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.     

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.     

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.     

Influence of Pt deposition on water-splitting hydrogen generation by highly-ordered TiO2 nanotube arrays

Highly-ordered TiO₂ nanotube arrays (TNTAs) were fabricated on Ti sheets by electrochemical anodization. Uniform Pt nanoparticles with an average diameter of 3 nm could be successfully located on the TiO₂ nanotubes on only one side (Pt/TNTAs) or both sides of the Ti sheet (Pt/TNTAs/Pt). Pt/TNTAs, the single-sided Pt deposited TNTAs, could be directly used to split water without a counter electrode. The hydrogen evolution rate can reach 120 μmol h⁻¹ cm⁻² in a mixed solution of 0.5 M Na₂SO₄ and 0.5 M ethylene glycol without any applied bias, which is six times of that by the pure TNTAs. In comparison to the traditional three electrode system, this single-sided Pt deposited TNTAs is a much more simple and efficient water splitting system. Meanwhile, the photoelectrical conversion mechanism has been investigated in detail.     

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.     

Arrayed porous iron-doped TiO2 as photoelectrocatalyst with controllable pore size

Arrayed porous iron-doped TiO₂ with controllable pore size was prepared by using polystyrene spheres and its structure, morphology, composition and photoelectrochemical properties were characterized with X-ray diffraction, scanning electron microscope, inductively coupled plasma-atomic emission spectrometer and electrochemical methods. It is found that the photoelectrochemical properties of the arrayed porous TiO₂ can be improved by doping adequate amount of iron in the lattice of TiO₂ and the sample doped with 0.01 wt% Fe (based on Ti) exhibits the best photoelectrochemical performance. With doping 0.01 wt% Fe in TiO₂, the photocurrent density of the sample is improved from 2.0 μA cm⁻² to 10.0 μA cm⁻² and its flat-band potential shifts from −0.38 V to −0.55 V (vs. SCE).     

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.     

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.     

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.     

Improvement of photocatalytic hydrogen generation from CdSe/CdS/TiO2 nanotube-array coaxial heterogeneous structure

The fabrication and characterization of CdSe/CdS/TiO₂ nanotube-array coaxial heterogeneous structure that has potential applications in photocatalytic water splitting and toxic pollutants degradation are investigated. CdSe(top)/CdS(under) double-layer is conformally deposited onto TiO₂ nanotubes by successive ionic layer adsorption and reaction (SILAR) and electrochemical atomic layer deposition (ECALD), respectively, for the CdS under layer and the CdSe top layer. Such double sensitized TiO₂ nanotubular photoelectrode exhibits significant enhancements in photoconversion efficiency, visible light response, and efficient hydrogen generation. The detailed synthesis process and the surface morphology, phase structure, elemental analysis, and photoelectrochemical properties of the resulting films with the CdSe/CdS/TiO₂ nanotube-array coaxial heterogeneous structure are discussed. The photoconversion efficiency of 9.47% and hydrogen generation rate of 10.24 ml h⁻¹ cm⁻² were observed. Both values are a 7-fold enhancement compared with that of the pure TiO₂ nanotube. The as-prepared photoelectrode presents potential application for industrialized photocatalytic hydrogen generation in the future.     

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.     

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.     

Photoelectrochemical water oxidation of LaTaON2 under visible-light irradiation

Lanthanum tantalum oxynitride (LaTaON₂) powders were prepared by one-step flux method. LaTaON₂ photoanodes, which are fabricated by using LaTaON₂ powders, are found to exhibit photoelectrochemical activity for overall water splitting. The photocurrent for LaTaON₂ photoelectrodes was ca. 120 μA cm⁻² at 1.5 V vs. reversible hydrogen electrode (RHE) in 1 M NaOH aqueous solutions (pH = 13.6) under AM 1.5 G simulated sunlight irradiation (100 mW cm⁻²). The photocurrent of LaTaON₂ photoelectrode from back-side illumination is much larger than that from front-side illumination, suggesting that the photoelectrochemical property is mainly limited by poor continuous electron transport in the bulk. Further efforts to ameliorate the electron transport in the bulk of LaTaON₂ photoelectrodes are expected to significantly improve their photoelectrochemical performance.     

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%.     

