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.     

High photoelectrochemical water splitting performance on nitrogen doped double-wall TiO2 nanotube array electrodes

The nitrogen doped double-wall TiO₂ nanotube arrays (N-DW-TiO₂ NTs) have been prepared by a facile two steps electrochemical anodization method, and the nitrogen has been successfully incorporated into the nanotubes in situ anodization process. The unique double walls tubular surface morphology has been achieved by conducting higher anodic voltage in second anodization process than that in the first anodized step. The nitrogen doping and following annealed process in nitrogen atmosphere did not damage the unique, ordered, and vertically aligned structures. Under illumination of simulated solar light (AM 1.5, 100 mW/cm²), the N-DW-TiO₂ NTs presented a high photoelectrochemical water splitting performance, which mainly ascribed to the high surface areas and expended optical absorbance to visible light region. The high surface areas, ordered structure for facilitating electron transfer, and visible light absorbance present the new avenue for improving the solar light application in photoelectrochemical water splitting process for practical hydrogen generation. The N-DW-TiO₂ NTs can be one of promising prototype nanomaterials, and much higher photoconversion efficiency can be expected for the co-doped or sensitized on the N-DW-TiO₂ NTs.     

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.     

Electrochemical reduction induced self-doping of oxygen vacancies into Ti–Si–O nanotubes as efficient photoanode for boosted photoelectrochemical water splitting

Self-doping of oxygen vacancies (V_O) states into TiO₂-based nanotubes was an efficient way for improving photoelectrochemical (PEC) water splitting properties. Here we induced oxygen vacancies into Si-doped TiO₂ (Ti–Si–O) nanotubes on Ti–Si alloy via a facile electrochemical surface reduction, and applied it for PEC water splitting. Systematic studies revealed that the self-doped oxygen vacancies not only promoted optical absorption of the doped nanotubes but also enhanced separation-transport processes of the photo-generated charge carriers, and thus resulted in improved PEC water splitting properties. The V_O/Ti–Si–O co-doping system exhibited a higher photocurrent density of 1.63 mA/cm² at 0 V vs. Ag/AgCl. Corresponding solar-to-hydrogen efficiency could reach 0.81%, which was about 5.4 times that of undoped TiO₂. It's believed that elements doping and oxygen vacancies self-doping synergistic strategy employed in this work, may provide theoretical and practical significance for designing and fabricating efficient TiO₂-based nanostructures photoanodes in PEC water splitting for boosted solar-to-hydrogen conversion.     

In2O3:Sn/TiO2/CdS heterojunction nanowire array photoanode in photoelectrochemical cells

The design of photoanode with highly efficient light harvesting and charge collection properties is important in photoelectrochemical (PEC) cell performance for hydrogen production. Here, we report the hierarchical In₂O₃:Sn/TiO₂/CdS heterojunction nanowire array photoanode (ITO/TiO₂/CdS-nanowire array photoanode) as it provides a short travel distance for charge carrier and long light absorption pathway by scattering effect. In addition, optical properties and device performance of the ITO/TiO₂/CdS-nanowire array photoanode were compared with the TiO₂ nanoparticle/CdS photoanode. The photocatalytic properties for water splitting were measured in the presence of sacrificial agent such as SO₃²⁻ and S²⁻ ions. Under illumination (AM 1.5G, 100 mW/cm²), ITO/TiO₂/CdS-nanowire array photoanode exhibits a photocurrent density of 8.36 mA/cm² at 0 V versus Ag/AgCl, which is four times higher than the TiO₂ nanoparticle/CdS photoanode. The maximum applied bias photon-to-current efficiency for the ITO/TiO₂/CdS-nanowire array and the TiO₂ nanoparticle/CdS photoanode were 3.33% and 2.09%, respectively. The improved light harvesting and the charge collection properties due to the increased light absorption pathway and reduced electron travel distance by ITO nanowire lead to enhancement of PEC performance.     

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.     

Pt modified TiO2 nanotubes electrode: Preparation and electrocatalytic application for methanol oxidation

Pt nanoparticles decorated TiO₂ nanotubes (Pt/TiO₂NTs) modified electrode has been successfully synthesized by depositing Pt in TiO₂NTs, which were prepared by anodization of the Ti foil. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical methods were adopted to characterize their structures and properties. The Pt/TiO₂NTs electrode shows excellent electrocatalytic activity toward methanol oxidation reaction (MOR) in alkaline electrolyte without UV irradiation.     

