Ag grid induced photocurrent enhancement in WO3 photoanodes and their scale-up performance toward photoelectrochemical H2 generation

The hydrogen generation from photoelectrochemical (PEC) water splitting under visible light was investigated using large area tungsten oxide (WO₃) photoanodes. The photoanodes for PEC hydrogen generation were prepared by screen printing WO₃ films having typical active areas of 0.36, 4.8 and 130 cm² onto the conducting fluorine-doped tin oxide (FTO) substrates with and without embedded inter-connected Ag grid lines. TiO₂ based dye-sensitized solar cell was also fabricated to provide the required external bias to the photoanodes for water splitting. The structural and morphological properties of the WO₃ films were studied before scaling up the area of photoanodes. The screen printed WO₃ film sintered at 500 °C for 30 min crystallized in a monoclinic crystal structure, which is the most useful phase for water splitting. Such WO₃ film revealed nanocrystalline and porous morphology with grain size of ∼70-90 nm. WO₃ photoanode coated on Ag grid embedded FTO substrate exhibited almost two-fold degree of photocurrent density enhancement than that on bare FTO substrate under 1 SUN illumination in 0.5 M H₂SO₄ electrolyte. With such enhancement, the calculated solar-to-hydrogen conversion efficiencies under 1 SUN were 3.24% and ∼2% at 1.23 V for small (0.36 cm²) and large (4.8 cm²) area WO₃ photoanodes, respectively. The rate of hydrogen generation for large area photoanode (130.56 cm²) was 3 mL/min.     

2D/3D WO3/BiVO4 heterostructures for efficient photoelectrocatalytic water splitting

Developing novel photoanodes with high efficiency for photoelectrochemical (PEC) water splitting has become the key to solar energy conversion and storage realm. Herein, 3D worm-like bismuth vanadate (BiVO₄) is grafted on 2D thin tungsten trioxide (WO₃) underlayer by electrodeposition to form mixed–dimensional structured photoanode, resulting in significant improvement of the photocatalytic performance and the charge separation efficiency. Characterization results prove that the mixed–dimensional structured can boost the photocatalytic activity by suppressing back reaction and charge recombination of the bulk BiVO₄. Simultaneously, the electrical conductivity of photoanode can be increased by W⁶⁺ doping. Furthermore, a robust catalyst NiCo₂O_x is coated onto the surface of WO₃/BiVO₄ photoanode, exhibiting a desirable photocurrent of 3.85 mA cm^?2 at 1.23 V vs. RHE and an excellent stability over 3 h. Both the excellent photocurrent density and great operational stability of this 2D/3D WO₃/BiVO₄ photoanode make it a promising material for practical applications.     

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.     

First demonstration of photoelectrochemical water splitting by commercial W–Cu powder metallurgy parts converted to highly porous 3D WO3/W skeletons

Hydrogen evolution through photoelectrochemical (PEC) water splitting by tungsten oxide-based photoanodes, as a stable and environmental-friendly material with moderate band gap, has attracted significant interest in recent years. The performance of WO₃ photoanode could be hindered by its poor oxygen evolution reaction kinetics and high charge carrier recombination rate. Additionally, scalable and cost-effective commercial procedure to prepare nanostructured electrodes is still challenging. We present, for the first time, a novel and scalable method to fabricate highly efficient self-supported WO₃/W nanostructured photoanodes from commercial W–Cu powder metallurgy (P/M) parts for water splitting. The electrodes were prepared by electrochemical etching of Cu networks followed by hydrothermal growth of WO₃ nanoflakes. Interconnected channels of W skeleton provided high active surface area for the growth of WO₃ nanoflakes with a thickness of ~40 nm and lateral dimension of ~250 nm. The optimized photoelectrode having 35% interconnected porosity exhibited an impressive current density of 4.36 mA cm⁻² comprising a remarkable photocurrent of 1.71 mA cm⁻² at 1.23 V vs. RHE under 100 mW cm⁻² simulated sunlight. This achievement is amongst the highest reported photocurrents for WO₃ photoelectrodes with tungsten substrate reported so far. Impedance and Mott-Schottky analyses evidenced fast charge transfer, low recombination rate, and accelerated O₂ detachment provided by optimum 3D porous WO₃/W electrode. Due to the nature of the commercial P/M parts and low-temperature hydrothermal processing, the procedure is cost-effective and scalable which can pave a new route for the fabrication of highly porous and efficient water splitting electrodes.     

