A review: Target-oriented transition metal phosphide design and synthesis for water splitting

With the scarcity of fuel energy, non-noble metal compounds assisted water of electrolysis is becoming a potential candidate for cost-effective and high-quality hydrogen production. To date, transition metal phosphide (TMP) has been considered as one of the most promising catalysts for water splitting because of its multitudinous but controlled constituent elements and stoichiometric ratios. In this review, the electronic structure analysis of TMP dialectically reveals the active derivation for catalyzing hydrogen evolution (HER) and oxygen evolution reaction (OER). And then the strategies of rationally designing the structure and composition of electrocatalyst to improve its intrinsic activity are discussed, especially interface engineering. Besides, this review also focuses on the negligible stability issue during the water splitting process. In the end, some key challenges and research orientations of TMPs are pointed out, which is instructive for developing high-efficient and stable electrocatalysts for water splitting.     

Alternate synthetic strategy for the preparation of CdS nanoparticles and its exploitation for water splitting

Cadmium sulphide nanoparticles (6–12 nm) are prepared by a precipitation process using different zeolite matrices as templates. The nanoparticles were characterized by UV-Vis, XRD, SEM, TEM and sorptometric techniques. XRD study shows the presence of hexagonal and cubic phases for the nanoparticles whereas in case of the bulk samples only the hexagonal phase is observed. These nanomaterials have been used as catalysts for the photocatalytic decomposition of water. The nanoparticles show a higher hydrogen evolution rate compared to the bulk samples which correlates well with the particle size and surface area. Noble metal (Pt, Pd, Rh, Ru)-loaded samples were subsequently prepared and tested for hydrogen evolution reaction. The presence of Pt metal is found to enhance the hydrogen production rate whereas the hydrogen production rate is retarded in the presence of Ru metal. This has been explained on the basis of metal hydrogen bond, redox potential and work function of the noble metal.     

Si/ZnO core-shell nanowire arrays for photoelectrochemical water splitting

n-Type Si nanowire (NW) arrays coated with a thin layer of ZnO were fabricated via a two-step route combined with metal-assisted chemical etching and sol-gel processes. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction were utilized to characterize the core/shell structure. The obtained Si/ZnO core/shell NW arrays exhibit about 8% optical reflectance in visible region, implying good optical absorption. Water splitting performance of Si/ZnO NW arrays was studied. The photoconversion efficiency for Si/ZnO NW arrays reaches 0.38% upon exposure to the illumination with a light intensity of 10 mW/cm², which is higher than those of the planar bilayer structure of Si/ZnO (0.19%) and the pure planar ZnO (0.09%). The relationship between the illumination intensity and the photoconversion efficiency of Si/ZnO NW arrays was also discussed.     

Enhanced photoelectrochemical water splitting via engineered surface defects of BiPO4 nanorod photoanodes

Herein, we report on the defect engineering of BiPO₄ nanorods (NRs) via a facile room-temperature template-free co-precipitation method, followed by hydrogen treatment. The hydrogen treatment temperature determined the type of induced defects in the fabricated BiPO₄ NRs and consequently their photocatalytic performance. Upon varying the annealing temperature, the x-ray diffraction (XRD) analysis showed phase transformation and x-ray photoelectron spectroscopy (XPS) analysis revealed variation in the oxygen vacancy content. At moderate treatment temperatures (200–300 °C), shallow defects were predominant, which extended the optical activity of the material to the visible region and increased the photocurrent 3 times when compared to that of bare BiPO₄ NRs. However, treatment at higher temperatures completely altered the crystalline structure, destructed the morphology of the BiPO₄ NRs, and severely affected the photoelectrochemical performance.     

An overview of photocells and photoreactors for photoelectrochemical water splitting

Solar hydrogen production from direct photoelectrochemical (PEC) water splitting is the ultimate goal for a sustainable, renewable and clean hydrogen economy. While there are numerous studies on solving the two main photoelectrode (PE) material issues i.e. efficiency and stability, there is no standard photocell or photoreactor used in the study. The main requirement for the photocell or photoreactor is to allow maximum light to reach the PE. This paper presents an overview of the PE configurations and the possible photocell and photoreactor design for hydrogen production by PEC water splitting.     

