Construction of ZnO@NiO heterostructure photoelectrodes for improved photoelectrochemical performance

In this report, a p-n junction has been constructed using ZnO/NiO heterostructured photoelectrode by spin coating NiO layers over vertically aligned ZnO nanorod arrays to demonstrate its potential in water splitting applications. Before investigating their PEC performance, we thoroughly studied the introduction of NiO layers on the structure, morphology and light absorption property of ZnO nanorods. 9 layered NiO coated ZnO nanorods exhibited optimum photocurrent density of 0.251 mA/cm² at 0.8 V vs. Ag/AgCl which is attributed to its high absorbance and better charge transfer as recorded from UV–Vis and EIS data. Furthermore, we also studied the effect of (cation (Mg) and anion (Cl)) doping in PEC performance of ZnO nanorods on this optimized sample. Cl_ZnO/NiO showed high J_ph of 1.282 mA/cm² at 1.2 V vs. Ag/AgCl under visible light illumination. The reason behind better photoresponse is its enhanced absorption and well-defined p-n heterojunction between Cl_ZnO and NiO which favoured the separation and transfer of the photocarriers. The results displayed in this work provides a suitable approach of building p-n junction for high performance PEC water oxidation.     

Hierarchically self-assembled ZnO architectures: Establishing light trapping networks for effective photoelectrochemical water splitting

Here we develop photoanodes based on hierarchical zinc oxide (ZnO) nanostructures such as vertically aligned nanorods (NR), nanorods interconnected by thin nanosheets (NR@TN) and nanorods interconnected by dense nanosheets (NR@DN). The morphological variations were successfully controlled by secondary growth time and the plausible formation mechanisms of these hierarchical ZnO architectures were explained based on the experiment analysis. Under simulated light illumination (AM 1.5, 100 mW cm^?2), NR@TN produced a photocurrent density of 0.62 mA/cm² at 1.23 V vs. reversible hydrogen electrode (vs. RHE). Importantly, 35% enrichment in photoconversion efficiency was observed for NR@TN at much lower bias potential (0.77 V vs. RHE) compared with NR (0.135%) and NR@DN (0.13% at 0.82 V vs. RHE). Key to the improved performance is believed to be synergetic effects of excellent light-trapping characteristics and the large surface-to-volume ratios due to the nanosheet structures. The nanorod connected with thin nanosheet structures improved the efficiency by means of improved charge transfer across the nanostructure/electrolyte interfaces, and efficient charge transport within the material. We believe that the hierarchical ZnO structures can be used in conjunction with doping and/or sensitization to promote the photoelectrochemical (PEC) performance. Further, the ZnO nanorod interconnected with nanosheets morphology presented in this article is extendable to other metal oxide semiconductors to establish a universal protocol for the development of high performance photoanodes in the field of PEC water splitting.     

Ge-doped ZnO nanorods grown on FTO for photoelectrochemical water splitting with exceptional photoconversion efficiency

In this study, a considerable effort has been devoted for the synthesis of Ge-doped ZnO nanorods on FTO as an efficient and robust photoanode material for solar water splitting. A unique, optimized, and ultra-rapid fabrication method to produce uniform nanorods (30–70 nm in diameter) has been demonstrated using radio frequency sputtering followed by electrochemical anodization. The effect of Ge doping on the conductivity, charge carrier concentration, optical, and photoelectrochemical properties of ZnO was investigated using scanning electron microscope (SEM), glancing angle X-ray diffraction (GAXRD), UV–Vis spectrometer, and Mott Schottky analysis. Glancing angle XRD confirmed the presence of wurtzite structure with a preferable orientation around (101) plane, which is of particular interest for many applications. As evidenced by the photoelectrochemical and transient photocurrent measurements, the fabricated Ge-doped ZnO nanorods exhibited enhanced photocurrent (12 mA/cm²) with an exceptional open circuit voltage of ?1.07 V_SCE (?0.416 V_RHE) under AM1.5G illumination, compared to the undoped ZnO based-photoanodes. Moreover, the Ge-doped ZnO nanorods showed unprecedented photoconversion efficiency of 3.6% under AM1.5G illumination. Therefore, the fabricated Ge-doped ZnO nanorods could be a promising conductive photoanode for water splitting.     