Simultaneously efficient light absorption and charge transport of CdS/TiO2 nanotube array toward improved photoelectrochemical performance

CdS has been widely used to modify TiO₂-based photoanodes for photoelectrochemical (PEC) water splitting. Due to the poor interface contact between chalcogenides and oxides, however, such CdS modified TiO₂ materials usually exhibit inefficient separation and transport of charges, leading to an unsatisfactory efficiency during the PEC water splitting process. Addressing this issue, we herein report a CdS/TiO₂ nanotube array (CdS/TNA) photoanode that was fabricated through a successive ion layer absorption and reaction (SILAR) method with an additional subsequent annealing. This post-annealing process is essential to enhance the interface contact between the CdS and the TNAs, resulting in an accelerated transfer of photogenerated electrons from the CdS to the TNAs. In addition, the post-annealing also improves the light absorption capability of the CdS/TNA photoanode. The simultaneous enhancement of charge transport and light absorption provided by the post-annealing is essential for improving the PEC performance of the CdS/TNA photoanode. The CdS/TNA photoanode obtained by this strategy exhibits a much enhanced PEC performance in water splitting, and its photocurrent density and solar-to-hydrogen conversion efficiency could reach 4.56 mA cm⁻² at 1.23 V vs. reversible hydrogen electrode and 5.61%, respectively. This simple but effective route can provide a general strategy for obtaining high-performance oxide-based photoelectrodes.     

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.     

An efficient tandem photoelectrochemical cell composed of FeOOH/TiO2/BiVO4 and Cu2O for self-driven solar water splitting

An integrated solar water splitting tandem cell without external bias was designed using a FeOOH modified TiO₂/BiVO₄ photoanode as a photoanode and p-Cu₂O as a photocathode in this study. An apparent photocurrent (0.37 mA/cm² at operating voltage of +0.36 V_RHE) for the tandem cell without applied bias was measured, which is corresponding to a photoconversion efficiency of 0.46%. Besides, the photocurrent of FeOOH modified TiO₂/BiVO₄–Cu₂O is much higher than the operating point given by pure BiVO₄ and Cu₂O photocathode (∼0.07 mA/cm² at +0.42 V_RHE). Then we established a FeOOH modified TiO₂/BiVO₄–Cu₂O two-electrode system and measured the current density-voltage curves under AM 1.5G illumination. The unassisted photocurrent density is 0.12 mA/cm⁻² and the corresponding amounts of hydrogen and oxygen evolved by the tandem PEC cell without bias are 2.36 μmol/cm² and 1.09 μmol/cm² after testing for 2.5 h. The photoelectrochemical (PEC) properties of the FeOOH modified TiO₂/BiVO₄ photoanode were further studied to demonstrate the electrons transport process of solar water splitting. This aspect provides a fundamental challenge to establish an unbiased and stabilized photoelectrochemical (PEC) solar water splitting tandem cell with higher solar-to-hydrogen efficiency.     

Iron doped nanostructured TiO2 for photoelectrochemical generation of hydrogen

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

Photoelectrochemical water splitting with black Ni/Si-doped TiO2 nanostructures

Black Ni/Si-doped TiO₂ nanostructures were successfully fabricated through electrochemical anodization of Ti–1Ni–5Si alloy and Sn-reduction treatment. After Sn-reduction treatment, the band gap of Ni/Si-doped TiO₂ became much smaller compared to other samples, which can be attributed to the synergetic effect of Ni/Si doping and the large quantity of Ti³⁺/oxygen vacancy species induced by Sn-reduction treatment. The black Ni/Si-doped TiO₂ nanostructures exhibited a remarkable enhancement in the photoelectrochemical (PEC) water splitting in comparison with the pure TiO₂ and Ni/Si-doped TiO₂. The highest photocurrent reached 2.15 mA/cm² (at 0 V versus Ag/AgCl), corresponding to a conversion efficiency (~1.10%) which was 5.8 times that of the pure TiO₂ nanotubes. The first-principles calculations using density-functional theory (DFT) showed that ion doping and self-doped Ti³⁺ defect levels in the forbidden gap induced through Sn-reduction treatment could improve the mobility of photogenerated carriers and suppress charge recombination, which was in well agreement with the experimental results.     

