Ultrasonication-assisted liquid-phase exfoliation enhances photoelectrochemical performance in α-Fe2O3/MoS2 photoanode

This study successfully manufactured a p-n heterojunction hematite (α-Fe₂O₃) structure with molybdenum disulfide (MoS₂) to address the electron–hole transfer problems of conventional hematite to enhance photoelectrochemical (PEC) performance. The two-dimensional MoS₂ nanosheets were prepared through ultrasonication-assisted liquid-phase exfoliation, after which the concentration, number of layers, and thickness parameters of the MoS₂ nanosheets were respectively estimated by UV–vis, HRTEM and AFM analysis to be 0.37 mg/ml, 10–12 layers and around 6 nm. The effect of heterojunction α-Fe₂O₃/MoS₂ and the role of the ultrasonication process were investigated by the optimized concentration of MoS₂ in the forms of bulk and nanosheet on the surface of the α-Fe₂O₃ electrode while measuring the PEC performance. The best photocurrent density of the α-Fe₂O₃/MoS₂ photoanode was obtained at 1.52 and 0.86 mA.cm⁻² with good stability at 0.6 V vs. Ag/AgCl under 100 mW/cm² (AM 1.5) illumination from the back- and front-sides of α-Fe₂O₃/MoS₂; these values are 13.82 and 7.85-times higher than those of pure α-Fe₂O₃, respectively. The results of electrochemical impedance spectroscopy (EIS) and Mott-Schottky analysis showed increased donor concentration (2.6-fold) and decreased flat band potential (by 20%). Moreover, the results of IPCE, ABPE, and OCP analyses also supported the enhanced PEC performance of α-Fe₂O₃/MoS₂ through the formation of a p–n heterojunction, leading to a facile electron–hole transfer.     

Photoelectrochemical properties of texture‐controlled nanostructured α‐Fe2O3 thin films prepared by AACVD

Nanostructured α‐Fe₂O₃ thin film electrodes were deposited by aerosol‐assisted chemical vapour deposition (AACVD) for photoelectrochemical (PEC) water splitting on conducting glass substrates using 0.1 M methanolic solution of Fe(acac)₃. The XRD analysis confirmed that the films are highly crystalline α‐Fe₂O₃ and free from other iron oxide phases. The highly reproducible electrodes have an optical bandgap of ～2.15 eV and exhibit anodic photocurrent. The current–voltage characterization of the electrodes reveals that the photocurrent density strongly depended on the film morphology and deposition temperature. Scanning electron microscopy (SEM) analysis showed a change in the surface morphology with the change in deposition temperature. The films deposited at 450 °C have nanoporous structures which provide a maximum electrode/electrolyte interface. The maximum photocurrent density of 455 µA/cm² was achieved at 0.25 V vs. Ag/AgCl/3M KCl (～1.23 V vs. RHE) and the incident photon to electron conversion efficiency (IPCE) was 23.6% at 350 nm for the electrode deposited at 450 °C. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Morphologically different WO3 nanocrystals in photoelectrochemical water oxidation

Different morphologies of WO₃ nanocrystals such as nanorods and nanoplates have been obtained under hydrothermal conditions using ammonium metatungstate as the precursor in presence of different organic acids such as citric, oxalic, and tartaric acid in the reaction medium. Detailed characterization of the crystal structure, particle morphology, and optical band gap of the synthesized powders have been done by X-ray diffraction, transmission electron microscopy, scanning electron microscopy and solid-state UV–visible spectroscopy study. The as-synthesized materials are WO₃ hydrates with orthorhombic phase which transform to the hexagonal WO₃ through dehydration upon heating at 350 °C. The resultant products are crystalline with nanoscale dimensions. Finally, the photoactivity of the synthesized materials annealed at 500 °C has been compared employing in photoelectrochemical water oxidation under the illumination of AM 1.5G simulated solar light (100 mWcm⁻²). The photocurrent measurements upon irradiation of light exhibit obvious photocatalytic activity with a photocurrent of about 0.77, 0.61, and 0.65 mAcm⁻² for the WO₃ film derived with the oxalic acid, tartaric, and citric acid assisting agents, respectively, at 1.8 V versus Ag/AgCl electrode.     