Efficient suppression of surface charge recombination by CoP-Modified nanoporous BiVO4 for photoelectrochemical water splitting

BiVO₄ is a promising photoanode material for water splitting due to its substantial absorption of solar light as well as favorable band edge positions. However, the poor water oxidation kinetics of BiVO₄ results in its insufficient photocurrent density. Herein, we demonstrate the use of CoP nanoparticles for facile surface modification of nanoporous BiVO₄ photoanode in potassium borate buffer solution (pH 9.0), which can generate a tremendous cathodic shift of ~430 mV in the onset potential for photoelectrochemical water oxidation. In addition, a remarkable photocurrent density of 4.1 mA cm^?2 is achieved at 1.23 V vs. RHE under AM 1.5G illumination. The photoelectrochemical measurement using sodium sulfite as a hole scavenger clearly shows that the greatly improved performances are attributed to the efficient suppression of interfacial charge recombination through loading of CoP catalyst. Moreover, the maximum surface charge injection yield can reach >81% at 1.23 V vs. RHE and the maximum IPCE of CoP/BiVO₄ can reach 75.8% at 420 nm, suggesting the potential application of CoP-modified BiVO₄ photoanode for overall solar water splitting in cost-effective tandem photoelectrochemical cells.     

Photoelectrode nanomaterials for photoelectrochemical water splitting

Photoelectrochemical (PEC) water splitting is among the most promising approaches for energy conversion due to its practical efficiency. Unfortunately, many works simply test typical cases without profound insight, and this does not lead us very far. Two concepts are usually neglected: (i) the rate-determining step is usually the electrocatalytic process conducting the water splitting, and thus, the interfacial reaction at the electrode surface can be practically more important that the absorption of photons by the semiconductors, and (ii) the architecture of nanomaterials can directly control both photon absorption and electrochemical catalysis. While narrating the importance of the first concept the primary focus of the present review focuses on the second concept to summarize the general effects of nanostructures on the PEC performance. The nano-architecture has a larger impact on the electrocatalytic properties of the photoelectrode rather than light harvesting capability, but this feature is usually neglected. In fact, designing a nano-architecture is a tuning process to balance a series of different processes, which are in competition in a complicated system, for optimizing the PEC performance. The most important task is to maximize the number of electrocatalytic sites and forming a more effective electrode/electrolyte interface while reducing the number of charge recombination centers. Nanostructuring is normally in favor of the former while unfavorably supporting the latter.     

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.     

Branched multiphase TiO2 with enhanced photoelectrochemical water splitting activity

An efficient hierarchical structure, nano-branch containing anatase TiO₂ nanofibers and rutile nanorods, was prepared via the combination of the electrospinning and hydrothermal processes. This novel configuration of TiO₂ multiphase possessed higher surface area, roughness, and fill factors compared with each single phase component prepared in the same condition, which significantly enhanced its light absorption. Our experimental results showed that within the interface of multiphase TiO₂, the heterojunction promoted the charge separation and improved the charge transfer rate, leading to higher efficiency for photoelectrochemical water splitting. The photocurrent density of the nano-branched TiO₂ electrode could reach 0.95 mA/cm², which was almost twice as large as that of the pristine TiO₂ nanorod. Our work provides a simple and feasible routine to synthesize complex TiO₂ nanoarchitectures, which lays a foundation for improving energy storage and conversion efficiency of TiO₂-based photoelectrodes.     