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.     

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

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

TiO2/CeO2 core/shell heterojunction nanoarrays for highly efficient photoelectrochemical water splitting

In this paper, novel TiO₂/CeO₂ core/shell heterojunction nanorod (NR) arrays were synthesized as photoanode for photoelectrochemical (PEC) water splitting via a simple and facial two-step hydrothermal approach. This synthesis route can obtain different amount of CeO₂ nanoparticles by controlling the hydrothermal time and eventually achieve uniform TiO₂/CeO₂ core/shell nanostructures. The uniform TiO₂/CeO₂ core/shell heterojunction nanoarrays exhibit a markedly enhanced photocurrent density of 5.30 mA·cm^?2 compared to that of pristine TiO₂ NR 1.79 mA·cm^?2 at 1.23 V vs. RHE in 1 M KOH solution. The superior PEC performance of the TiO₂/CeO₂ core/shell heterojunction is primarily due to much enhanced visible light absorption and appropriate gradient energy gap structure. This work not only offers the synthesis route for the novel TiO₂/CeO₂ core/shell heterojunction, but also suggests that this new core/shell heterojunction has a great potential application for efficient PEC water splitting devices.     

Core-shell hetero-phase reduced Ti–Ni–O nanotubes photoanode with enhanced optical absorption and charge transport for boosted photoelectrochemical water splitting

Bulk-phase doping and surface oxygen-defective engineering of TiO₂-based nanostructures are identified as effective routes for enhanced photoelectrochemical (PEC) water splitting. Here, we reported a reduced Ti–Ni–O nanotubes photoanode with anatase-rutile crystalline-core and oxygen vavancies amorphous-shell for boosted PEC water splitting. The core-shell hetero-phase reduced Ti–Ni–O nanotubes were fabricated through phase-structure modulation by a thermal treatment of anodized Ti–Ni–O nanotubes on Ti–Ni alloy and with one-step electrochemical reduction. Microstructure, optical and PEC measurement results confirmed effective bulk-phase Ni-doping and surface oxygen vacancies self-doping into the reduced mixed-phase Ti–Ni–O nanotubes, which enabled high capability of optical-absorption and simultaneously favored charge separation-transfer for remarkably improved the PEC water splitting. A higher photocurrent density of 1.66 mA/cm² at 0 V vs. Ag/AgCl and solar-to-hydrogen efficiency of 0.79% were achieved for the reduced Ti–Ni–O system, which was 5.35 and 5.27 times that of undoped TiO₂, respectively. This work may shed an insight view on fabricating high-performance Ti-based nano-photoanodes with enhanced light harvesting and carrier kinetics for efficient PEC water splitting, through synergistic strategy of bulk-phase elements doping and surface oxygen vacancies self-doping.     

Active and robust novel bilayer photoanode architectures for hydrogen generation via direct non-electric bias induced photo-electrochemical water splitting

Photo-electrochemical (PEC) water splitting is a promising and environmentally benign approach for generation of hydrogen using solar energy with minimum greenhouse gas emissions. The development of semiconductor materials for photoanode with superior optoelectronic properties combined with excellent photoelectrochemical activity and stability is vital for the realization of viable commercial development of PEC water splitting systems. Herein, we report for the very first time, the study of nanoscale bilayer architecture of WO₃ and Nb and N co-doped SnO₂ nanotubes (NTs), wherein WO₃ NTs are coated with (Sn_0.95Nb_0.05)O₂:N-600 (annealed in NH₃ at 600 °C) layer of different thicknesses, as a potential semiconductor photoanode material for PEC water splitting. An excellent long term photoelectrochemical stability under illumination in the acidic electrolyte solution combined with a solar-to-hydrogen efficiency (STH) of ～3.83% (under zero applied potential) is obtained for the bilayer NTs, which is the highest STH obtained thus far, to the best of our knowledge compared to the other well studied semiconductor materials, such as TiO₂, ZnO and Fe₂O₃. These promising results demonstrate the excellent potential of bilayer NTs as a viable and promising photoanode in PEC water splitting.     