ZnO/Cu2O-decorated rGO: Heterojunction photoelectrode with improved solar water splitting performance

In present work, we report a facile fabrication process to improve the photoelectrochemical (PEC) performance of ZnO-based photoelectrodes. In order to achieve that, the Cu₂O nanocubes are cathodic-deposited on the as-prepared ZnO nanorods. Then rGO nanosheets are electrodeposited on the ZnO/Cu₂O heterostructures. The fabricated photoelectrodes are systematically studied in detail by different characterization techniques such as powder X-ray diffraction, micro-Raman, X-ray photoelectron spectroscopy, ultraviolet diffused reflectance spectroscopy and photoluminescence spectroscopy analysis. Morphologies of the fabricated photoelectrodes are investigated through electron microscopy in scanning and transmission mode. To evaluate the PEC performance of the fabricated photoelectrodes, the line scan voltammetry (LSV) measurement is performed using a three-electrode system in 0.5-M Na₂SO₄ electrolyte solution under stimulated light illumination at 100 mW/cm² from a 300-W Xenon Arc lamp coupled with an AM 1.5G filter using a three-electrode system. The photocurrent measurement demonstrates that the photoelectrodes based on ZnO/Cu₂O/rGO possess enhanced PEC performance compared to the pristine ZnO and ZnO/Cu₂O photoelectrodes. The photocurrent density of ZnO/Cu₂O/rGO-15 photoelectrode (10.11 mA/cm²) is ∼9 and ∼3 times higher than the photoelectrodes based on pristine ZnO (1.06 mA/cm²) and ZnO/Cu₂O (3.22 mA/cm²). The enhanced PEC performance of ZnO/Cu₂O/rGO photoelectrode is attributed to the excellent light absorption properties of Cu₂O and excellent catalytic and charge transport properties of rGO. Experimental results reveal that the proposed functional nanomaterials have a great potential in water splitting applications.     

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.     

Photoelectrochemical water splitting at nanostructured α-Fe2O3 electrodes

In this study, nanostructured α-Fe₂O₃ thin films were deposited by simple electrodeposition for photoelectrochemical water splitting. Post-annealing temperature was found to have drastic effect on photoactivity of these films. SEM analysis illustrated that size of nanoparticles increases with annealing temperature. The current–potential characteristics showed that the water-splitting photocurrent strongly depends on post-annealing temperature. A maximum photocurrent density of 0.67 mA/cm² was observed at 1.23 V versus reversible hydrogen electrode (RHE) under standard illumination conditions (AM 1.5 G 100 mW/cm²), and the water-splitting current was over 1.0 mA/cm² before the dark current flow starts (at 1.55 V versus RHE). The electrode shows an onset potential as low as 0.8 V (versus RHE) for water photooxidation, which is one of the best results reported for hematite photoanodes. This high photoactivity of electrodes is attributed to the preferential growth of hematite nanostructures along the most conductive plane (001) and incorporation of Sn in film from the substrate at high annealing temperature. The best-performing electrode shows an incident photon conversion efficiency (IPCE) of 12% at 400 nm (in 1 M NaOH at 1.23 V versus RHE), which indicate the improved light-harvesting properties of these nanostructures.     