Hydrogen production from water splitting over Eosin Y-sensitized mesoporous-assembled perovskite titanate nanocrystal photocatalysts under visible light irradiation

The photocatalytic water splitting is a promising process for producing H₂ from two abundant renewable sources of water and solar light, with the aid of a suitable photocatalyst. In this work, a combination of sensitizer addition and noble metal loading was employed to modify perovskite photocatalysts in order to achieve the enhancement of photocatalytic H₂ production under visible light irradiation. The dependence of the H₂ production on type of mesoporous-assembled perovskite titanate nanocrystal photocatalysts (MgTiO₃, CaTiO₃, and SrTiO₃), calcination temperature of photocatalyst, Pt loading, type and concentration of electron donor (diethanolamine, DEA; and triethanolamine, TEA), concentration of sensitizer (Eosin Y, E.Y.), photocatalyst dosage, and initial solution pH, was systematically studied. The experimental results showed that the 0.5 wt.% Pt-loaded mesoporous-assembled SrTiO₃ nanocrystal synthesized by a single-step sol-gel method and calcined at 650 °C exhibited the highest photocatalytic H₂ production activity from a 15 vol% DEA aqueous solution with dissolved 0.5 mM E.Y. Moreover, the optimum photocatalyst dosage and initial solution pH for the maximum photocatalytic H₂ production activity were found to be 6 g/l and 11.6, respectively.     

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.     

Transient phenomenological modeling of photoelectrochemical cells for water splitting - Application to undoped hematite electrodes

A phenomenological model is proposed for a better understanding of the basic mechanisms of photoelectrochemical (PEC) cells. The main assumptions of the one-dimensional transient phenomenological model are: i) bulk recombination of the conduction band electrons with holes in the valence band; ii) the mobile charge transport takes place via diffusion, which arises from the concentration profiles, and migration, caused by a macroscopic electric field; iii) negligible effects of microscopic electric fields in the cell and screening effects, as well as negligible Helmholtz and diffuse layers. For modeling purposes, the photoanode was assumed to be a homogeneous nanocrystalline hematite structure, with thickness L, porosity ?_p and tortuosity τ. The TCO/semiconductor interface was modeled as an ideal ohmic contact, while the electrolyte/platinized TCO interface was described by a Butler-Volmer approach. An alkaline electrolyte solution was used, allowing the transport of the ionic species from the counter-electrode to the photoanode. The continuity and transport governing equations are defined for the mobile species involved: electrons in the conduction band of the semiconductor, holes in the valence band and hydroxyl ions in the electrolyte. Simulated I-V characteristics were computed and the corresponding results compared with the experimental values. The simulated results were in straight agreement with the experimental data.     

Recent progress in the development of visible light-driven powdered photocatalysts for water splitting

Many photocatalyst materials for water splitting have been developed, particularly since the second half of the 1990s. Highly efficient water splitting on tantalate photocatalysts under UV irradiation has been achieved. Moreover, band engineering by doping, valence band formation, and synthesis of solid solutions, has led to the development of a large number of visible light-driven photocatalysts for _H2${\mathrm{H}}_2$ or _O2${\mathrm{O}}_2$ evolution from aqueous solutions containing electron donors or acceptors. Z-scheme photocatalyst systems for water splitting to _H2${\mathrm{H}}_2$ and _O2${\mathrm{O}}_2$ under visible light irradiation have been developed. This progress in the development of visible light-driven photocatalysts for water splitting is reviewed.     

Synthesis and high photocatalytic hydrogen production of SrTiO3 nanoparticles from water splitting under UV irradiation

Cubic SrTiO₃ powders were synthesized by three methods: the polymerized complex (PC) method, the solid state reaction, and the milling assistant method. The samples obtained were characterized by X-ray diffraction (XRD), UV–vis spectroscopy (UV–vis), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The mean diameters of the as-synthesized SrTiO₃ particles were 30 nm by the polymerized complex method, 140 nm by the solid state reaction, and 30 nm by the milling assistant method. The photocatalytic activity of hydrogen evolution from water splitting over SrTiO₃ powders by the polymerized complex method is higher than that by the solid state reaction and the milling assistant method. Particle size, uniformity of components, and particle aggregation extent affect the photocatalytic activity of SrTiO₃ for hydrogen evolution. The best rate of photocatalytic hydrogen evolution over SrTiO₃ by the polymerized complex method under UV illumination is as high as 3.2 mmol h⁻¹ g⁻¹.     

