Photoelectrochemical water splitting on highly smooth and ordered TiO2 nanotube arrays for hydrogen generation

To improve the photoelectrochemical (PEC) water splitting efficiency for hydrogen production, we reported the fabrication of lotus-root-shaped, highly smooth and ordered TiO₂ nanotube arrays (TiO₂ NTs) by a simple and effective two-step anodization method. The TiO₂ NTs prepared in the two-step anodization process (2-step TiO₂ NTs) showed better surface smoothness and tube orderliness than those of TiO₂ NTs prepared in one-step anodization process (1-step TiO₂ NTs). Under illumination of 100 mW/cm² (AM 1.5, simulated solar light) in 1 M KOH solution, water was oxidized on the 2-step TiO₂ NTs electrode with higher efficiency (incident-photon-to-current efficiency of 43.4% at 360 nm and photocurrent density of 0.90 mA/cm² at 1.23 V_RHE) than that on the 1-step TiO₂ NTs electrode. The effective photon-to-hydrogen conversion efficiency was found to be 0.18% and 0.49% for 1-step TiO₂ NTs and 2-step TiO₂ NTs, respectively. These results suggested that the structural smoothness and orderliness of TiO₂ NTs played an important role in improving the PEC water splitting application for hydrogen generation.     

Enhanced photoelectrochemical-response in highly ordered TiO2 nanotube-arrays anodized in boric acid containing electrolyte

We examine the photoelectrochemical properties of highly ordered titanium dioxide nanotube-array photoanodes, fabricated by anodization of titanium in a nitric acid/hydrofluoric acid electrolyte, with and without the addition of boric acid. Under UV–Vis illumination the photocurrent densities achieved with TiO₂ nanotube-arrays fabricated in the H₃BO₃–HNO₃–HF electrolyte are a factor of seven greater than the TiO₂ nanotube-array samples obtained in the commonly used HNO₃–HF electrolyte, indicating the ability to control the photoelectrochemical response of the highly ordered nanotube arrays by tailoring the electrolyte composition. For 560 nm long boric-acid fabricated nanotube arrays, a photoconversion efficiency of 7.9% is achieved upon a 320–400 nm illumination at an intensity of 98 mW/cm², with hydrogen generated by water photoelectrolysis at the power-time normalized rate of 1708-μmol/h W (42 ml/h W). The resulting nanotube-arrays demonstrate excellent photocorrosion stability, with no detectable degradation in photoconversion properties over 6 months of testing. While the titania bandgap is not suitable for high visible spectrum efficiencies, the high photoconversion efficiency achieved under UV illumination indicates the suitability of the highly ordered nanotube-array architecture for hydrogen generation by water photoelectrolysis.     

Surface modification of aligned TiO2 nanotubes by Cu2O nanoparticles and their enhanced photo electrochemical properties and hydrogen generation application

In this work, we report the synthesis of cuprous oxide (Cu₂O) nanoparticles modified vertically oriented aligned titanium dioxide (TiO₂) nanotube arrays through wet chemical treatment of TiO₂ nanotubes and their multi-functional application as enhanced photo electrochemical and hydrogen generation. The synthesized samples were characterized by X-ray diffraction, SEM, TEM, and UV–Vis spectroscopy. The structural characterization revealed that the admixed Cu₂O nanoparticles on the TiO₂ surface did not alter its crystalline structure of vertically oriented aligned TiO₂ nanotube. The photocatalytic performance and hydrogen generation of as synthesized Cu₂O nanoparticles modified aligned TiO₂ nanotube was found to highly depend on the Cu₂O content. The optical characterizations reveal that the presence of Cu₂O nanoparticles extends its absorption into the visible region which improves the photocurrent density in comparison to pristine aligned TiO₂ nanotubes electrodes due to enhanced photoactivity and better charge separation. The optimum photocurrent density and hydrogen generation rate has been found to be 3.4 mA cm^?2 and 127.5 μmole cm^?2 h^?1 in 1 M Na₂SO₄ electrolyte solution under 1.5 AM solar irradiance of white light with illumination intensity of 100 mW cm^?2.     