Carbon fiber supported Co/Co3O4-embedded N-doped carbon microparticles for efficient overall seawater splitting and oxygen reduction

Due to low cost and abundance, direct seawater splitting to produce hydrogen is an encouraging strategy to alleviate the consumption of fossil energy, while also avoiding freshwater stress. However, when natural seawater is utilized as the electrolyte, the catalysts on the cathode and anode of water splitting should not only have high activity to promote energy efficiency, but also have good stability and durability to resist the corrosion of chloride ions. Herein, a hierarchical carbon-based catalyst for hydrogen and oxygen evolution, ZIF-67/CF-1, was prepared by annealing a composite of ZIF-67 and carbon fiber (CF). It exhibits good electrocatalytic activity and stability for overall splitting in natural seawater and neutral PBS solution. Impressively, when an electrolyzer consisting of ZIF-67/CF-1||ZIF-67/CF-1 is applied to overall seawater splitting, the current density of 10 mA/cm² is achieved with a drive voltage of 2.46 V, which is only 0.28 V higher than precious metal-based electrolyzer (Pt/C||IrO₂). Meanwhile, ZIF-67/CF-1 shows outstanding catalytic ability for oxygen reduction (E_1/2 = 0.84 V, Tafel slope = 66.9 mV/dec), also demonstrating its application potential in rechargeable batteries and fuel cells.     

Mixed-metal organic framework-coated ZnO nanowires array for efficient photoelectrochemical water oxidation

Designing of high-performance photoanodes is essential for efficient solar energy conversion in photoelectrochemical (PEC) water splitting. Herein, we report an effective approach to synthesize three dimensional (3D) mixed-metal organic framework-coated ZnO nanowires array (ZnNi MOF@ZnO) for the effective PEC performance. The ZnO nanowires act as photon absorber as well as rapid charge transporter; whilst the ZnNi MOF provides the active sites for PEC process by lowering the energy barrier of water oxidation and suppressing electron-hole recombination. The 3D nanostructure of ZnNi MOF@ZnO nanowires array provides intimate interfacial contact through covalent interactions between the ZnNi MOF and ZnO nanowires which facilitates the rapid charge transfer during photocatalytic oxygen evolution reactions. As a result, the ZnNi MOF@ZnO nanowires array exhibited excellent photoelectrochemical water oxidation with very low onset potential (0.31 V vs. RHE) and high photocurrent density (1.40 mA/cm²) as compared to the Zn MOF @ZnO and ZnO nanowires array. This facile strategy provides a promising direction towards high performance photoanode design for adequate solar energy conversion.     

Seed-layer-free deposition of well-oriented ZnO nanorods thin films by SILAR and their photoelectrochemical studies

Morphological forms of ZnO nanostructures play a vital role in deciding properties such as high internal surface area, efficient light scattering and harvesting, lowest charge transfer resistance, etc. which are important for photoelectrochemical (PEC) performance. Herein successful deposition of well oriented ZnO nanorods thin films over fluorine doped tin oxide (FTO) coated glass substrate is achieved by using simple, soft solution and scalable method known as successive ionic layer adsorption and reaction (SILAR). For the first time a compact ZnO layer over large area is deposited in one step synthesis approach, without any assistance of seed layer, by using hydrazine hydrate as a source of hydroxyl ions. The plausible growth mechanism of the morphological variation (alignment and orientation) happening with increasing SILAR cycles and its consequence on PEC performance are discussed in detail. All ZnO thin films show wurtzite crystal structure, however variations in their texture coefficients were found with SILAR cycles, which turns out to be a major aspect for PEC application. Anodic shift was observed in flat band potential values with increment in number of SILAR cycles. The ZnO thin films deposited for 120 cycles showed preferential orientation along (0002) plane and showed better PEC performance with photocurrent of 0.19 mA/cm² (1 V) and maximum photo conversion efficiency of 0.084% at 0.45 V. On the other hand, film deposited for 60 (photocurrent of 0.11 mA/cm² (1 V); efficiency of 0.055%) and 180 cycles (photocurrent of 0.15 mA/cm² (1 V); efficiency of 0.063%) demonstrated inferior PEC performance.     