Effective water splitting using N-doped TiO2 films: Role of preferred orientation on hydrogen production

N-doped TiO₂ film with preferred (211) orientation, deposited by RF magnetron sputtering, was investigated for the water-splitting hydrogen production. It is found that the preferred crystal growth orientation of the films can be controlled by N₂ flow rate during the deposition. The results reveal that not only the N-doping, but also the preferred orientation (i.e., large percentage of exposed (211) facet), can effectively enhance the activity of TiO₂-based photocatalyst. With the increase of exposed (211) facets, the hydrogen production rates of N-doped TiO₂ films rise from 760 μmol H₂ h⁻¹ m⁻² to 4500 μmol H₂ h⁻¹ m⁻², indicating that high performance of TiO₂-based photocatalyst can be achieved by controlling the preferred orientation of the films.     

Noble metal-free cobalt oxide (CoOx) nanoparticles loaded on titanium dioxide/cadmium sulfide composite for enhanced photocatalytic hydrogen production from water

In this present paper, cobalt oxide (CoO_x) is studied as an effective cocatalyst in a photocatalytic hydrogen production system. CoO_x-loaded titanium dioxide/cadmium sulfide (TiO₂/CdS) semiconductor composites were prepared by a simple solvothermal method and characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS), and X-ray photoelectron spectroscopy (XPS). Photocatalytic hydrogen production was studied using the as-synthesized photocatalysts in aqueous solution containing sodium sulfide (Na₂S)/sodium sulfite (Na₂SO₃) as hole scavengers under visible light irradiation (λ > 400 nm). The optimal cobalt content in CoO_x-loaded TiO₂/CdS composite is determined to be 2.1 wt% and the corresponding rate of hydrogen evolution is 660 μmol g⁻¹ h⁻¹, which is about 7 times higher than TiO₂/CdS and CdS photocatalysts under the same condition. Visible light-driven photocurrents of the semiconductor composites were further measured on a photoelectrochemical electrode, revealing that the photocorrosion of CdS can be prevented due to the presence of TiO₂–CoO_x.     

Photoelectrocatalytic hydrogen production of heterogeneous photoelectrodes with different system configurations of CdSe nanoparticles,Au nanocrystals and TiO2 nanotube arrays

The different configurations of CdSe nanoparticles, Au nanocrystals and TiO₂ nanotube arrays play an important role in the photoelectrochemical behavior and photoelectrocatalytic hydrogen production of this heterogeneous photoelectrode system. It is discovered that the photoelectrocatalytic hydrogen production of the TiO₂–CdSe–Au photoelectrode (1.724 mmol g⁻¹ h⁻¹) is about 4 times that of the TiO₂–Au–CdSe photoelectrode (0.430 mmol g⁻¹ h⁻¹) under visible light irradiation. From the comprehensive investigation of their photoelectrochemical behaviors, it is illustrated that the interfacial electrical field has distinct effects on the separation and transportation of photogenerated carriers in these heterostructure photoelectrodes. The directions of the interfacial electrical fields formed at TiO₂–Au and Au–CdSe interfaces are opposite in the TiO₂–Au–CdSe photoelectrode, which hinders the separation of photogenerated electron-hole pairs and subsequent transportation of photogenerated carriers. On the contrary, the directions of the interfacial electrical fields formed at TiO₂–CdSe and CdSe–Au interfaces are identical in the TiO₂–CdSe–Au photoelectrode, which promotes the separation of photogenerated excitons and subsequently enhances their transportation for enlarged photocurrent density. The results of photoelectrocatalytic hydrogen production also confirm our assumption.     

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.     

An excellent room-temperature hydrogen sensor based on titania nanotube-arrays

Hydrogen sensors have been fabricated from highly ordered TiO₂ nanotube arrays through anodization of a Ti substrate in an ethylene glycol solution containing NH₄F. The vertically oriented TiO₂ nanotube arrays containing Pt electrodes exhibit an ability to detect a wide-range of hydrogen concentrations at room temperature. On exposure to 2000 ppm (parts per million) hydrogen, the sensors exhibit seven orders of magnitude change in resistance with a response time of 13 s at room temperature. The TiO₂ nanotube arrays sensor equipped with Pt electrodes exhibited a diode-type current–voltage (I–V) characteristic in air, but nearly ohmic behavior in hydrogen balanced with argon. A significant response to hydrogen was observed without the presence of oxygen in the base atmosphere. The response of two kinds of sensors with either Pt or Pt/Ti electrodes to 500 ppm hydrogen was measured and the results suggested that the excellent hydrogen sensing properties in air resulted primarily from the variation of the Schottky barrier height at the Pt/TiO₂ interface.     

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.