Performance of a new polymer electrolyte incorporated with diphenylamine in nanocrystalline dye-sensitized solar cell

A new solvent-free composite polymer electrolyte consisting of poly(ethylene oxide) (PEO) incorporated into diphenyl amine (DPA) along with KI and I₂ has been developed. The current-voltage characteristics of this nanocrystalline dye-sensitized solar cell measured under simulated sunlight with 1.5 AM at 60 mW/cm² have indicated that this cell generates a photocurrent of 10.2 mA/cm², together with a photovoltage of 810 mV and fill factor of 0.47 yielding an overall energy conversion efficiency of 6.5%. This result suggests that the electron donicity of DPA influences the interaction of nanocrystalline TiO₂ electrode and I⁻/I₃⁻ electrolyte, leading to a high performance of the fabricated solar cell.     

Synthesis of reduced graphene oxide–TiO2 nanoparticle composite systems and its application in hydrogen production

The utilization of solar energy for the conversion of water to hydrogen and oxygen has been considered to be an efficient strategy to solve crisis of energy and environment. Here, we report the synthesis of reduced graphene oxide–TiO₂ nanoparticle composite system through the photocatalytic reduction of graphite oxide using TiO₂ nanoparticles. Photoelectrochemical characterizations and hydrogen evolution measurements of these nanocomposites reveal that the presence of graphene enhances the photocurrent density and hydrogen generation rate. The optimum photocurrent density and hydrogen generation rate has been found to be 3.4 mA cm⁻² and 127.5 μmole cm⁻²h⁻¹ in 0.5 M Na₂SO₄ electrolyte solution under 1.5AM solar irradiance of white light with illumination intensity of 100 mW cm⁻². In graphene–TiO₂ nanocomposite, photogenerated electrons in TiO₂ are scavenged by graphene sheets and percolate to counter electrode to reduce H⁺ to molecular hydrogen thus increasing the performance of water-splitting reaction.     

TiO2 nanotubes for hydrogen generation by photocatalytic water splitting in a two-compartment photoelectrochemical cell

Highly ordered TiO₂ nanotube arrays for hydrogen production have been synthesized by electrochemical anodization of titanium sheets. Under solar light irradiation, hydrogen generation by photocatalytic water splitting was carried out in the two-compartment photoelectrochemical cell without any external applied voltage. The hydrogen gas and oxygen generated on Pt side and on TiO₂ nanotubes side respectively were efficiently separated. The effect of anodization time on the morphology structures, photoelectrochemical properties and hydrogen production was systematically investigated. Due to more charge carrier generation and faster charge transfer, a maximum photoconversion efficiency of 4.13% and highest hydrogen production rate of 97 μmol h⁻¹cm⁻² (2.32 mL h⁻¹cm⁻²) were obtained from TiO₂ nanotubes anodized for 60 min.     

Photocurrent and photoelectrochemical hydrogen production with tin porphyrin and platinum nanowires immobilized with nafion on glassy carbon electrode

Platinum nanowires mixed with Tin meso-tetra (4-pyridyl) porphine dichloride and nafion solution was used to modify the surface of glassy carbon electrode for photocurrent generation and photo-electrochemical hydrogen production. Different concentrations of porphyrin (50 μM, 100 μM, 300 μM and 500 μM) and platinum loading (200 μg/cm², 400 μg/cm², 600 μg/cm² and 800 μg/cm²) were tested at −150 mV Vs Ag/AgCl in reaction cell containing the modified glassy carbon electrode as working electrode, platinum wire as counter electrode and Ag/AgCl as reference electrode, under illumination to determine the optimum, based on photocurrent production in 50 mM potassium hydrogen phthalate buffer (pH 3) containing 0.1Na₂SO₄ as supporting electrolyte. Optimum photocurrent was obtained at 100 μM tin porphyrin and 600 μg/cm² platinum loading. Detectable amount of hydrogen was produced at −350 mV Vs Ag/AgCl under irradiation with visible light.     