Effect of oxygen concentration and distribution on holes transfer and photoelectrocatalytic properties in hematite

The holes transfer efficiency is a key issue in the process of photoelectrocatalytic water splitting. Here, we found that the oxygen concentration and distribution in hematite evidently affected the bulk and surface holes transfer, and thus influenced the performance of photoelectrocatalytic water splitting. Two macro-changes on oxygen were observed during the thermal treatment. The first-stage led to a lower bulk O/Fe ratio of only 1/1 and the generation of adsorbed oxygen, obtaining porous nanorods (NRs) with a ~1.4 nm FeO_x layer. Bulk charge recombination centers and surface deep traps caused a lower bulk and surface charge transfer. The second-stage led to a bulk O/Fe ratio of nearly 3/2 and single high crystallization NRs. Major increases in charge transfer constant from 0.27 to 4.5 s^?1 and in photocurrent density (vs.1.23 V_RHE) from 0.0235 to 1.20 mA/cm² were observed, which demonstrates the higher holes transfer efficiency. Furthermore, the connection of oxygen migration and charge transfer was derived. This work could provide effective guidance for further optimization of semiconductor photoanodes.     

Polyoxometalate@ZIF-67 derived carbon-based catalyst for efficient electrochemical overall seawater splitting and oxygen reduction

Electrochemical water splitting, metal-air batteries and fuel cells are the representatives of energy storage/conversion technology, which can solve the shortage of traditional fossil energy and environmental issues. However, under neutral conditions, especially in natural seawater, there is still a lack of catalysts with efficient catalytic activity and stability, which hinders the development of hydrogen production. We herein designed a facile strategy to fabricate an efficient and stable multifunctional carbon-based electrocatalyst, PMA@ZIF-67-C-AT, by carbonization and acid treatment of H₃PMo₁₂O₄₀@ZIF-67 precursor. It not only performs good catalytic activity for oxygen evolution in 0.2 M phosphate buffer solution (PBS) and actual seawater, but also exhibits hydrogen evolution overpotential of 650 mV (j = 3 mA/cm²) in PBS and even as low as 570 mV (j = 10 mA/cm²) in seawater. Besides, it also displays excellent catalytic performance for oxygen reduction (E_1/2 at 0.83 V and the Tafel slope of 63 mV/dec). By investigating the composition and morphology of the materials, it was found that acid treatment changed the active components and carbon matrix of the catalysts, thus affecting the catalytic performance.     

Overall noble metal free Ni and Fe doped Cu2ZnSnS4 (CZTS) bifunctional electrocatalytic systems for enhanced water splitting reactions

Herein, we report an inexpensive synthesis of sonochemical nickel and iron (M = Ni, Fe) doped Cu₂ZnSnS₄ (CZTS) and their utility as a nanoelectrodes for improved electrocatalytic water splitting performance. The as-synthesized electrode materials were characterized further by Transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman and X-ray photoelectron (XP) spectroscopic studies. Significantly, Ni doped CZTS electrocatalyst exhibits low overpotential approximately 214 and 400 mV for the hydrogen evolution reactions (HER) in 0.5 M H₂SO₄ and 1 M KOH electrolyte solutions respectively, and 1.29 V vs RHE for the oxygen evolution reactions (OER) in 1 M KOH at 10 mA/cm² current density. Small Tafel slopes and tested durability for longer time i.e. upto 500 min for water splitting, demonstrates that Ni doped CZTS is efficient bifunctional electrocatalyst having high activity along with extraordinary current/potential stability. Moreover, Fe doped CZTS electrocatalyst shows relatively poor response, i.e. overpotential 300 mV in 0.5 M H₂SO₄ and 445 mV in 1.0 M KOH towards HER and overpotential 1.54 V for the OER in 1 M KOH reaches at 10 mA/cm². This highly efficient bifunctional electrocatalysts that can meet the existing energy anxiety.     

