InP/TiO2 heterojunction for photoelectrochemical water splitting under visible-light

Hydrogen production through photoelectrochemical (PEC) water splitting on photocatalyst is a green and clean method. In this study, we use density functional theory (DFT) calculations to find that the cage-like InP quantum dots (QDs) sensitized TiO₂ is an effective photocatalyst for PEC water splitting under visible-light. A 16-ps first-principle molecular dynamics (FPMD) simulation results indicate that the cage-like InP-12, InP-16, InP-20, InP-24, InP-28, and InP-36 QDs are stable at room temperature (300 K). Furthermore, the calculated energy gaps of InP-16, InP-20, InP-24, InP-28, and InP-36 QDs are about 2.0 eV, which are suitable for visible-light absorption. Stable InP-20/TiO₂ heterojunction structure was also obtained by FPMD simulation, and the electronic structure calculation result indicates that the InP-20/TiO₂ heterojunction has a favorable type-II band aligment, which could prevent the recombination of photoexcited carriers. Finally, the possible reaction pathways of hydrogen production on InP-20/TiO₂ heterojunction were investigated. It is found that energy barrier of hydrogen production of the InP-20/TiO₂ is 2.56 eV lower than pure TiO₂. Our calculations imply that InP QDs sensitized anatase TiO₂ is an effective photocatalyst for visible-light PEC water splitting.     

TiO2-rutile/anatase homojunction with enhanced charge separation for photoelectrochemical water splitting

The mismatched interfaces of heterojunction usually have lots of defects, deriving in recombination of generated electron-hole pairs. On the other hand, homojunction interfaces are considered to be beneficial to the separation of charge carriers due to the similar characteristics in two sides of homojunction. TiO₂ have rutile and anatase two typical photoactive phases in nature. In this work, TiO₂-rutile/anatase (TiO₂-R/A) homojunction photoanode is fabricated by in situ growth of anatase TiO₂ on TiO₂-R surface. By contrast with TiO₂-rutile/rutile (TiO₂-R/R) photoanode, TiO₂-R/A displays higher photocurrent density (1.70 mA cm^?2 at 0.6 V vs. SCE). Deep insight into the mechanism suggests that TiO₂-R/A homojunction has intense band bending and enhanced surface area, which facilitate the charge separation and transmission. This study offers some novel insights to design and fabricate semiconductors photoanodes for highly efficient photocatalytic reactions.     

Enhancing the PEC water splitting performance of In2O3 nanorods by a wet chemical reduction

Generating oxygen vacancies is an effective way to improve photoelectrochemical (PEC) water splitting performance of semiconductor materials owing to the formation of shallow donor level and the supply of additional electron donor. Herein, oxygen vacancies were introduced into In₂O₃ nanorods by a hydrothermal reduction method using NaBH₄ solution as the reductant, and the effects of hydrothermal reduction time on the oxygen vacancy concentration, optoelectronic property and PEC water splitting activity over In₂O₃ nanorods were systematically investigated. The results of LSV, EIS and MS showed that the reduced samples displayed superior PEC performance and In₂O_3-x-1 exhibited a highest photocurrent density of 0.97 mA cm^?2 at 1.23 V vs. RHE under the irradiation of visible light, which was roughly 4 times of bare In₂O₃. The remarkable performance of In₂O_3-x-1 is mainly ascribed to the introduction of oxygen vacancies, which leads to better light absorption capacity, higher carrier concentration, and increased electron transport efficiency at the electrode/electrolyte interface.     

Decorating Cu2O with Ni-doped metal organic frameworks as efficient photocathodes for solar water splitting

Severe photocorrosion and fast photoexcited charges recombination hinder the application of Cu₂O in photoelectrochemical (PEC) water splitting. In this work, Ni-doped metal-organic frameworks is firstly applied to improve the performance of electrodeposited Cu₂O. A decorative layer of Ni-doped Cu₃(BTC)₂ (Ni-CuBTC) was in-suit constructed on Cu₂O through solvothermal followed by ion-exchange. Cu₂O/Ni-CuBTC photocathodes increase absorption edge to ∼800 nm, positive shift flat band position to 0.4 V, and decrease Tafel value to 74 mV/dec. These results confirm the decorative layer can extend light absorption, facilitate photoexcited charge separation and transfer, and enhance HER activity. A photocurrent density of −1.51 mA/cm² at 0 V_RHE is obtained with the decoration of Ni-CuBTC, which is 3.4 times of pristine Cu₂O photocathode. Here, the PEC water splitting performance of electrodeposited Cu₂O has been significantly improved with noble-metal-free decorations, which provides a new idea for solving the defects of Cu₂O based photocathode.     