The WO3/WS2 nanostructures: Preparation,characterization and optical absorption properties

The WO₃/WS₂ nanostructures were successfully prepared using a two-step hydrothermal/gas phase method. The physical properties of the nanostructures were characterized using XRD, SEM, TEM, UV–visible spectroscopy. The WO₃/WS₂ nanostructures obtained were coexistence of WO₃ and WS₂ in the same particle. The WO₃/WS₂ nanostructures contained a wide and intensive absorption in the UV–visible light region of 245–750 nm, which showed that the WO₃/WS₂ nanostructures may have a potential application as an UV–visible photocatalyst.     

Cu-doped flower-like hematite nanostructures for efficient water splitting applications

This study reports the successful preparation of Cu-doped hematite (α-Fe₂O₃) flower-like nanostructures with different Cu concentrations on FTO glass substrates using a facile hydrothermal method. The Cu-doped α-Fe₂O₃ flower-like nanostructure combines the advantage of p-type doping with the feature of a flower-like architecture. The prepared nanostructure film was applied as a photocathode in a photoelectrochemical (PEC) water splitting experiment and achieved a significantly improved photocurrent density of −5.34 mA cm⁻² at −0.6 V vs. reversible hydrogen electrode (RHE) for 1 mol% Cu doping. The obtained photocurrent is about 4.85 times higher than that of the pure α-Fe₂O₃ based photoelectrode. The incorporation of Cu into α-Fe₂O₃ results in a dramatic enhancement in the water splitting performance. The enhancement is gained through an improvement in light harvesting and charge carrier separation. The copper-modified α-Fe₂O₃ sample also exhibited an up shift in the conduction band edge potential, which is energetically favorable for the water reduction reaction. This result demonstrated high performance PEC water splitting as a potential route for the production of hydrogen gas using a single Cu-doped α-Fe₂O₃ photoelectrode without the need for other catalysts and hybrid structures.     

Flame synthesis of WO3 nanotubes and nanowires for efficient photoelectrochemical water-splitting

Tungsten trioxide (WO₃) is a technologically important material for photoelectrochemical (PEC) water-splitting for the solar production of hydrogen fuel from water. For PEC water-splitting, high aspect ratio WO₃ nanostructures such as nanowires (NWs) and nanotubes (NTs) are superior to planar WO₃ films because they orthogonalize the directions of light absorption (along the long axis) and charge transport (across the short radius), leading to both efficient light absorption and charge carrier collection. However, PEC water-splitting requires the growth of WO₃ on delicate transparent conducting oxide (TCO) substrates that cannot tolerate high temperature processing. To date, the large-scale, rapid, economical synthesis of high aspect ratio WO₃ nanostructures on these delicate TCO substrates remains a major challenge. Previously, we synthesized WO₃ NW arrays by a rapid, atmospheric and scalable flame vapor deposition (FVD) method, in which a flame oxidizes and evaporates tungsten metal to produce tungsten oxide vapors that condense onto a colder substrate in the form of NWs. Nevertheless, at substrate temperatures low enough to ensure the health of the TCO, the growth of WO₃ NW arrays was non-uniform and sparse due to limitations of the experimental design. Herein, we significantly improve the FVD design to grow uniform and densely packed WO₃ nanostructures on TCO substrates, thereby enabling the application of these WO₃ nanostructures to PEC water-splitting. The morphology of the nanostructures varied from densely packed multi-shell NTs and single-shell NTs to NWs as we increased the substrate temperature in the range 530–700 °C. Importantly, the WO₃ NTs synthesized by FVD had higher areal number density and longer length than state-of-the-art WO₃ NW photoanodes grown by chemical vapor deposition and hydrothermal methods, resulting in stronger light absorption and superior PEC water-splitting performance. Thus, in addition to being scalable, rapid and economical, the FVD method also synthesizes materials of high quality.     

