In this study, we undertook detailed experiments to increase hydrogen production efficiency by optimizing the thickness of titanium dioxide (TiO2) thin films. TiO2 films were deposited on p-type silicon (Si) wafers using atomic layer deposition (ALD) technology. The main goal was to identify the optimal thickness of TiO2 film that would maximize hydrogen production efficiency while maintaining stable operating conditions. The photoelectrochemical (PEC) properties of the TiO2 films of different thicknesses were evaluated using open circuit potential (OCP) and linear sweep voltammetry (LSV) analysis. These techniques play a pivotal role in evaluating the electrochemical behavior and photoactivity of semiconductor materials in PEC systems. Our results showed photovoltage tended to improve with increasing thickness of TiO2 deposition. However, this improvement was observed to plateau and eventually decline when the thickness exceeded 1.5 nm, showing a correlation between charge transfer efficiency and tunneling. On the other hand, LSV analysis showed bare Si had the greatest efficiency, and that the deposition of TiO2 caused a positive change in the formation of photovoltage, but was not optimal. We show that oxide tunneling-capable TiO2 film thicknesses of 1~2 nm have the potential to improve the efficiency of PEC hydrogen production systems. This study not only reveals the complex relationship between film thickness and PEC performance, but also enabled greater efficiency and set a benchmark for future research aimed at developing sustainable hydrogen production technologies.

This work reported the electrochemical and photoelectrochemical (PEC) properties of a new photoelectrode based on hematite Co-Fe2O3@NiO, a photoactive semiconductor, was prepared using a process involving a combination of the co-precipitation and microwave-assisted synthesis of Fe2O3, Co-Fe2O3 and Co-Fe2O3@NiO, respectively. The obtained products were characterized by X-Ray powder Diffraction (XRD), Scanning Electron Microscope (SEM), Energy Dispersive X-ray analysis (EDX), Ultraviolet–Visible (UV–vis) analysis, Fourier Transform Infrared spectroscopy (FT-IR). X-ray diffraction (XRD) pattern of the sample determined the crystal structure of α-Fe2O3 nanoparticles. The SEM image shows spherical nanoparticles. FTIR spectrospy spectrum confirmed the phase purity and chemical bond for the sample. Optical studies show a variation of band gap from 2.118 to 2.07 eV. The electrochemical and photoelectrochemical (PEC) performance of the films were examined by cyclic voltammetry, linear sweep voltammetry and chronoamperometry. The electrochemical oxidation of water achieved by Cobalt-doped Fe2O3@ GCE modified electrode exhibited the current density of 21 mA/g at 0.5 V vs. SCE for 5 at% of Co and reveals enhanced specific capacitance of 352.11 F/g. The catalytic performance of urea oxidation was measured by cyclic voltammetry on Co-Fe2O3@NiO nanoparticles modified glassy carbon electrode (GCE) in alkaline medium. The electrode Co-Fe2O3@NiO without annealing showed a peak current density of 1.59 mA/cm2 at 0.1 M urea in 1.0 M NaOH, which was 3.6 fold higher than that of Co-Fe2O3@NiO with annealing. In another part, this work reported the photoelectrochemical (PEC) properties of photoanode prepared by spin coating. The highest photocurrent 0.042 mA/cm2 at 0.5 V Vs SCE was obtained for 5% Co-Fe2O3@NiO while the photocatalytic oxidation of urea.

The development of advanced materials to improve the efficiency of photoelectrochemical (PEC) water splitting paves the way for widespread renewable energy technologies. Efficient photoanodes with strong absorbance in visible light increases the effectiveness of solar energy conversion systems. MoS2 in a two-dimensional semiconductor that has excellent absorption performance in visible light and high catalytic activity, showing considerable potential as an agent of PEC water splitting. In this study, we successfully modulated the MoS2 morphology on indium tin oxide substrate by using the metalorganic chemical vapor deposition method, and applied the PEC application. The PEC photocurrent of the vertically grown MoS2 nanosheet structure significantly increased relative to that of MoS2 nanoparticles because of the efficient transfer of charge carriers and high-density active sites. The enhanced photocurrent was attributed to the efficient charge separation and improved light absorption of the MoS2 nanosheet structure. Meanwhile, the photocurrent property of thick nanosheets decreased because of the limit imposed by the diffusion lengths of carriers. This study proposes a valuable photoelectrode design with suitable nanosheet morphology for efficient PEC water splitting.