High-performing photoanodes with a cost-effective n-InGaN/p-Cu2O heterostructure for water splitting

InGaN nanorods are highly desirable candidates for photoelectrochemical water splitting photoelectrodes because of their inherent material properties. However, their use is hindered by their low carrier separation efficiency and high production cost. Therefore, in this work, InGaN nanorods were grown by a low-cost HCVD method, and, p-n heterojunction n-InGaN/p-Cu₂O photoanodes were successfully constructed by electrodeposition to address the low carrier separation efficiency. The optimized InGaN/Cu₂O photoelectrodes with uniform morphology have a maximum photocurrent density of 4.2 mA cm^?2 at 1.23 V vs. RHE, which is 8.4 times that of pure InGaN nanorod photoelectrodes. A comprehensive experimental study showed that this approach of constructing p-n heterojunctions greatly enhances the carrier separation efficiency and alleviates the charge transfer kinetic bottleneck at photoelectrodes.     

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.     

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.     

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.     

Characterization of photoelectrochemical cells for water splitting by electrochemical impedance spectroscopy

The photocurrent-voltage characteristic of a photoelectrochemical cell for solar hydrogen production via water splitting, using undoped-hematite as photoanode, was obtained. Photoelectrochemical characteristics of the cell were also investigated by electrochemical impedance spectroscopy. Both techniques were carried out in the dark and under illumination. The analysis of the frequency spectra for the real and imaginary parts of the complex impedance allowed obtaining equivalent electrical analogs for the PEC cell operating in the dark and under 1 sun simulated illumination. Additionally, different electrode configurations were used (two and three-electrode arrangements). The two-electrode configuration allowed the study of the overall charge transfer phenomena occurring at the semiconductor, within the electrolyte and at the counter-electrode side of the cell, whereas the three-electrode configuration gave more detailed information concerning the double charged layer at the semiconductor/electrolyte interface.     

Hierarchical mesoporous SnO2/BiVO4 photoanode decorated with Ag nanorods for efficient photoelectrochemical water splitting

Bismuth vanadate has been extensively investigated as a potential visible light photoanode for PEC water splitting. The performance of BiVO₄ is restricted by fast charge recombination and slow oxygen evolution reaction kinetic. To address these issues, hierarchical SnO₂ (HSN) mesoporous support is developed via a novel sol-electrophoretic approach, and BiVO₄ film is decorated with silver nanorods (Ag NRs). The photocurrent density of HSN/BiVO₄ photoanode is 3.98 mA/cm² at 1.23 V vs. reversible hydrogen electrode (RHE) and onset potential (V_onset) of 0.5 V vs. RHE. The PEC performance is attributed to the appropriate band alignment between SnO₂ and BiVO₄, as well as the hierarchical structure of SnO₂. Ag-HSN/BiVO₄ photoanode shows photocurrent density of 4.30 mA/cm² at 1.23 V vs. RHE and V_onset of 0.28 V vs. RHE. The enhanced photocurrent and negatively shifted V_onset can be attributed to radiative localized surface plasmon resonance decay and catalytic effect of Ag NRs, respectively.     

Nanostructured Ni:BiVO4 photoanode in photoelectrochemical water splitting for hydrogen generation

Photoelectrochemical water splitting using bismuth vanadate (BiVO₄) is drawing attention but on account of presence of high charge recombination and poor water oxidation kinetics its performance is restricted. Present study attempts to understand the role of dopant Ni on BiVO₄ in a) reducing the charge recombination and b) to improve water oxidation kinetics. Ni doped BiVO₄ thin films are prepared via electrodeposition method and photoelectrochemical properties are investigated in 0.1 M phosphate buffer solution with and without sodium sulfite hole scavenger. Photocurrent density of 1.36 mA/cm² at 1.23 V vs. RHE has been obtained using 1.5% Ni doped BiVO₄. This sample also offered lower flat band potential, high open circuit potential and applied bias photon-to-current conversion efficiency. Addition of hole scavenger significantly increases the photoelectrochemical performance. Ni as a dopant therefore can play an important role in not only suppressing the electron-hole pair recombination but also in offering significantly enhanced photoelectrochemical response.     