Photoinduced deposition of gold nanoparticles on TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> nanotube films as efficient photoanodes for solar water splitting

Gold-modified TiO₂–WO₃ nanotubes with different amounts of gold were obtained by two methods; photoassisted deposition and one-step electrochemical anodizing method. The morphology, crystallinity and elemental composition were studied by FE-SEM, XRD and EDX. The photoelectrochemical performance was examined under Xe light illumination in 1 M NaOH electrolyte. Characterization of the as-prepared TiO₂–WO₃ samples indicated that sodium tungstate concentration in anodizing solution significantly influenced the morphology and photoelectrochemical activity of fabricated films. Also, photoelectrochemical characterizations show that the photocatalytic activity of Au/TiO₂–WO₃ nanotubes was improved as compared with that of bare TiO₂–WO₃ nanotubes. The experimental results showed that the photocatalytic activities of Au/TiO₂–WO₃ were significantly affected by the amount of Au nanoparticles. The amount of gold nanoparticles was effectively controlled by time of photoreduction of the chloroauric acid solution. These new photoanodes showed enhanced high photocurrent density with good stability and are a highly promising photoanodes for photocatalytic hydrogen production.     

Visible photocurrent response of TiO2 anode

The photoelectrochemical response to the electromagnetic radiation over the visible range is particularly sought for from the point of view of the efficiency of hydrogen generation by water photolysis in a photoelectrochemical solar cell, PEC. The PEC used in this work comprises thin film TiO₂ - based photoanode, Pt foil covered with Pt black as a cathode and SCE as a reference electrode, immersed in an electrolyte solution. Titanium dioxide thin films are deposited by means of rf reactive sputtering and modified, when necessary, by Au or Ag ultra-thin overcoatings. Here we show that even unmodified TiO₂ photoanode, shows a photocurrent peak over the visible range of the light spectrum (λ = 500-650 nm). The effect of the surface modification by noble metals and properties of the aqueous electrolyte on the visible photocurrent are studied. The optical spectra indicate an increased absorption due to noble metal deposits at 410 nm for Ag and at 600 nm for Au. In contrast, the photocurrent peak over the visible range (500 nm < λ < 650 nm) changes its symmetry and decreases in intensity with the increasing thickness of noble metals layers. The visible photoresponse is explained in terms of OH formation at the interface between TiO₂ electrode and aqueous electrolyte.     

Rapid sonochemical synthesis of irregular nanolaminar-like Bi2WO6 as efficient visible-light-active photocatalysts

Irregular Bi₂WO₆ nanolaminars have been successfully synthesized via a rapid sonochemical approach using bismuth nitrate and tungstic acid as precursors in an aqueous solution. The characteristics of them were investigated in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption, pore value, PL spectroscopy and UV–vis diffuse reflectance spectroscopy (UV–vis DRS). These irregular nanolaminars are of geometric shapes of orthorhombic Bi₂WO₆ with their basal plane being (0 0 1). They possess high crystallinity, lager surface area and pore value, which means fewer traps and stronger photocatalytic activity. The growth mechanism of such special nanolaminar was related to the sonochemical synthesis route, which played a key role in the formation of Bi₂WO₆ nanolaminar. Simultaneously, it was found that the formation of Bi₂WO₆ nanolaminar is a time dependent process. The Bi₂WO₆ nanolaminar has higher photocatalytic activity than bulk Bi₂WO₆ nanoparticle obtained by refluxing method for rhodamine B (Rh.B) degradation under visible light irradiation (λ > 400 nm).     