Nitrogen-doped carbon dot anchored 1-D WO3 for enhanced solar water splitting: A nano surface imaging evidence of charge separation and accumulation

Combining WO₃ with suitable materials to form heterojunction is essential to overcome the limitations of WO₃ to enhance its photoelectrochemical (PEC) water splitting activity. Moreover, a clear understanding of photo-response and charge behavior of materials could lead to the rational design of efficient photoelectrodes. Given this, an efficient strategy is applied to fabricate WO₃ heterojunction with nitrogen-doped carbon dots (NCDs) and in-depth characterization to investigate the surface charge dynamics using nano imaging in a relation to the enhanced PEC water splitting activity. The optimized NCDs loading to the WO₃ NRs exhibited the enhanced photocurrent density of 1.54 mA cm⁻² at 1.23V vs RHE under AM 1.5 G illumination, highest IPCE of ~82 % (at 308.32 nm). The Kelvin probe force microscopy and electrostatic force microscopy reveal that after loading NCDs to the WO₃, a relatively smooth charge transport has been observed, which improves the PEC. Furthermore, this work demonstrates the effect of photogenerated charges caused by the NCDs that assist in enhancing the increased photocurrent, hydrogen production efficiency, and stability of the PEC water splitting system. Significantly, the nano imaging characterization utilized in this work could be extended to various photoanodes to study the surface charge dynamics.     

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.     

Photoelectrochemical hydrogen generation with nanostructured CdS/Ti–Ni–O composite photoanode

Composite photocatalysts have aroused great interest due to combination of favorable electronic and optical properties. Herein, novel CdS/Ti–Ni–O composite photoanodes were constructed through anodic fabrication of nanostructured Ni-doped TiO₂ (Ti–Ni–O) oxide films and CdS deposition by successive ionic layer adsorption and reaction (SILAR). The morphology and composition evolution, optical properties and photoelectrochemical (PEC) performance of the photoanodes were investigated. The composite nanofilms mainly consisted of micropores and nanotubes. The CdS/Ti–Ni–O composite photoanode demonstrated remarkable PEC hydrogen generation properties with a high photocurrent density (6.72 mA·cm^?2 at 0 V vs Ag/AgCl) which was 18.2 times to that of the bare Ti–Ni–O photoanode. The synergy of Ni-doping and CdS-coupling on the enhancement of PEC performance offers useful ideas to the exploitation of effective photocatalysts and contributes to the development of solar-driven PEC hydrogen generation.     

Photodeposited CoOx as highly active phases to boost water oxidation on BiVO4/WO3 photoanode

Surface decoration of photoanodes with oxygen evolution cocatalysts is an efficient approach to improve the photoelectrochemical water splitting performance. Herein, ultrafine CoO_x was selectively immobilized on the surface of BiVO₄/WO₃ photoanode by using the photogenerated holes to in-situ oxidize Co₄O₄ cubane. The composited photoanode (CoO_x/BiVO₄/WO₃) displayed an enhanced photoelectrochemical (PEC) water oxidation performance, with a photocurrent density of 2.3 mA/cm² at 1.23 V_RHE under the simulated sunlight irradiation, which was 2 times higher than that of bare BiVO₄/WO₃. The characterization results for the morphological, optical and electrochemical properties of the photoelectrodes revealed that, the enhanced PEC performances could be attributed to the improved charge carrier separation/transport behaviors and the promoted water oxidation kinetics when the photoelectrodes were loaded with CoO_x.     

Bi2S3 entrenched BiVO4/WO3 multidimensional triadic photoanode for enhanced photoelectrochemical hydrogen evolution applications

The catalytic reactivity and photoactivity of WO₃ and BiVO₄ oxide semiconductors have general obstacles as electrodes in emergent photo-electrochemical (PEC) hydrogen evolution applications. The present work comprises the integration of photocatalyst with wide visible photon absorption material which is vital for hydrogen evolution in photo-electrocatalytic water splitting. Herein, the 1D WO₃ NWs have been integrated with stable water oxidation photocatalysts of BiVO₄ and Bi₂S₃ as a photoanode (Bi₂S₃/BiVO₄/WO₃) for photoelectrochemical hydrogen evolution reactions. The morphological variations in the Bi₂S₃/BiVO₄/WO₃ heterostructure manifest catalytic activity and rapid charge transfer characteristics owing to band alignment and a wide range of visible photon absorption. The optimized Bi₂S₃/BiVO₄/WO₃ multidimensional photoanode accomplishes a superior photocurrent density of 1.52 mA/cm², a seven-fold higher than pristine WO₃ photoanode counterpart (0.2 mA/cm²) at 1 V vs. RHE. A prodigious lowest onset potential of ?0.01 V vs. RHE) has been achieved which enables very high solar to hydrogen conversion. The photoelectrode with entangled morphology such as nanosheets, nanocrystals and nanorods expanded their surface to volume ratio having enhanced catalytic performance. The hybrid photoanodes have demonstrated the lowest charge transfer resistance of 360 Ohm/cm² with a 7-fold rise in hydrogen evolution performance. The resultant triadic Bi₂S₃/BiVO₄/WO₃ heterostructure appeared to be an emerging stable photo-electro catalyst for hydrogen evolution applications.     