Cost effective and facile low temperature hydrothermal fabrication of Cu2S thin films for hydrogen evolution reaction in seawater splitting

Electrolysis of seawater gets an attention to produce hydrogen for renewable energy technology. It significantly reduces the use of fresh water instead of seawater. Development of low temperature fabrication of electrocatalyst can explore seawater splitting by avoiding chloride reduction during the hydrogen production. In the present work, we fabricated low temperature hydrothermal growth of Cu₂S electrocatalyst on Ni foam at constant temperature of 80 °C at different growth times of 1–3 h. The prepared Cu₂S electrocatalyst grown for 1 h exhibited low overpotentials of 76 and 118 mV at 10 mA/cm² (289 and 358 mV overpotentials at 100 mA/cm²) in 1 M KOH deionized water and seawater, respectively for hydrogen evolution reaction (HER). The Tafel plot of Cu₂S catalyst grown for 1 h showed lesser Tafel slope value of 128 mVdec^?1 than that of other growth times 2 h (136 mVdec^?1) and 3 h (142 mV dec^?1) indicating elevated electrocatalytic behaviour of Cu₂S grown for 1 h. Electrochemical impedance spectroscopy (EIS) showed charge transfer resistance of 12.8Ω, 19.6 Ω and 25.7Ω, for Cu₂S grown for 1, 2 and 3 h, respectively, this lower charge transfer resistance indicated higher charge transfer properties. The Cu₂S electrocatalyst grown for 1 h sustained retention of 80% after 12 h continuous stability test. Therefore, the cost-effective and low temperature fabrication of Cu₂S electrocatalyst proceeds for development of largescale seawater splitting for hydrogen production.     

Fabrication of ZnO/SrTiO3 nanoarrays and its photoelectrochemical performances

The ZnO/SrTiO₃ nanomaterials were fabricated by a chemical conversion hydrothermal method in order to utilize the high electron transfer rate of one-dimensional ZnO nanorods and photocatalytic activity of SrTiO₃. The technological parameters, such as TiO₂ sol concentration, TiO₂ sol dipping cycle, Sr(NO₃)₂ concentration and reaction temperature, were investigated in the synthetic process and the reaction mechanism of the ZnO/SrTiO₃ nanomaterials was proposed. A photocurrent density of 7.53 mA/cm² was obtained for the as-prepared ZnO/SrTiO₃ photocatalyst, attributed to its improved absorption spectrum and appropriate nanostructure, which indicates a potential application in photoelectrochemical water splitting.     

Photoelectrocatalytic degradation of amoxicillin over quaternary ZnO/ZnSe/CdSe/MoS2 hierarchical nanorods

Quaternary semiconductor film consists of ZnO, ZnSe, CdSe and MoS₂ was designed to establish a core-shell structure to achieve the photoelectrochemical oxidation of amoxicillin. The hybrid photoelectrode was fabricated on a FTO substrate from bath deposition methods. The hierarchical ZnSe/CdSe/MoS₂ shell was covered uniformly on ZnO nanorod core which provided a direct pathway for electron transfer, large surface area to enhance light absorption and increase active sites. The quaternary photoelectrode exhibited a photocurrent density of 26.86 mA/cm² at 0 V vs. Ag/AgCl under UV–visible light illumination, which was 31.9 times, 16.7 times and 1.6 times of that of the bare ZnO nanorods, binary ZnO/ZnSe and ternary ZnO/ZnSe/CdSe photoelectrodes, respectively. 10 ppm of amoxicillin was completely degraded in 30 min by the quaternary working electrode with an applied bias of 0.5 V vs. Ag/AgCl. The reusability and stability of quaternary electrode was demonstrated by 3-run recycling experiments. The enhanced photoelectrochemical performance of quaternary photoelectrode can be attributed to the enhancement of light absorption and increased active sites from the coverage of visible-active layers, the accelerated charge separation from the formation of p-n junction and reduced photocorrosion of CdSe from the protection of MoS₂ on the surface.     