We report the growth and enhanced photoelectrochemcial (PEC) water-splitting reactivity of few-layer MoS2 nanosheets on TiO2 nanowires. TiO2 nanowires with lengths of ~1.5 ~ 2.0 μm and widths of ~50~300 nm are synthesized on fluorine-doped tin oxide substrates at 180 oC using hydrothermal methods with Ti(C4H9O)4. Few-layer MoS2 nanosheets with heights of ~250 ~ 300 nm are vertically grown on TiO2 nanowires at a moderate growth temperature of 300 oC using metalorganic chemical vapor deposition. The MoS2 nanosheets on TiO2 nanowires exhibit typical Raman and ultraviolet-visible light absorption spectra corresponding to few-layer thick MoS2. The PEC performance of the MoS2 nanosheet/TiO2 nanowire heterostructure is superior to that of bare TiO2 nanowires. MoS2/TiO2 heterostructure shows three times higher photocurrent than that of bare TiO2 nanowires at 0.6 V. The enhanced PEC photocurrent is attributed to improved light absorption of MoS2 nanosheets and efficient charge separation through the heterojunction. The photoelectrode of the MoS2/TiO2 heterostructure is stably sustained during on-off switching PEC cycle.

In this work, Ag3PO4/In2S3 nanocomposites with low loading of In2S3 (5-15 wt %) are fabricated by two step chemical precipitation approach. The microstructure, composition and improved photoelectrochemical properties of the asprepared composites are studied by X-ray diffraction pattern (XRD), field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photocurrent density, EIS and amperometric i-t curve analysis. It is found that most of In2S3 nanoparticles are deposited on the surfaces of Ag3PO4. The as-prepared Ag3PO4/ In2S3 composite (10 wt%) is selected and investigated by SEM and TEM, which exhibits special morphology consisting of lager size substrate (Ag3PO4), particles and some nanosheets (In2S3). The introduction of In2S3 is effective at improving the charge separation and transfer efficiency of Ag3PO4/In2S3, resulting in an enhancement of photoelectric behavior. The origin of the enhanced photoelectrochemical activity of the In2S3-modified Ag3PO4 may be due to the improved charge separation, photocurrent stability and oriented electrons transport pathways in environment and energy applications.

Synthesizing nanostructured thin films of oxide semiconductors is a promising approach to fabricate highly efficient photoelectrodes for hydrogen production via photoelectrochemical (PEC) water splitting. In this work, we investigate the feasibility as an efficient photoanode for PEC water oxidation of zinc oxide (ZnO) nanostructured thin films synthesized via a simple method combined with sputtering Zn metallic films on a fluorine-doped tin oxide (FTO) coated glass substrate and subsequent thermal oxidation of the sputtered Zn metallic films in dry air. Characterization of the structural, optical, and PEC properties of the ZnO nanostructured thin film synthesized at varying Zn sputtering powers reveals that we can obtain an optimum ZnO nanostructured thin film as PEC photoanode at a sputtering power of 40 W. The photocurrent density and optimal photocurrent conversion efficiency for the optimum ZnO nanostructured thin film photoanode are found to be 0.1 mA/cm2 and 0.51 %, respectively, at a potential of 0.72 V vs. RHE. Our results illustrate that the ZnO nanostructured thin film has promising potential as an efficient photoanode for PEC water splitting.

Synthesizing one-dimensional nanostructures of oxide semiconductors is a promising approach to fabricate highefficiency photoelectrodes for hydrogen production from photoelectrochemical (PEC) water splitting. In this work, vertically aligned zinc oxide (ZnO) nanorod arrays are successfully synthesized on fluorine-doped-tin-oxide (FTO) coated glass substrate via seed-mediated hydrothermal synthesis method with the use of a ZnO nanoparticle seed layer, which is formed by thermally oxidizing a sputtered Zn metal thin film. The structural, optical and PEC properties of the ZnO nanorod arrays synthesized at varying levels of Zn sputtering power are examined to reveal that the optimum ZnO nanorod array can be obtained at a sputtering power of 20W. The photocurrent density and the optimal photocurrent conversion efficiency obtained for the optimum ZnO nanorod array photoanode are 0.13 mA/cm2 and 0.49 %, respectively, at a potential of 0.85 V vs. RHE. These results provide a promising avenue to fabricating earth-abundant ZnO-based photoanodes for PEC water oxidation using facile hydrothermal synthesis.