Fabrication of dye-sensitized solar cells by transplanting highly ordered TiO2 nanotube arrays

Highly ordered TiO₂ nanotube arrays fabricated by anodization are very attractive to dye-sensitized solar cells (DSCs) due to their superior charge percolation and slower charge recombination. However, the efficiency of TiO₂-nanotube-based DSCs is 6.89%, which is still lower than that of TiO₂-nanoparticle-based DSCs. We have suggested the transplanting the highly ordered TiO₂ nanotube arrays to FTO glass to improve the performance of TiO₂-nanotube-based DSCs. DSCs based on transplanted TiO₂ nanotube arrays and TiO₂ nanoparticles were fabricated by same process and materials to exclude the unexpected factors. In TiO₂ thickness of ca. 15 μm, the efficiency of 2.91% in front-side illuminated DSCs based on TiO₂ nanotube arrays was higher than those in back-side illuminated DSCs based on TiO₂ nanotube arrays and in front-side illuminated DSCs based on TiO₂ nanoparticle. Front-side illuminated DSCs based on TiO₂ nanotube arrays having various thicknesses were successfully fabricated. The efficiency in DSCs having 20.0 μm thick TiO₂ nanotube arrays was improved to 5.36% by TiCl₄ treatment.     

Synthesis of highly-ordered TiO2 nanotubes for a hydrogen sensor

Highly-ordered, vertically oriented TiO₂ nanotubes are synthesized, and their hydrogen sensing properties are investigated. Self-organized TiO₂ nanotube arrays are grown by anodic oxidation of a titanium foil in an aqueous solution that contains 1 wt% hydrofluoric acid at 20 °C. We use a potential ramp at a rate of 100 mV s⁻¹, increasing from the initial open-circuit potential (OCP) to 20 V, and this final potential of 20 V is then held constant during the anodization process. The fabricated TiO₂ nanotubes are approximately 1 μm in length and 90 nm in diameter. For the sensor measurements, two platinum pads are used as electrodes on the TiO₂ nanotube arrays. The hydrogen sensing characteristics of the sensor are analyzed by measuring the sensor responses ((I − I₀)/I₀) in the temperature interval of 20–150 °C. We find that the sensitivity of the sensor is approximately 20 for 1000 ppm H₂ exposure at room temperature, and increases with increasing temperature. The sensing mechanism of the TiO₂ nanotube sensor could be explained with chemisorption of H₂ on the highly active nanotube surface.     

Effect of anodization voltage on performance of TiO2 nanotube arrays for hydrogen generation in a two-compartment photoelectrochemical cell

Highly ordered TiO₂ nanotube arrays were prepared by anodic oxidation of Ti foil under different anodization voltages in ethylene glycol electrolyte. The morphology and photoelectrochemical performance of the TiO₂ nanotubes (NTs) samples were characterized by FESEM and electrochemical working station. Hydrogen production was measured by splitting water in the two-compartment photoelectrochemical (PEC) cell without any external applied voltage or sacrificial agent. The results indicated that anodization voltage significantly affects morphology structures, photoelectrochemical properties and hydrogen production of TiO₂ NTs. The pore diameter and layer thickness of TiO₂ samples increased linearly with the anodization voltage, which led to the enhancement of active surface area. Accordingly, the photocurrent response, photoconversion efficiency and hydrogen production of TiO₂ nanotubes were also linearly correlated with the anodization voltage.     