Fabrication of large area nanorod like structured CdS photoanode for solar H2 generation using spray pyrolysis technique

Large area nanorod like structured CdS films (9 × 9 cm²) were deposited on the FTO glass substrate using simple and economic spray pyrolysis deposition technique for photoelectrochemical (PEC) hydrogen production. With an intention of electrode scaling-up, the deposition area of photoanode was varied to evaluate its effect on the PEC hydrogen generation capability. High photocurrent of 5 mA has been achieved from the PEC active area of 37.5 cm². Its unit area (1 cm²) counterpart yielded Solar-to-Hydrogen (STH) conversion efficiency of 0.20% at a bias of 0.2 V vs Ag/AgCl using sacrificial reagents under solar simulator (AM1.5) with 80 mW/cm² irradiance. The 500 nm thick film exhibiting uniformly distributed nano-rod features yielded 3-times more photocurrent, as well as hydrogen evolution than other films. It exhibited an enhanced photo-activity as indicated by the higher IPCE values (5–9%) in the wavelength range of 450–550 nm. It exhibited superior optical properties (E_g ∼2.4 eV), and formation of high crystallinity hexagonal CdS phase with space group P63MC. The superior performance of the photoanode is attributed to the nanostructured morphology acquired under optimized spray pyrolysis conditions. Large area photoanodes showed unaltered photo-activity indicating the homogeneity in the film properties even in scaled-up version.     

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.     

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.     

Recent trends in development of hematite (α-Fe2O3) as an efficient photoanode for enhancement of photoelectrochemical hydrogen production by solar water splitting

Solar-assisted water splitting using photoelectrochemical (PEC) cell is an environmentally benign technology for the generation of hydrogen fuel. However, several limitations of the materials used in fabrication of PEC cell have considerably hindered its efficiency. Extensive efforts have been made to enhance the efficiency and reduce the hydrogen generation cost using PEC cells. Photoelectrodes that are stable, efficient and made of cost-effective materials with simple synthesizing methods are essential for commercially viable solar water splitting through PEC technology. To this end, hematite (α-Fe₂O₃) has been explored as an excellent photoanode material to be used in the application of PEC water oxidation owing to its suitable bandgap of 2.1 eV that can utilize almost 40% of the visible light. In this study, we have summarized the recent progress of α-Fe₂O₃ nanostructured thin films for improving the water oxidation. Strategic modifications of α-Fe₂O₃ photoanodes comprising nanostructuring, heterojunctions, surface treatment, elemental doping, and nanocomposites are highlighted and discussed. Some prospects related to the challenges and research in this innovative research area are also provided as a guiding layout in building design principles for the improvement of α-Fe₂O₃ photoanodes in photoelectrochemical water oxidation to solve the increasing environmental issues and energy crises.     

Boosting the performance of hematite photoanodes for solar water oxidation by synergistic W-incorporation and Zr-passivation

Incorporating impurities into hematite is an effective approach to enhance the photoelectrochemical (PEC) water splitting performance of hematite photoanode. Here, we report an efficient W-incorporation in hematite (W-Fe₂O₃) to enhance the PEC performance by depositing a WO₃ underlayer onto the FTO substrate. The W-incorporation dramatically enhances the photocurrent density of hematite by a factor of ∼2. Moreover, it can be well coupled with Zr to achieve a high photocurrent of 2.0 mA cm⁻² at 1.23 V vs. RHE by simultaneously depositing a ZrO₂ underlayer on the FTO substrate. A large cathodic shift of the onset potential up to 120 mV can also be obtained. The boosted PEC performance can be attributed to the synergistic effect of W and Zr in hematite, which can both improve the carrier density (by W-incorporation) and suppress the charge recombination (by Zr-passivation).     

