaction, the development and application of α-Fe₂O₃ is seriously hindered. Recently, the introduction of oxygen vacancies is an effective method to improve the efficiency of α-Fe₂O₃ photoelectric conversion. In this work, oxygen vacancy was introduced in Fe₂O₃ photoanode by simple solvothermal method with ethylene glycol as solvent at 160 °C. The photoelectric catalytic activity of eg-Fe₂O₃ was significantly improved for solvothermal process. At 0.186 V_SCE (1.23 V_RHE), the photocurrent density of eg-Fe₂O₃ photoanode could reach 2.8 mA/cm², which is 1–2 orders of magnitude higher than that of pristine Fe₂O₃ photoanode (0.1 mA/cm²). XPS test results show that the solvothermal process with ethylene glycol at 160 °C introduces oxygen vacancy to Fe₂O₃ photoanode. The tests of electrochemical impedance spectroscopy and photoelectrochemical impedance spectroscopy indicate that the introduction of the oxygen vacancy significantly improve the conductivity of the Fe₂O₃ photoanode and reduces the resistance of charge transmission between the electrode catalytic material and the electrolyte, which are the main reasons for the improvement of photoelectric water oxidation activity. This work provides a new method for improving the photoelectrochemical water oxidation by iron oxide photoanode.     

Experimental investigation of various copper oxide electrodeposition conditions on photoelectrochemical hydrogen production

In this study, an experimental investigation of photosensitive material copper oxide electrodeposition on various substances is performed under different experimental conditions in order to evaluate the effects on photoelectrochemical hydrogen production system. The experimental setup consists of solar simulator, electrodeposition chemicals, hydrogen sensor, pH meter, graphite and platinum electrodes, heating plate, stirrer, temperature sensors, cathode and anode plates, concentrating lens and potentiostat. The overall aim is to optimize the efficiencies by generating higher currents and eventually hydrogen as light enhances the separation of water process. The results obtained in this study are promising for photoelectrochemical hydrogen production under the solar simulator and concentrated light irradiation conditions. Furthermore, an electrolysis setup using the coated metals and graphite rod is built to investigate the amount of photocurrent production. The characterization is also conducted under light and no-light conditions, where the amount of produced current and hydrogen increased in light compared to no-light condition. At the applied voltage of ?0.6 V and ?0.4 V vs. Ag/AgCl, the photocurrent densities of 0.8 mA/cm² and 0.27 mA/cm² are obtained with a solar conversion efficiency of 0.86% and 0.24%, respectively.     

Copper oxide photocathodes prepared by a solution based process

Solution based processes are well known by their low-cost trait to fabricate semiconductor devices. In this study, we devised an economical solution based route to photoelectrochemical (PEC) cells, taking copper nitrate as the copper ion source and adding an alkali hydroxide, here NaOH, to produce high aspect ratio (3.1–9.7) CuO nanoparticles. These CuO particles were used for splitting water and generation of hydrogen via a PEC cell. CuO nanoparticle morphology, i.e. rod-like, spindle-like, and needle-like, was dependent on the processing temperature. Sintering the spin coated CuO films, improved crystallinity. The bandgaps for these films were estimated to be 1.35 eV and 1.64 eV for sintering temperatures of 600 °C and 400 °C for 1 h, respectively. The porous structure of the nano-sized CuO films increased surface area and thus led to a high photocurrent, i.e. 1.20 mA/cm², for powder prepared at 60 °C and sintered at 600 °C for 1 h. These films demonstrated 0.91% solar conversion efficiency at an applied voltage of −0.55 V vs. Ag/AgCl in 1 M KOH electrolyte with 1 sun (AM1.5G) illumination. The charge carrier density was estimated to be 6.1 × 10²⁰ cm⁻³. This relatively high charge carrier density may be due to the high surface area and short transport distance to the electrode/electrolyte interface in the porous nanostructure.     

Morphology control of the hematite photoanodes for photoelectrochemical water splitting

The morphology of hematite photoanode is a significant relevant factor in its photoelectrochemical (PEC) performance. Hematite nanowires and nanocubes as well as nanorods with intentional Sn doping were prepared by hydrothermal processes containing disparate additives. The band-gap decreases in the sequence of nanowires, nanorods and nanocubes. Compared with nanorods, nanowires show higher carrier density but a lower light absorbance. With both inhibited bulk and surface charge recombination, nanowires achieve an enhanced photocurrent. Meanwhile, it is more complicated for the charge conversion in the hematite nanocubes. Light absorption is limited due to the compact arrangement of nanocubes. Besides, nanocubes show a highly oriented (104) plane which is unfavorable to the charge conductivity. Despite the negative factors hindering its PEC performance, the extremely high carrier density in the nanocubes benefits to the distinctly enhanced photocurrent collected from the hematite samples annealed at 550 and 650 °C respectively. However, the superiority of hematite nanocubes annealed under 800 °C is restricted by the high onset potential. Still, attributed to the high surface charge transfer efficiency, the hematite nanocubes achieve the highest photocurrent among the samples at biases above 1.3 V. Electrodes made of hematite nanorods, nanowires and nanocubes annealed at 800 °C achieve a photocurrent of 1.01, 1.30 and 1.40 mA cm⁻² at 1.6 V vs. RHE, respectively.     