Highly stable CdS-modified short TiO2 nanotube array electrode for efficient visible-light hydrogen generation

A highly stable photoelectrocatalytic electrode made of CdS-modified short, robust, and highly-ordered TiO₂ nanotube array for efficient visible-light hydrogen generation was prepared via sonoelectrochemical anodization and sonoelectrochemical deposition method. The short nanotube electrode possesses excellent charge separation and transfer properties, while the sonoelectrochemical deposition method improves the combination between CdS and TiO₂ nanotubes, as well as the dispersion of CdS nanoparticles. Different characterization techniques were used to study the nanocomposite electrode. UV-vis absorption and photoelectrochemical measurements proved that the CdS coating extends the visible spectrum absorption and the solar spectrum-induced photocurrent response. Comparing the photoactivity of the CdS/TiO₂ electrode obtained using sonoelectrochemical deposition method with others that synthesized using plain electrochemical deposition, the current density of the former electrode is ∼1.2 times higher that of the latter when biased at 0.5 V. A ∼7-fold enhancement in photocurrent response is obtained using the sonoelectrochemically fabricated CdS/TiO₂ electrode in comparison with the pure TiO₂ nanotube electrode. Under AM1.5 illumination the composite photoelectrode generate hydrogen at a rate of 30.3 μmol h⁻¹ cm⁻², nearly 13 times higher than that of pure titania nanotube electrode. Recycle experiments demonstrated the excellent stability and reliability of CdS/TiO₂ electrode prepared by sonoelectrochemical deposition. This composite electrode, with its strong mechanical stability and excellent combination of CdS and TiO₂ nanotubes, offers promising applications in visible-light-driven renewable energy generation.     

Photoelectrochemical water splitting for hydrogen generation on highly ordered TiO2 nanotubes fabricated by using Ti as cathode

Sonication assisted anodization of titanium in a fluorinated ethylene glycol and water electrolyte using Ti itself as a cathode is investigated. The prepared anodic film has a highly ordered nanotube-array surface architecture. The resulting TiO₂ nanotubes at potential 20-40 V have various diameters (30-100 nm), tube length (3-12 μm) and wall thicknesses (6-15 nm). The tube diameter and wall thickness are increased with the anodization time while the overall length of the nanotube arrays is controlled by the duration of the anodization time. In addition, apart from the anodization time, formation of nanotubes is governed by the distance and supplied voltages between the two electrodes, for a given electrolyte. The crystal structure and surface morphology of the annealed anodic films are investigated by XRD and SEM, respectively. The corresponding photoelectrochemical water splitting efficiency (PCE) was calculated under UV light. Our results show a very high PCE under UV (315-400 nm, 100 mW/cm²) irradiation. The maximum value of PCE for hydrogen generation obtained was 29% which is one of the best results reported in literature [1].     

Effect of length of anodized TiO2 tubes on photoreactivity: Photocurrent, Cr(VI) reduction and H2 evolution

Anodized tubular TiO₂ electrodes (ATTEs) are prepared using an organic additive consisting of either (i) ethylene glycol (EG) or (ii) glycerol (Gly) to make various photoanodes with different length of TiO₂ tubes and thereby to investigate the effect of their length on the photo-driven activity for hydrogen evolution and Cr(VI) reduction, as well as on the photocurrent. The ATTEs with EG have longer TiO₂ tubes (3.42-15.6 μm) than those with Gly (0.26-1.95, 6.82 μm). The former samples exhibit higher photocurrent densities (22.8-32.8 mA cm⁻²) than the latter (8.0-19.4, 20.3 mA cm⁻²). The latter samples (tube length of less than 7 μm) clearly exhibit a change of the rate-determining step from electron migration to photohole capture as the scanned applied bias increases, since the photocurrent shows a plateau for tube lengths above 2 μm. Meanwhile, the samples with EG remain in the electron migration step up to a tube length of 16 μm and is due to the difference of the morphology, crystal phase and crystallinity. This favourable characteristic is also applied to and well matched with the results from the reactions of Cr(VI) reduction and hydrogen evolution (up to ca. 250 μmol h⁻¹).     