We report on the fabrication and characterization of an oxide photoanode with a zinc oxide (ZnO) nanorod array embedded in cuprous oxide (Cu2O) thin film, namely a ZnO/Cu2O oxide p-n heterostructure photoanode, for enhanced efficiency of visible light driven photoelectrochemical (PEC) water splitting. A vertically oriented n-type ZnO nanorod array is first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type Cu2O thin film is directly electrodeposited onto the vertically oriented ZnO nanorod array to form an oxide p-n heterostructure. The introduction of Cu2O layer produces a noticeable enhancement in the visible light absorption. From the observed PEC current density versus voltage (J-V) behavior under visible light illumination, the photoconversion efficiency of this ZnO/Cu2O p-n heterostructure photoanode is found to reach 0.39 %, which is seven times that of a pristine ZnO nanorod photoanode. In particular, a significant PEC performance is observed even at an applied bias of 0 V vs Hg/Hg2Cl2, which makes the device self-powered. The observed improvement in the PEC performance is attributed to some synergistic effect of the pn bilayer heterostructure on the formation of a built-in potential including the light absorption and separation processes of photoinduced charge carriers, which provides a new avenue for preparing efficient photoanodes for PEC water splitting.

Recent industrialization has led to a high demand for the use of fossil fuels. Therefore, the need for producing hydrogen and its utilization is essential for a sustainable society. For an eco-friendly future technology, photoelectrochemical water splitting using solar energy has proven promising amongst many other candidates. With this technique, semiconductors can be used as photocatalysts to generate electrons by light absorption, resulting in the reduction of hydrogen ions. The photocatalysts must be chemically stable, economically inexpensive and be able to utilize a wide range of light. From this perspective, cuprous oxide(Cu2O) is a promising p-type semiconductor because of its appropriate band gap. However, a major hindrance to the use of Cu2O is its instability at the potential in which hydrogen ion is reduced. In this study, gold is used as a bottom electrode during electrodeposition to obtain a preferential growth along the (111) plane of Cu2O while imperfections of the Cu2O thin films are removed. This study investigates the photoelectrochemical properties of Cu2O. However, severe photo-induced corrosion impedes the use of Cu2O as a photoelectrode. Two candidates, TiO2 and SnO2, are selected for the passivation layer on Cu2O by by considering the Pourbaix-diagram. TiO2 and SnO2 passivation layers are deposited by atomic layer deposition(ALD) and a sputtering process, respectively. The investigation of the photoelectrochemical properties confirmed that SnO2 is a good passivation layer for Cu2O.

Hydrothermal synthesis of highly crystalline TiO2 nanorods is a well-developed technique and the nanorods have been widely used as the template for growth of various core-shell nanorod structures. Magneli/CdS core-shell nanorod structures are fabricated for the photoelectrochemical cell (PEC) electrode to achieve enhanced carrier transport along the metallic magneli phase nanorod template. However, the long and thin TiO2 nanorods may form a high resistance path to the electrons transferred from the CdS layer. TiO2 nanorods synthesized are reduced to magneli phases, TixO2x-1, by heat treatment in a hydrogen environment. Two types of magneli phase nanorods of Ti4O7 and Ti3O5 are synthesized. Structural morphology and X-ray diffraction analyses are carried out. CdS nano-films are deposited on the magneli nanorods for the main light absorption layer to form a photoanode, and the PEC performance is measured under simulated sunlight irradiation and compared with the conventional TiO2/CdS core-shell nanorod electrode. A higher photocurrent is observed from the stand-alone Ti3O5/CdS coreshell nanorod structure in which the nanorods are grown on both sides of the seed layer.

We report on the fabrication and photoelectrochemical(PEC) properties of a Cu2O thin film/ZnO nanorod array oxide p-n heterojunction structure with ZnO nanorods embedded in Cu2O thin film as an efficient photoelectrode for solardriven water splitting. A vertically oriented n-type ZnO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type Cu2O thin film was directly electrodeposited onto the vertically oriented ZnO nanorods array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were characterized using X-ray diffraction and scanning electron microscopy as well as Raman scattering. The PEC properties of the fabricated Cu2O/ZnO p-n heterojunction photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the Cu2O/ZnO photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., 0.77 mA/cm2 at 0.5 V vs Hg/HgCl2 in a 1 mM Na2SO4 electrolyte, revealing an effective operation of the oxide heterostructure. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs Hg/ HgCl2, which made the device self-powered. The observed PEC performance was attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential, including the light absorption and separation processes of photoinduced charge carriers.