Structural engineering of Ti-Mn bimetallic phosphide nanotubes for efficient photoelectrochemical water splitting

Designing next-generation advanced electrode materials by engineering their structural and compositional features can provide a feasible strategy to enhance the electrochemical performance of energy conversion devices. In this study, the rational pathway to design and fabricate nanotube arrays of titanium manganese phosphide via etching of titanium-manganese alloy followed by plasma phosphidation in PH₃ environment is presented and discussed. The structural and elemental analyses of the air-annealed electrodes before plasma treatment confirmed the presence of different binary oxides; TiO₂, MnO, and Mn₂O₃. However, the XPS fitting showed the presence of Ti³⁺ and higher ratio of MnO when annealed in hydrogen atmosphere. The presence of composite oxides resulted in a band gap reduction, which increased the light harvesting capability of the material. This synergetic effect resulted also in a shift in the open-circuit voltage (V_OC) and almost 10-fold increase in the photocurrent density compared to the performance of the nanotubes annealed in air. Mott-Schottky analysis showed a four-orders of magnitude enhancement in the carrier density for the electrodes annealed in Hydrogen and treated in PH₃-plasma compared to those annealed in O₂ or air, ascribed to the creation of Ti³⁺ defects and phosphidation. Our study thus paves the way to a new approach for creating high-performance hybrid electrodes for PEC water splitting.     

Molybdenum doped bilayer photoanode nanotubes for enhanced photoelectrochemical water splitting

Conversion of solar energy into hydrogen energy via photoelectrochemical (PEC) water splitting is one of the most promising approaches for generation of clean and sustainable hydrogen energy in order to address the alarming global energy crisis and environmental problems. To achieve superior PEC performance and solar to hydrogen efficiency (STH), identification, synthesis, and development of efficient photoelectrocatalysts with suitable band gap and optoelectronic properties along with high PEC activity and durability is highly imperative. With the aim of improving the performance of our previously reported bilayer photoanode of WO₃ and Nb and N co-doped SnO₂ nanotubes i.e. WO₃-(Sn_0.95Nb_0.05)O₂:N NTs, herein, we report a simple and efficient strategy of molybdenum (Mo) doping into the WO₃ lattice to tailor the optoelectronic properties such as band gap, charge transfer resistance, and carrier density, etc. The Mo doped bilayer i.e. (W_0.98Mo_0.02)O_3-(Sn_0.95Nb_0.05)O₂:N revealed a higher light absorption ability with reduced band gap (1.88 eV) in comparison to that of the undoped bilayer (1.94 eV). In addition, Mo incorporation offered improvements in charge carrier density, photocurrent density, with reduction in charge transfer resistance, contributing to a STH (～3.12%), an applied bias photon-to-current efficiency (ABPE ～ 8% at 0.4 V), including a carrier density (N_d ～ 7.26 × 10²² cm^?3) superior to that of the undoped bilayer photoanode (STH ～2%, ABPE ～ 5.76%, and N_d ～5.11 × 10²² cm^?3, respectively). The substitution of Mo⁶⁺ for W⁶⁺ in the monoclinic lattice, forming the W–O–Mo bonds altered the band structure, realizing further enchantments in the PEC reaction and charge transfer kinetics. Additionally, doped bilayer photoanode revealed excellent long term PEC stability under illumination, suggesting its robustness for PEC water splitting. The present work herein provides a simple and effective Mo doping approach for generation of high performance photoanodes for PEC water splitting.     