Carbon-incorporated TiO2 photoelectrodes prepared via rapid-anodic oxidation for efficient visible-light hydrogen generation

Carbon-incorporated titanium dioxide (TiO₂) photoelectrodes with different structural features were prepared via rapid-anodic oxidation under different electrical potentials and exposure times. The interstitial carbon arising from the pyrogenation of ethylene glycol electrolytes induced a new C2p occupied state at the bottom of the conduction band, which lowered the band gap energy to ∼2.3 eV and consequently enabled the visible-light responsiveness. Photoelectrodes with nanotubular structures provided higher photoconversion efficiency (η) and hydrogen (H₂) evolution capability than those with irregular structures. The increased aspect ratio, wall thickness, and pore size of the nanotube arrays contributed to η through greater photon excitation and penetration. However, this contribution is limited by the high recombination of the charge carriers at ultra-high aspect ratios. Photoelectrodes with a nanotube length of ∼19.5 μm, pore size of ∼103 nm, wall thickness of ∼17 nm, and aspect ratio of ∼142.5 exhibited remarkable capability to generate H₂ at an evolution rate of up to ∼508.3 μL min⁻¹ cm⁻² and η of ∼2.3%.     

Transient phenomenological modeling of photoelectrochemical cells for water splitting - Application to undoped hematite electrodes

A phenomenological model is proposed for a better understanding of the basic mechanisms of photoelectrochemical (PEC) cells. The main assumptions of the one-dimensional transient phenomenological model are: i) bulk recombination of the conduction band electrons with holes in the valence band; ii) the mobile charge transport takes place via diffusion, which arises from the concentration profiles, and migration, caused by a macroscopic electric field; iii) negligible effects of microscopic electric fields in the cell and screening effects, as well as negligible Helmholtz and diffuse layers. For modeling purposes, the photoanode was assumed to be a homogeneous nanocrystalline hematite structure, with thickness L, porosity ?_p and tortuosity τ. The TCO/semiconductor interface was modeled as an ideal ohmic contact, while the electrolyte/platinized TCO interface was described by a Butler-Volmer approach. An alkaline electrolyte solution was used, allowing the transport of the ionic species from the counter-electrode to the photoanode. The continuity and transport governing equations are defined for the mobile species involved: electrons in the conduction band of the semiconductor, holes in the valence band and hydroxyl ions in the electrolyte. Simulated I-V characteristics were computed and the corresponding results compared with the experimental values. The simulated results were in straight agreement with the experimental data.     

Copper oxide nanoparticle made by flame spray pyrolysis for photoelectrochemical water splitting - Part II. Photoelectrochemical study

A scalable method for hydrogen generation by splitting water via a photoelectrochemical cell was studied. Flame spray pyrolysis and spin coating processing methods were used for preparing copper oxide nanoparticles and copper oxide photocathodes. Copper oxide p-type semiconductor nanoparticles made by flame spray pyrolysis were spin coated on conducting ITO substrates and served as photocathodes for photoelectrochemical splitting of water. The film thickness was controlled by the concentration of the CuO suspension solution and numbers of layer deposited on the substrate. As sintering temperature increased to 600 °C, crystalline diameter increased from 28 nm (before sintering) to 110 nm and the bandgaps decreased from 1.68 eV to 1.44 eV. A 387 nm thickness CuO film with bandgap 1.44 eV was demonstrated to have 1.48% total conversion efficiency and 0.91% photon-to-hydrogen generation efficiency. The net photocurrent density (photocurrent - dark current) was measured to be 1.20 mA/cm² at applied voltage of −0.55 V vs. Ag/AgCl in 1 M KOH electrolyte with 1 sun (AM1.5G) illumination. Based on the Mott-Schottky plot, the carrier density was estimated to be 1.5 × 10²¹ cm⁻³ and the flatband potential to be 0.23 V vs. Ag/AgCl. Furthermore, the valence band edge and conduction band levels were found to lie at −5.00 eV and −3.56 eV respect to the vacuum respectively.     

Photoelectrochemistry of tin-doped iron oxide electrodes

Ceramic semiconductor photoelectrodes made of Fe₂O₃ with up to 2 at.% Sn-doping were synthesized. Results of investigations of their electroconductivity are presented. The ionization energy of donor centers created by tin is determined. The capacitance–voltage characteristics of the photoelectrodes and the dynamic polarization with chopped light were investigated. The anodic photocurrent onset potential, the flat band potential and the shallow and deep donor density of these materials were determined. The spectral characteristics of manufactured photoelectrodes were measured. The threshold photon energies corresponding to the inter-band optical transitions near the edge of the fundamental absorption of the semiconductor photoelectrode were calculated. The structure of the two-phase interface was studied using electrochemical impedance spectroscopy.     

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.