Investigation of plasmonic Cu with controlled diameter over TiO2 photoelectrode for solar-to-hydrogen conversion

Plasmonic metal nanoparticles (NPs) have been used to improve the solar-to-hydrogen conversion efficiency. Relative to Au and Ag, Cu is cheaper and more abundant. In the present work, Cu NPs with the controlled diameter were deposited on TiO₂ nanotube arrays (TNTAs) by using a pulse electrochemical deposition method. When the deposition was cycled 3600 times, the size of Cu NPs can be tuned to approximately 30 nm with the most uniform distribution, resulting in the remarkable characteristic peak of surface plasmon resonance and higher photocurrent density. The hydrogen production rates remained unchanged during irradiation (AM 1.5, 100 mW/cm²) of 2 h, indicating a good stability of the resultant Cu/TNTAs electrode. The photoelectrochemical performances of as-prepared Cu/TNTAs can also be comparable to those of Ag/TNTAs electrode fabricated by the same method.     

A novel photoelectrochemical cell with self-organized TiO2 nanotubes as photoanodes for hydrogen generation

A photoelectrochemical (PEC) cell with an innovative design for hydrogen generation via photoelectrocatalytic water splitting is proposed and investigated. It consisted of a TiO₂ nanotube photoanode, a Pt/C cathode and a commercial asbestos diaphragm. The PEC could generate hydrogen under ultraviolet (UV) light-excitation with applied bias in KOH solution. The Ti mesh was used as the substrate to synthesize the self-organized TiO₂ nanotubular array layers. The effect of the morphology of the nanotubular array layers on the photovoltaic performances was investigated. When TiO₂ photocatalyst was irradiated with UV-excitation, it prompted the water splitting under applied bias (0.6 V vs. Normal Hydrogen Electrode, NHE.). Photocurrent generation of 0.58 mA/cm² under UV-light irradiation showed good performance on hydrogen production.     

Photocorrosion-less stable heterojunction photoanode for efficient visible-light driven solar hydrogen generation

In this work, a heterostructure CdS/TiO₂ nanotubes (TNT) photoelectrode is decorated with Ni nanoparticles (NPs) to enhance hydrogen generation via the photoelectrochemical method. Herein, we report a systematic study of the effect of Ni NPs heterostructure photoelectrode to improve light absorption and photoelectrochemical (PEC) performance. The fabricated photoelectrodes were evaluated for photoelectrochemical hydrogen generation under simulated sunlight. The optimized Ni/CdS/TNT photoelectrode exhibited an improved photocurrent density of 6.5 mA cm^?2 in poly-sulfide aqueous media at a low potential of 0 V. Owing to the enhanced photocurrent density, Ni NPs also played a significant role in improving the stability of the photoelectrode. The synergistic effect with semiconductor ternary junction incites the surface plasmon resonance (SPR) for light-harvesting to enhance photoelectrochemical hydrogen generation.     

Photoelectrical and charge transfer properties of hydrogen-evolving TiO2 nanotube arrays electrodes annealed in different gases

TiO₂ nanotube arrays were fabricated by sonoelectrochemical anodic oxidation and calcined in nitrogen, air, or 5% hydrogen/nitrogen which was denoted as TNT-A, TNT-N, and TNT-H, respectively. All annealed TiO₂ nanotube arrays samples exhibited similar surface morphology. With UV illumination (365 ± 15 nm), the photocurrent density of the TNT-A, TNT-N and TNT-H was about 0.27 mA/cm², 0.45 mA/cm² and 0.60 mA/cm², respectively. The trapped electron at the Ti⁴⁺ center of TiO₂ nanotube arrays shows absorption at around 500-700 nm. From the XPS measurement, it was found that annealing in 5% hydrogen/nitrogen helped the sample obtain a greater defect density. Because of the reduction of Ti⁴⁺ and the formation of oxygen vacancies, the charge transfer resistance appeared in this order: TNT-A > TNT-N > TNT-H. Thus TNT-H harvested the greatest charge carrier density of 9.86 × 10²⁰ cm⁻³, TNT-N and TNT-A obtained a charge carrier density of 1.38 × 10²⁰ cm⁻³ and 1.06 × 10²⁰ cm⁻³, respectively. Accordingly, the hydrogen production rate by water splitting over TNT-A, TNT-N and TNT-H (320-780 nm irradiation, 3 h) was about 120 μL/h cm², 159 μL/h cm² and 231 μL/h cm², respectively.     