Template synthesis of porous hierarchical Cu2ZnSnS4 nanostructures for photoelectrochemical water splitting

Environmentally friendly and low-cost Cu₂ZnSnS₄ (CZTS) is a promising light absorber for photoelectrochemical (PEC) hydrogen production from water splitting due to the earth-abundant elements, high absorption coefficient, and narrow bandgap. Herein, the hierarchical CZTS film with porous nanostructures was successfully synthesized by a template method. The hierarchical CZTS film was composed of flower-like particles, which were assembled with thin CZTS nanosheets. Macropores were generated owing to the aggregation of flower-like spheres, and mesopores were formed from the stacking of CZTS nanosheets. Compared to the dense CZTS film, the porous hierarchical CZTS film showed a much higher PEC property for water splitting. The improved performance could be attributed to three merits of the porous hierarchical morphology: enhanced light absorption, improved charge separation and transfer, and enlarged electrochemically active surface area. This study provides a useful idea to design efficient semiconductor photoelectrodes for water splitting with delicately controlled morphology.     

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.     

Pulsed sonoelectrodeposition of leaf-like Bi2WO6 film with exposed [001] facet as a photocathode with a remarkable high photovoltage in water splitting

Bi₂WO₆ is one of the promising triplet bismuth compound that has a layered structure with a high photocatalytic activity for photo-electrochemical (PEC) water splitting systems. Here, Bi₂WO₆ synthesizes by the sonoelectrochemical method in pulse mode of ultrasound. Unexpectedly, synthetic samples show photocathode rather than photoanode activity in PEC systems. Applying of this method creates a leaf-like morphology with exposed [001] crystal facet and controllable amount of surface defects. The co-existence of oxygen and metal vacancies play a significant role in suppressing charge recombination and enhancing charge transporting in photoelectrodes. The creation of high surface vacancies leads to change the conduction and valence band positions and cause hydrogen evolution by Bi₂WO₆ photoelectrodes. Another surprising result for the synthesized film by pulse mode is the creation of high photovoltage about 1.25 V that has a remarkable effect in suppressing charge recombination rate and proposed driving force for water reduction. Furthermore, the onset potential of the photoelectrodes improves and records high efficiencies (ABPE = 2.46% at −0.8 V and IPCE≈28% at 450 nm). The obtaining results introduces the sonoelectrochemical method as a promising method for the synthesis of highly efficient photoelectrodes.     

Cobalt oxide as photocatalyst for water splitting: Temperature-dependent phase structures

This study investigated the best phases of cobalt oxide for the photochemical and photoelectrochemical (PEC) water-splitting reaction. Cobalt oxide was produced via a hydrothermal process of cobalt nitrate hexahydrate and then annealed at different temperatures from 450 °C to 950 °C. The Co₃O₄ phase was produced during pre-annealing and annealing at 450 °C. The mixed phase of Co₃O₄ and CoO was produced during annealing at 550 °C and 650 °C, and pure CoO was produced during annealing from 750 °C to 950 °C. The Co₃O₄ phase produced the highest photocurrent density with a value of 1.15 mA cm⁻² at a −0.4 V potential bias vs. Ag/AgCl. This value two times higher than that reported by other researchers at the same potential bias. Furthermore, the highest rate of hydrogen collected by Co₃O₄ was ~272.6 μmol h⁻¹ g⁻¹ after 8 h photocatalytic process. The amount of collected hydrogen was stable until 12 h of the process.     

An iron oxide -copper bismuth oxide photoelectrochemical cell for spontaneous water splitting

Highly efficient water splitting reaction on hematite photoelectrode has been encumbered by its low photovoltage and photocurrent in a water splitting cell. In this work, a nanostructured hematite photoanode was prepared via a hydrothermal method, and its water oxidation activity was greatly enhanced by the synergetic application of uniform in-situ cobalt-doping and surface modification with fine cobalt iron oxide nanoparticles electrocatalyst. As a result, its remarkable low onset potential of 0.55 V_RHE for water oxidation allows the construction of tandem cell with a novel metal oxide photocathode CuBi₂O₄, which has already proven reasonably robust photoactivity for water reduction reaction. The photocurrent and long-term stability of this metal oxides based device in alkaline electrolyte for unassisted overall water splitting reaction were investigated. A solar to hydrogen efficiency of 0.15% was measured accordingly on this spontaneous hydrogen production device, without the involvement of precious metal components.