WS<Subscript>2</Subscript> layer formation on multi-walled carbon nanotubes

Time-dependent powder X-ray-diffraction analyses reveal that the conversion of WO₃ into WS₂ on carbon nanotube surfaces in the presence of H₂S is a one-step process. The WS₂ layers grow simultaneously along the tube in the radial and axial directions. Received: 17 June 2002 / Accepted: 19 June 2002 / Published online: 15 January 2003 RID="*" ID="*"Corresponding author. Fax: +44-1273/677-196, E-mail: d.walton@sussex.ac.uk     

Synthesis and characterization of TiO2 thin films coated on metal substrate

Nanostructured titanium dioxide (TiO₂) thin films have been prepared on metal substrates using a facile layer-by-layer dip-coating method. The phase structure and morphologies of preparing samples were characterized by means of X-ray powder diffraction (XRD) and field-emission scanning electron microscopy (FESEM). The results confirm that films are highly crystalline anatase TiO₂ and free from other phases of titanium dioxide. Scanning electron microscopy (SEM) shows that the nanoparticles are sintered together to form a compact structure. The electrical properties of samples were investigated by cutternt-voltage analysis, the result indicates that a rectifying junction between the nanocrystalline TiO₂ film and metal substrate was formed. The photoelectrochemical characteristics recorded under 1.5 AM illumination indicates that the as-fabricated thin film electrode possesses the highest photocurrent density at 450 °C, which is 1.75 mA/cm² at 0 V vs. Ag/AgCl.     

Facile fabrication of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Ag<Subscript>2</Subscript>S heterojunction with enhanced photoelectrochemical water splitting property

The α-Fe₂O₃/Ag₂S p-n heterojunction has been prepared via a facile room temperature successive ionic layer adsorption and reaction (SILAR) method. The heterojunction exhibits higher photoelectrochemical property compared to bare α-Fe₂O₃. The amount of Ag₂S has a significant effect on the PEC performance, which could be controlled by varying the number of SILAR cycles. The α-Fe₂O₃/Ag₂S p-n heterojunction prepared via 6 cycles of SILAR processes displays the best photoelectrochemical performance, which exhibits 1.8 times enhancement of photocurrent density and 70 mV cathodic shift of onset potential compared to bare α-Fe₂O₃. The improved PEC performance could be attributed to the formation of p-n junction between Ag₂S and α-Fe₂O₃, which not only enhanced the optical absorption ability, but also facilitated the separation efficiency of photogenerated charge carriers and passivized the surface state.     

Sonochemical fabrication of morpho-genetic TiO<Subscript>2</Subscript> with hierarchical structures for photocatalyst

Titanium oxides (TiO₂) with hierarchical structures have been successfully replicated from biotemplate using a sonochemical method. The bio-templates, cedarwoods, were irradiated under ultrasonic waves in TiCl₄ solutions and then calcined at temperatures between 450 and 600 °C. The fine replications of the biotemplates in TiO₂ down to nanometer’s level were verified using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The photocatalytic activities were assessed by measuring the percentage degradation of methylene blue using UV–vis spectroscopy. The calcination temperature has a strong effect on the structural replication and photocatalytic activity of the replicas. It appears that the calcination temperature of 450 °C results in the best structural replication with the highest surface area of 54.8 m² g⁻¹, and thus has the best photocatalytic properties. This method provides a simple, efficient, and versatile technique for fabricating TiO₂ with hierarchical structures, and it has the potential to be applied to other systems for producing functional hierarchical materials for chemical sensor and nanodevices.     

Scaling up the fabrication of wafer-scale Ni-MoS2/WS2 nanocomposite moulds using novel intermittent ultrasonic-assisted dual-bath micro-electroforming