Improved photon management in a photoelectrochemical cell with Nd-modified TiO2 thin film photoanode

Photon management involving particularly an up-conversion process is proposed as a relatively novel strategy for improving the efficiency of hydrogen generation in photoelectrochemical cells (PEC) with wide-band gap photoanodes. Optically active photoanode has been constructed by electrodeposition of titanium dioxide nanopowders containing Nd³⁺ ions, synthesized via a sol-gel method, onto ITO/TiO₂(thin film) substrates. Thin films of TiO₂ have been deposited by means of RF magnetron sputtering in an ultra-high-vacuum system. X-ray diffraction, scanning electron microscopy, UV-VIS-NIR spectrophotometry, and photoluminescence have been applied to assess the properties of photoanodes. In experiments involving photon-assisted water splitting, an external up-converter containing Yb³⁺/Er³⁺ rare-earth ions has been used. Photocurrent as a function of voltage (V_B) under illumination with white light is relatively high (280 μA at V_B = 0 V) for pure TiO₂ thin films and it is not affected by the electrodeposition of TiO₂:Nd³⁺ powders. NIR-driven up-conversion with laser excitation at λ = 980 nm has been found responsible for a 13-fold increase in photocurrent at V_B = 0 V in the modified PEC configuration.     

Piezoelectric polarization assisted WO3/CdS photoanode improved carrier separation efficiency via CdS phase regulation

The key factor for efficient photoelectrochemical (PEC) water splitting is to design a semiconductor as photoanode with high carrier separation. Piezoelectric polarization is a considerable method to improve the carriers separation efficiency via providing a powerful built-in electric field. Herein, we synthesized WO₃/CdS type II heterojunction and firstly explored the influence of CdS phase transition from sphalerite β-CdS to wurtzite α-CdS on piezoelectric polarization for WO₃/CdS. Benefited from the asymmetric structure of α-CdS, fluctuation swings can be seen in the LSV curves of WO₃/α-CdS due to piezoelectric polarization under ultrasound. The photocurrent density of WO₃/α-CdS are enhanced with the increase of ultrasound frequency and the maximum of 2.13 mA/cm² at 1.23 V vs. RHE, which is 1.61 times before ultrasound. The outstanding PEC performances of WO₃/α-CdS under ultrasonic conditions are contributed to carrier separation driven by enhancing internal electric field between heterojunction, the built-in electric field inside the α-CdS and ballast carriers participating in water splitting reaction. This work provides a promising strategy for improving carrier separation efficiency in photoelectrodes via piezoelectric polarization.     

Fast and low-cost fabrication of 1D hematite photoanode in pure water vapor and air atmosphere: Investigation the effect of the oxidation atmosphere on the PEC performance of the hematite photoanodes

In this study, hematite photoanodes were successfully fabricated by thermal oxidation of the commercial cold-rolled steel at 500 °C in pure water vapor and air atmosphere. The crystal phase structure, surface morphology, and optical properties of the hematite photoanodes were characterized using an X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM) and UV–VIS spectrophotometer, respectively. The results showed that hematite photoanodes had high crystalline phase and the annealing atmosphere influenced the morphology of the hematite photoanodes. Moreover, nanowhisker and nanorod shaped nanostructures were observed on the substrate. The optical band gap values of the hematite photoanodes varied between 2.38 and 2.70 eV. Photoelectrochemical (PEC) studies of the hematite photoanodes were assessed in the 0.1 M NaOH electrolyte solution using the Mott–Schottky analysis and electrochemical impedance spectroscopy techniques. The PEC findings exhibited that the hematite photoanode annealed 15-min in water vapor had best PEC performance achieving photocurrent density 0.244 mA/cm² at 1.6 V vs. V_RHE and highest carrier density value (N_D = 1.15 × 10²¹ cm^?3). Furthermore, the photoanodes annealed in water vapor atmosphere revealed at least three times higher PEC performance than that of photoanodes annealed in air. Thermal oxidation method in water vapor is an efficient methods for fabrication of hematite photoanodes.     

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.     

Photoanode of LDH catalyst decorated semiconductor heterojunction of BiVO4/CdS to enhance PEC water splitting efficiency

BiVO₄ is an ideal photoanode material for solar-driven photoelectrochemical (PEC) water splitting but it easily suffers from the recombination of photogenerated electrons and holes due to its low carrier mobility thus cause low efficiency of PEC water splitting. Herein, the BiVO₄/CdS/NiCo-LDH photoanode was prepared by combining methods of metal organic decomposition, chemical and electrodeposition. The photoanode photocurrent density reaches 2.72 mA cm⁻² at 1.23 V (vs. RHE), which is 3.6 folds of pure BiVO₄ photoanode and onset potential shifts 450 mV toward cathodic. The incident photon-to-electron conversion efficiency (IPCE) value is 2.86 folds of BiVO₄, the calculated photon–to–current efficiency (ABPE) is 1.24% at 0.62 V (vs. RHE). The obtained results are higher than that of most BiVO₄ based photoanodes published so far. The enhancement benefits from increase of visible light absorption capacity, enhancement of separation efficiency of photoexcited electron-hole and fast transfer of holes accumulated on electrode/electrolyte surface for water oxidation, which has been confirmed by calculating carrier density and carrier transport rate.