Sn self-doped α-Fe2O3 nanobranch arrays supported on a transparent,conductive SnO2 trunk to improve photoelectrochemical water oxidation

We produced hierarchically branched Fe₂O₃ nanorods on a Sb:SnO₂ transparent conducting oxide (TCO) nanobelt structure as photoanodes for photoelectrochemical water splitting. Single-crystalline SnO₂ nanobelts (NBs) surrounded by Fe₂O₃ nanorods (NRs) were synthesized by thermal evaporation, then underwent chemical bath deposition and annealing. When Fe₂O₃ was crystallized by annealing, Sn was diffused from SnO₂ NBs and incorporated to Fe₂O₃ NRs, which was confirmed through Energy dispersive spectroscopy. Unlike previous high temperature sintering (∼800 °C), Sn doped hematite NRs were obtained at a low temperature (∼650 °C). This occurred since SnO₂ NBs directly connected to Fe₂O₃ NRs are an abundant source of Sn dopant. The 3D hematite NRs on SnO₂ NBs annealed at 650 °C produce a photocurrent density of 0.88 mA/cm² at 1.23 V vs. RHE, which is 3 times higher than that of hematite NRs on a fluorine doped tin oxide (FTO) glass substrate annealed at the same temperature. The enhanced photocurrent is attributed to the improved electrical conductivity of Fe₂O₃ NRs by Sn doping, the efficient electron transport pathway by TCO nanowire and the increased surface area by hierarchically branched structure.     

Thermally oxidized iron oxide nanoarchitectures for hydrogen production by solar-induced water splitting

Thermally oxidized iron oxide (α-Fe₂O₃, Hematite) nanostructures are investigated as photoanodes that convert solar energy into hydrogen by splitting water. α-Fe₂O₃ is stable for water photo-oxidation, it has a favorable band gap energy and is a non-toxic common material. However, α-Fe₂O₃ photoanodes suffer from high loss due to electron-hole recombination; therefore nanoarchitectures with high aspect ratio that allows photons to be absorbed close to the photoanode/electrolyte interface are preferred. The thermal oxidation of iron is a simple way to produce nanostructured iron oxide electrodes. Different morphologies, aspect ratios, and oxide thicknesses result depending on the process parameters. Nanorod structures were obtained by annealing iron foils in oxygen rich atmosphere, whereas annealing in oxygen lean atmosphere resulted in nanocoral-like morphology. The nanorod-structured photoanodes achieved moderate photocurrent density of 0.9 mA/cm² while the nanocoral morphology achieved 2.6 mA/cm² (both at 1.8 V vs. the reversible hydrogen electrode). The effect of the oxidation process and oxide layer on performance is discussed.     

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.     

Surface modification of the p-type Cu2ZnSnS4 photocathode with n-type zinc oxide nanorods for photo-driven salt water splitting

The sulfurization of co-sputtering Cu–Zn–Sn metal precursors was employed to prepare the quaternary copper-zinc-tin-sulphide (Cu₂ZnSnS₄, CZTS) photocathodes on substrates. Influence of [Zn]/[Sn] ratios in CZTS photocathodes on their phases, morphologies, and the efficiencies of photo-driven salt-water splitting was examined. Pristine p-type CZTS photocathodes showed the highest photo-driven performance of 0.61 mA cm^?2 in an electrolyte containing 1 M sodium chloride with the external bias kept at ?1.0 V vs. Ag/AgCl. An n-type zinc oxide (ZnO) nanorod arrays layer was then coated on the CZTS photocathode to improve its photo-driven salt-water splitting performance. The CZTS/ZnO photoelectrode had the best photo-driven performance of 1.87 mA cm^?2 in the 1 M NaCl solution under illumination with the external bias set at ?1.0 V vs. Ag/AgCl. From results of electrochemical impedance spectra measurements for the samples in the electrolyte, the CZTS/ZnO sample had good photo-driven salt-water splitting performance due to its lowest charge transfer resistance and p-n junction formed at the sample. Intensity modulated photocurrent spectroscopy and electrochemical impedance spectra results of samples indicated that the surface states at the CZTS/ZnO interface were the recombination centers with the electrons from the CZTS sample and holes from the ZnO and therefore improved its photo-driven salt-water splitting performance.     

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.