The design and fabrication of photoelectrochemical (PEC) electrodes for efficient water splitting is important for developing a sustainable hydrogen evolution system. Among various development approaches for PEC electrodes, the chemical vapor deposition method of atomic layer deposition (ALD), based on self-limiting surface reactions, has attracted attention because it allows precise thickness and composition control as well as conformal coating on various substrates. In this study, recent research progress in improving PEC performance using ALD coating methods is discussed, including 3D and heterojunction-structured PEC electrodes, ALD coatings of noble metals, and the use of sulfide materials as co-catalysts. The enhanced long-term stability of PEC cells by ALD-deposited protecting layers is also reviewed. ALD provides multiple routes to develop improved hydrogen evolution PEC cells.

We report on the fabrication and characterization of a novel Cu2O/CuO heterojunction structure with CuO nanorods embedded in Cu2O thin film as an efficient photocathode for photoelectrochemical (PEC) solar water splitting. A CuO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method; then, a Cu2O thin film was electrodeposited onto the CuO nanorod array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were examined using X-ray diffraction and scanning electron microscopy, as well as Raman scattering. The PEC properties of the fabricated Cu2O/CuO heterojunction photocathode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the Cu2O/CuO photocathode was found to exhibit negligible dark current and high photocurrent density, e.g. −1.05 mA/cm2 at −0.6 V vs. Hg/HgCl2 in 1 mM Na2SO4 electrolyte, revealing the effective operation of the oxide heterostructure. The photocurrent conversion efficiency of the Cu2O/CuO photocathode was estimated to be 1.27% at −0.6 V vs. Hg/HgCl2. Moreover, the PEC current density versus time (J-T) profile measured at −0.5 V vs. Hg/HgCl2 on the Cu2O/CuO photocathode indicated a 3-fold increase in the photocurrent density compared to that of a simple Cu2O thin film photocathode. The improved PEC performance was attributed to a certain synergistic effect of the bilayer heterostructure on the light absorption and electron-hole recombination processes.

Photoelectrochemical cells have been used in photolysis of water to generate hydrogen as a clean energy source. A high efficiency electrode for photoelectrochemical cell systems was realized using a ZnO hierarchical nanostructure. A ZnO nanofiber mat structure was fabricated by electrospinning of Zn solution on the substrate, followed by oxidation; on this substrate, hydrothermal synthesis of ZnO nanorods on the ZnO nanofibers was carried out to form a ZnO hierarchical structure. The thickness of the nanofiber mat and the thermal annealing temperature were determined as the parameters for optimization. The morphology of the structures was examined by field-emission scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The performance of the ZnO nanofiber mat and the potential of the ZnO hierarchical structures as photoelectrochemical cell electrodes were evaluated by measurement of the photoelectron conversion efficiencies under UV light. The highest photoconversion efficiency observed was 63 % with a ZnO hierarchical structure annealed at 400˚C in air. The morphology and the crystalline quality of the electrode materials greatly influenced the electrode performance. Therefore, the combination of the two fabrication methods, electrospinning and hydrothermal synthesis, was successfully applied to fabricate a high performance photoelectrochemical cell electrode.

Self-standing TiO2 nanotube arrays were fabricated by potentiostatic anodic oxidation method using pure Ti foil as a working electrode and ethylene glycol solution as electrolytes with small addition of NH4F and H2O. The influences of anodization temperature and time on the morphology and formation of TiO2 nanotube arrays were investigated. The fabricated TiO2 nanotube arrays were applied as a photoelectrode to dye-sensitized solar cells. Regardless of anodizing temperature and time, the average diameter and wall thickness of TiO2 nanotube show a similar value, whereas the thickness show a different trend with reaction temperature. The thickness of TiO2 nanotube arrays anodized at 20℃ and 30℃ was time-dependent, but on the other hand its at 10℃ are independent of anodization time. The conversion efficiency is low, which is due to a morphology breaking of the TiO2 nanotube arrays in manufacturing process of photoelectrode.

Titanium oxide films and powders are attached onto carbon cloths via RF reactive sputtering and an epoxy resin mixture, respectively. TiO2/carbon composite materials were used to investigate the photoelectrochemical degradation of perchlorate ions in water. The energy band gaps of the RF-sputtered TiO2 thin films ranged from 3.35-3.44 eV. A photocurrent of the powdered TiO2 as illuminated by ultra-violet light for 30 min. was 2.79 mA/cm2. Perchlorate ions in water were shown to be degradable by a UV-illuminated TiO2 powder/carbon/Nafion/carbon composite.