In situ synthesis of MoO3/Ag/TiO2 nanotube arrays for enhancement of visible-light photoelectrochemical performance

A ternary composites of MoO₃/Ag/TiO₂ nanotube arrays were synthesized by in-situ annealing of TiO₂ nanotube arrays impregnated with AgNO₃ over MoO₃ powders. During the annealing process, the crystallization of the TiO₂ nanotubes, the thermo-decomposition of AgNO₃ to Ag nanoparticles, and the sublimation of MoO₃ occur jointly. The photoelectrochemical measurements of the resultants indicate that MoO₃/Ag/TiO₂ nanotube arrays present better photoelectrochemical properties compared with Ag/TiO₂ nanotube arrays and pristine TiO₂ nanotube arrays. Especially, the highest photocurrent and open circuit voltage are up to 21.29 μA/cm² and 0.058 V under visible light irradiation, whereas 1.77 and 3.87 times larger than those of TiO₂ nanotube arrays, respectively. Superior photoelectrochemical stability and larger photo-conversion efficiency of the ternary composites are also demonstrated. The improved photoelectrochemical properties are related to the close interfacial contact among MoO₃, Ag, and TiO₂ as well as the surface plasma resonance of Ag in the ternary composites, which broaden the range of light response and enhance the efficiency of charge separation. This study provides a skillful solution to construct TiO₂-based composite materials and demonstrates it is an unique architecture to promote the visible light driven photocatalytic application of TiO₂.     

Determination of photo conversion efficiency of nanotubular titanium oxide photo-electrochemical cell for solar hydrogen generation

Anodized and annealed titanium oxide nanotubes show enhanced photo activity and can be used as photo anodes for water electrolysis in hydrogen generation. Application of an external potential to the photo anode is required for enhancement of the photocurrent. This additional electrical energy input complicates the photo conversion efficiency calculation. In this investigation, the photo-electrochemical behavior of anodized titanium oxide nanotubular arrays have been characterized in various electrolytes. Increase in the applied potential increased the photocurrent under illumination with visible light. A simple experimental method for calculating the photo conversion efficiency has been proposed. According to this method, the potential difference between the photo anode and cathode is measured with and without light illumination. The product of the photocurrent and the increase in potential due to light irradiation is considered as the net power output. The photocurrent and the conversion efficiency increased with increase in the pH of the electrolyte. TiO₂ nanotubular arrays annealed at 350 °C for 6 h in nitrogen atmosphere showed a maximum photo conversion efficiency of ∼4% in 1 M KOH electrolyte and ∼3% in 3.5 wt.% sodium chloride solution. The results indicate that nanotubular TiO₂ can be potentially used for the photo electrolysis of seawater to generate hydrogen.     

Self-organized TiO2 nanotube arrays with uniform platinum nanoparticles for highly efficient water splitting

Highly efficient water splitting electrode based on uniform platinum (Pt) nanoparticles on self-organized TiO₂ nanotube arrays (TNTAs) was prepared by a combination of multi-step electrochemical anodization with facile photoreduction process. Uniform platinum (Pt) nanoparticles with an average diameter of 8 nm are distributed homogeneously on nanoporous top layer and underneath TiO₂ nanotube wall. In comparison to pristine TNTAs, Pt@TNTAs show substantially enhanced photocurrent density and the incident photon-to-current conversion efficiency (IPCE) in the entire wavelength window. The maximum photocurrent density and IPCE from the optimized Pt@TNTAs photoelectrode (Pt, ～1.57 wt%) were about 24.2 mA cm⁻² and 87.9% at 350 nm, which is much higher than that of the pure nanotubes sample (16.3 mA cm⁻² and 67.3%). The resultant Pt@TNTAs architecture exhibited significantly enhanced photoelectrochemical activities for solar water splitting with hydrogen evolution rate up to 495 μmol h⁻¹ cm⁻² in 2 M Na₂CO₃ + 0.5 M ethylene glycol under the optimal external bias of −0.3 V_SCE.