In the scale-up fabrication process for electroformed Ni-MoS₂/WS₂ composite moulds, the formulation of nanosheets is critical, since the size, charge, and their distribution can largely affect the hardness, surface morphology and tribological properties of the moulds. Additionally, the long-term dispersion of hydrophobic MoS₂/WS₂ nanosheets in a nickel sulphamate solution is problematic. In this work, we studied the effect of ultrasonic power, processing time, surfactant types and concentrations on the properties of nanosheets to elaborate their dispersion mechanism and control their size and surface charge in divalent nickel electrolyte. The formulation of MoS₂/WS₂ nanosheets was optimized for effective electrodeposition along with nickel ions. A novel strategy of intermittent ultrasonication in the dual bath was proposed to resolve the problem of long-term dispersion, overheating, and deterioration of 2D material deposition under direct ultrasonication. Such strategy was then validated by electroforming 4-inch wafer-scale Ni-MoS₂/WS₂ nanocomposite moulds. The results indicated that the 2D materials were successfully co-deposited into composite moulds without any defects, along with the mould microhardness increasing by ∼2.8 times, the coefficient of friction reducing by two times against polymer materials, and the tool life increasing up to 8 times. This novel strategy will contribute to the industrial manufacturing of 2D material nanocomposites under ultrasonication process.     

Bi2MoO6纳米片/TiO2纳米棒阵列复合材料的制备及其可见光响应光电催化性能研究

Novel Bi₂MoO₆/TiO₂ heterojunction was fabricated by growing Bi₂MoO₆ nanosheets arrays on the vertically aligned TiO₂ nanorods arrays via a two-step solvothermal method. The obtained Bi₂MoO₆/TiO₂ hierarchical heterojunction showed excellent visible light photoelectrochemical performance. Compared with the pure TiO₂ and Bi₂MoO₆, the photocurrent density of the heterojunction was increased 57 and 29 times, respectively. Furthermore, the hydrogen generation rate of the Bi₂MoO₆/TiO₂ for photoelectrocatalytic water-splitting was about 6 times higher than that of the pure Bi₂MoO₆. The improved performance can be attributed to the synergistic effects of enhanced absorption of visible light, increase of migration rate and separation efficiency of photo-induced carriers.     

Synthesis and characterization of TiO2/Fe2O3 core-shell nanocomposition film and their photoelectrochemical property

TiO₂/Fe₂O₃ core-shell nanocomposition film has been fabricated via two-step method. TiO₂ nanorod arrays are synthesized by a facile hydrothermal method, and followed by Fe₂O₃ nanoparticles deposited on TiO₂ nanorod arrays through an ordinary chemical bath deposition. The phase structures, morphologies, particle size, chemical compositions of the composites have been characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and ultraviolet-visible (UV-vis) spectrophotometer. The results confirm that Fe₂O₃ nanoparticles of mean size ca. 10 nm coated on the surface of TiO2 NRs. After depositing Fe₂O₃, UV-vis absorption property is induces the shift to the visible-light range, the annealing temperature of 600 °C is the best condition for UV-vis absorption property of TiO₂/Fe₂O₃ nanocomposite film, and increasing Fe content, optical activity are enhanced one by one. The photoelectrochemical (PEC) performances of the as-prepared composite nanorods are determined by measuring the photo-generated currents under illumination of UV-vis light. The TiO₂ NRs modified by Fe₂O₃ show the photocurrent value of 1.36 mA/cm² at 0 V vs Ag/AgCl, which is higher than those of unmodified TiO₂ NRs.     

TiO<Subscript>2</Subscript> Nanorod Arrays Sensitized with CdS Quantum Dots for Solar Cell Applications: Effects of Rod Geometry on Photoelectrochemical Performance

CdS quantum dot (QD) sensitized TiO₂ nanorod array (NRA) film electrodes with different rod geometries were fabricated via a solvothermal route followed by a sequentialchemical bath deposition (S-CBD) process. By controlling the solution growth conditions, the rod geometries, especially the tip structures, of the TiO₂ NRAs were tuned. The results indicated that the vertically aligned hierarchical NRAs possessed conically shaped tip geometry, which was favorable for film electrodes due to the reduced reflectance, enhanced light harvesting, fast charge-carrier separation and transfer, suppression of carrier recombination, sufficient electrolyte penetration and subsequent efficient QD assembly. CdS QD sensitized TiO₂ NRA film electrodes with tapered tips exhibited an enhanced photoelectrochemical (PEC) performance, a photocurrent intensity of 5.13 mA/cm² at a potential of 0 V vs. saturated calomel electrode, an open-circuit potential of −0.68 V vs. saturated calomel electrode and an incident photon to current conversion efficiency (IPCE) of 22% in the visible-light region from 400 to 500 nm. The effects of rod geometry on the optical absorption, reflectance, hydrophilic properties and PEC performance of bare TiO₂ and CdS QD sensitized TiO₂ NRA film electrodes were investigated. The mechanism of charge-carrier generation and transfer in these CdS QD sensitized solar cells based on vertically aligned TiO₂ nanorods is discussed.     