TiO2 nanotubes for hydrogen generation by photocatalytic water splitting in a two-compartment photoelectrochemical cell

Highly ordered TiO₂ nanotube arrays for hydrogen production have been synthesized by electrochemical anodization of titanium sheets. Under solar light irradiation, hydrogen generation by photocatalytic water splitting was carried out in the two-compartment photoelectrochemical cell without any external applied voltage. The hydrogen gas and oxygen generated on Pt side and on TiO₂ nanotubes side respectively were efficiently separated. The effect of anodization time on the morphology structures, photoelectrochemical properties and hydrogen production was systematically investigated. Due to more charge carrier generation and faster charge transfer, a maximum photoconversion efficiency of 4.13% and highest hydrogen production rate of 97 μmol h⁻¹cm⁻² (2.32 mL h⁻¹cm⁻²) were obtained from TiO₂ nanotubes anodized for 60 min.     

Improvement of TiO2 nanotubes for photoelectrochemical water splitting: Review

Photoelectrochemical (PEC) water splitting is an ideal method to produce clean hydrogen. Developing photoelectrodes that fulfill the PEC water-splitting criteria has become the greatest challenge for commercialization of this technology. Titanium dioxide, the first material used for this application, remain appealing due to its one-dimensional nanotube structure. However, the bandgap of TiO₂ nanotubes, ~3.0 eV, is relatively wide, leading to problems such as limited utilization of light energy and easy recombination of the photogenerated products, i.e., electrons and holes. Several approaches have been developed to overcome this problem, including (i) modification of surface morphology to enhance the active catalytic area, (ii) band structure modification to reduce photogenerated charge recombination, and (iii) surface sensitization to improve light absorption ability. This review reports the improvements achieved by all of these approaches for TiO₂ nanotubes, including the basic principles of the photocatalytic water-splitting process and the preparation and polymorphs of TiO₂ nanotubes. This review also discusses combinations of several methods that enable high photocurrent density with fabulous stability.     

Photocatalytic water splitting for hydrogen production on Au/KTiNbO5

Gold nanoparticles were deposited on potassium titanoniobate, KTiNbO₅ using deposition-precipitation (DP), conventional impregnation (IMP) and photodeposition method in order to improve photocatalytic hydrogen production from water splitting. The effect of synthesis pH value of a HAuCl₄ aqueous solution used in the DP process on the morphology of gold nanoparticles, optical property and photocatalytic activity of water splitting under UV light irradiation was investigated. These catalysts were characterized by powder X-ray diffraction patterns (XRD), inductively coupled plasma mass spectrometry (ICP-MS), UV–visible spectroscopy (UV–vis), and Transmission Electron Microscopy (TEM). The Au/KTiNbO₅ catalysts prepared by the DP method consisted of a good metal–semiconductor interface which allowed for a much higher efficient electron-hole separation. The 0.63 wt% Au/KTiNbO₅ catalyst prepared by the DP method at pH = 10 showed a uniform dispersion of gold nanoparticles with an average gold particle size of 4.2 nm and exhibited an ultra-high photocatalytic water splitting activity (3522 μmol g⁻¹ h⁻¹), about 47 times higher than that exhibited by the KTiNbO₅ photocatalyst.     

Flexible polypyrrole activated micro-porous paper-based photoanode for photoelectrochemical water splitting

We herein demonstrate polypyrrole decorated micro-porous laboratory filter paper (PFP) as photoanode (PA) for efficient and stable water splitting. The straddling band position with water redox and the measured band gap of ~1.98 eV, make these PFP-PAs effective for water splitting reactions. The results manifest excellent photo-anodic PEC activity of these PFP-PAs, yielding a photocurrent density of ~9.5 mA/cm² (at 1.23 V vs. RHE) in a three-electrode configuration. The incident photon-to-current efficiency (IPCE) and applied bias photon-to-current efficiency (ABPE) was measured to be 43.19% and ~1%, respectively. Moreover, the robustness of these flexible PFP-PAs was visualized by the provided stability for more than ~160 min in alkaline conditions. The current study provides a proof-of-concept for the realization of a cost-effective, flexible, and efficient paper-based artificial catalyst (like a natural leaf) for solar-driven water splitting.