Low-temperature oxygen plasma treatment of TiO2 film for enhanced performance of dye-sensitized solar cells

The effects of low-temperature O₂ plasma treatment of a TiO₂ film are studied with the objective of improving the performance of dye-sensitized solar cells (DSSCs). X-ray photoelectron spectra (XPS) reveal that the ratio of titanium dioxide to titanium sub-oxides is increased in the O₂ plasma-treated TiO₂ film, compared with that of the untreated TiO₂ film. This increase suggests that the oxygen vacancies in the film are effectively reduced. The near-edge X-ray absorption fine structure (NEXAFS) spectra results agree with the XPS result. It is proposed that there is a correlation between the shifts of the peaks in the NEXAFS spectra and the adsorption of N719 dye on the TiO₂ particles. A DSSC having an O₂ plasma-treated, 4 μm thick TiO₂ film electrode renders a short-circuit photocurrent of 7.59 mA cm⁻², compared with 6.53 mA cm⁻² for a reference cell with an untreated TiO₂ electrode of the same thickness. As a result of these changes, the solar-to-electricity conversion efficiency of the O₂ plasma-treated cell is found to be 4.0% as compared with 3.5% for the untreated cell. This improvement in the performance is rationalized on the basis of increased N719 dye adsorption on to the TiO₂, due to the reduction in the number of oxygen vacancies caused by the oxygen plasma treatment.     

Remarkable improvement of photoelectrochemical water splitting in pristine and black anodic TiO2 nanotubes by enhancing microstructural ordering and uniformity

Efficient photoelectrochemical (PEC) water splitting is crucial for future energy and sustainable world. We here report on the improvement of PEC activity of anodic TiO₂ nanotubes (TNTs) by enhancing tube ordering and subsequent electrochemical reduction. TNTs were prepared by two-step anodic oxidisation from an organic electrolyte containing fluoride ions. The effects of first-step anodisation time on the ordering of TNTs and subsequent electrolytic reduction were investigated on the PEC performance under simulated solar light spectrum. The photocurrent densities of TNTs anodised for 1 h, 4 h and subsequently reduced are about 25.12 μA cm⁻², 51.76 μA cm⁻² and 126.89 μA cm⁻², respectively, at 1.23 V vs RHE and their conversion efficiency of light to electrical energy achieved are about 0.016%, 0.04% and 0.08% respectively. Electrochemical impedance spectroscopy (ESI) curves revealed the improved PEC water splitting confirmed by sharper charge carrier separation and enhanced charge transfer in highly ordered pristine and black TNTs. This improvement of PEC in dopant-free TNT is at the first instance interpreted by enhancing TNT ordering and uniformity achieved by prolonging of the first-step anodisation time and its effect on the electronic band structure of TNTs. This significant effect on PEC performance of pristine TNT under visible light absorption takes place due to the induced surface defects and slower recombination rates of hole and electron. This demonstrates an efficient economic materials production appraoch for PEC hydrogen production.     

Dye-sensitized solar cells with a micro-porous TiO2 electrode and gel polymer electrolytes prepared by in situ cross-link reaction

The ionic conductivities and performances of dye-sensitized solar cells (DSSCs) of gel polymer electrolytes (GPEs) prepared by in situ cross-link reaction with different cross-linkers were investigated. The poly(imidazole-co-butylmethacrylate)-based GPE containing the 1,2,4,5-tetrakis(bromomethyl)benzene (B4Br) cross-linker showed a higher ionic conductivity than that containing cross-linkers with a linear structure, due to the formation of micro-phase separation that resulted in an increase in ion transport paths in the GPE. Moreover, the co-adsorbent ((4-pyridylthio) acetic acid, PAA) co-adsorbed with N3 dye on the TiO₂ electrode not only reduced dye aggregation, but also reacted with the cross-linkers in the GPE at the TiO₂/GPE interface. A decrease in the charge transport resistance at the TiO₂/GPE interface was noted after forming the gel; thus the value of J_SC significantly increased from 7.72 to 10.00 mA cm⁻². In addition, in order to reduce the ionic diffusion resistance within the TiO₂ electrode, incorporation of monodispersed PMMA in the TiO₂ paste was considered. With the optimal weight ratio of PMMA/TiO₂ (w/w=3.75), the TiO₂ electrode exhibited larger pores (ca. 350 nm) uniformly distributed after sintering at 500 °C, and the ionic diffusion resistance within the TiO₂ film could significantly be reduced. The cell conversion efficiency increased from 3.61% to 5.81% under illumination of 100 mW cm⁻², an improvement of ca. 55%.