Free-standing WS<Subscript>2</Subscript><Emphasis Type="Strikethrough">-</Emphasis>MWCNTs hybrid paper integrated with polyaniline for high-performance flexible supercapacitor

As two-dimensional layered nanomaterials, the tungsten disulfide (WS₂) nanosheets can be used as building blocks of paper-like electrodes for high-performance FSs. However, poor conductivity and mechanical property of WS₂ nanosheets (NSs) paper greatly hinders their capacitance and/or rate performance. To solve these problems, we fabricated the WS₂-multiwalled carbon nanotubes (MWCNTs)/polyaniline (PANI) composite papers based on liquid exfoliation and electrochemical deposition for high-performance flexible supercapacitors. The WS₂-MWCNTs/PANI with conductive PANI chains linked WS₂ NSs and MWCNTs takes the advantages of high-electronic double-layer capacitance originated from the internal surface areas of MWCNTs and effective pseudocapacitance generated by exfoliated WS₂ NSs and PANI. Electrochemical studies showed that the gravimetric-specific capacitance of WS₂-MWCNTs/PANI can reach ~760.1 F/g at a current density of 1 A/g. A symmetric flexible solid-state supercapacitor was also assembled and studied. The WS₂-MWCNTs/PANI-assembled FS device also has an excellent area specific capacitance of 1158.7 mF/cm² at a current density of 0.5 mA/cm² together with a high-capacity retention of ~82.5% after 2000 cycles.     

Density functional theory study of NO2-sensing mechanisms of pure and Ti-dopedWO3 （002） surfaces

Density functional theory (DFT) calculations are employed to explore the NO₂-sensing mechanisms of pure and Ti-doped WO₃ (002) surfaces. When Ti is doped into the WO₃ surface, two substitution models are considered: substitution of Ti for W_6c and substitution of Ti for W_5c. The results reveal that substitution of Ti for 5-fold W forms a stable doping structure, and doping induces some new electronic states in the band gap, which may lead to changes in the surface properties. Four top adsorption models of NO₂ on pure and Ti-doped WO₃ (002) surfaces are investigated: adsorptions on 5-fold W (Ti), on 6-fold W, on bridging oxygen, and on plane oxygen. The most stable and likely NO₂ adsorption structures are both N-end oriented to the surface bridge oxygen O_1c site. By comparing the adsorption energy and the electronic population, it is found that Ti doping can enhance the adsorption of NO₂, which theoretically proves the experimental observation that Ti doping can greatly increase the WO₃ gas sensor sensitivity to NO₂ gas.     

Effects of annealing temperature on GO–Cu2O composite films grown by electrochemical deposition for PEC photoelectrode

In this work, graphene oxide–cuprous oxide (GO–Cu₂O) composite films were grown on fluorine-doped tin oxide substrates by electrochemical deposition. We investigated the effects of the annealing temperature on the morphological, structural, optical and photoelectrochemical (PEC) properties of GO–Cu₂O composite films. As a result, our work shows that while GO–Cu₂O composite films exhibit the highest XRD (111) peak intensity at 300 °C sample, the highest photocurrent density value obtained was −4.75 mA/cm² at 200 °C sample (using 0.17 V versus a reversible hydrogen electrode (RHE)). In addition, a reduction reaction at 300 °C sample was observed using XPS analysis from the shift in the O1s peak in addition to a weaker O1s peak intensity.