Nano multi-layered HfO2/α-Fe2O3 nanocomposite photoelectrodes for photoelectrochemical water splitting.

This study marks a significant stride in enhancing photoelectrochemical (PEC) water splitting applications through the development of a type II nano-heterojunction comprising HfO2 and α - Fe2O3. Fabricated via Physical Vapor Deposition/Radio Frequency (PVD/RF) sputtering, this nano-heterojunction effectively addresses the efficiency limitations inherent in traditional α - Fe2O3photoanodes. The integration of HfO2 leads to a substantial increase in photocurrent density, soaring from 62 µA/cm2 for pure α - Fe2O3 to 1.46 mA cm-2 at 1.23 V versus the Reversible Hydrogen Electrode (RHE). This enhancement, a 23-fold increase, is primarily attributed to the improved absorption of photons in the visible range and the facilitation of more efficient charge transfer. The enhanced performance and long-term stability of the HfO2/α - Fe2O3 nano-heterojunction, validated through XRD, XPS, Raman Spectroscopy, EDS, SEM, EIS, and UPS analyses, demonstrate its potential as a promising and cost-effective solution for PEC water splitting applications, leveraging renewable energy sources.

Heterostructured WO3-TiVO4 thin-film photocatalyst for efficient photoelectrochemical water splitting.

Photoelectrochemical water splitting via solar irradiation has garnered significant interest due to its potential in large-scale renewable hydrogen production. Heterostructure materials have emerged as an effective strategy, demonstrating enhanced performance in photoelectrochemical water-splitting applications compared to individual photocatalysts. In this study, to augment the performance of sprayed TiVO4 thin films, a hydrothermally prepared WO3 underlayer was integrated beneath the spray pyrolised TiVO4 film. The consequent heterostructure demonstrated notable enhancements in optical, structural, microstructural attributes, and photocurrent properties. This improvement is attributed to the strategic deposition of WO3 underlayer, forming a heterostructure composite electrode. This led to a marked increase in photocurrent density for the WO3/TiVO4 photoanode, reaching a peak of 740 µA/cm2 at an applied potential of 1.23 V vs RHE, about nine-fold that of standalone TiVO4. Electrochemical impedance spectroscopy revealed a reduced semicircle for the heterostructure, indicating improved charge transfer compared to bare TiVO4. The heterostructure photoelectrode exhibited enhanced charge carrier conductivity at the interface and sustained stability over 3 h. The distinct attributes of heterostructure photoelectrode present significant opportunities for devising highly efficient sunlight-driven water-splitting systems.

Enhanced Photoelectrochemical Performance Using Cobalt-Catalyst-Loaded PVD/RF-Engineered WO3 Photoelectrodes.

Critical to boosting photoelectrochemical (PEC) performance is improving visible light absorption, accelerating carrier separation, and reducing electron-hole pair recombination. In this investigation, the PVD/RF method was employed to fabricate WO3 thin films that were subsequently treated using the surface treatment process, and the film surface was modified by introducing varying concentrations of cobalt nanoparticles, a non-noble metal, as an effective Co catalyst. The results show that the impact of loaded cobalt nanoparticles on the film surface can explain the extended absorption spectrum of visible light, efficiently capturing photogenerated electrons. This leads to an increased concentration of charge carriers, promoting a faster rate of carrier separation and enhancing interface charge transfer efficiency. Compared with a pristine WO3 thin film photoanode, the photocurrent of the as-prepared Co/WO3 films shows a higher PEC activity, with more than a one-fold increase in photocurrent density from 1.020 mA/cm2 to 1.485 mA/cm2 under simulated solar radiation. The phase, crystallinity, and surface of the prepared films were analysed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The PVD/RF method, scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM) were employed to assess the surface morphology of the fabricated film electrode. Optical properties were studied using UV-vis absorbance spectroscopy. Simultaneously, the photoelectrochemical properties of both films were evaluated using linear sweep voltammetry and electrochemical impedance spectroscopy (EIS). These results offer a valuable reference for designing high-performance photoanodes on a large scale for photoelectrochemical (PEC) applications.

Fabrication and Characterization of Tantalum-Iron Composites for Photocatalytic Hydrogen Evolution.

Photocatalytic hydrogen evolution represents a transformative avenue in addressing the challenges of fossil fuels, heralding a renewable and pristine alternative to conventional fossil fuel-driven energy paradigms. Yet, a formidable challenge is crafting a high-efficacy, stable photocatalyst that optimizes solar energy transduction and charge partitioning even under adversarial conditions. Within the scope of this investigation, tantalum-iron heterojunction composites characterized by intricate, discoidal nanostructured materials were meticulously synthesized using a solvothermal-augmented calcination protocol. The X-ray diffraction, coupled with Rietveld refinements delineated the nuanced alterations in phase constitution and structural intricacies engendered by disparate calcination thermal regimes. An exhaustive study encompassing nano-morphology, electronic band attributes, bandgap dynamics, and a rigorous appraisal of their photocatalytic prowess has been executed for the composite array. Intriguingly, the specimen denoted as 1000-1, a heterojunction composite of TaO2/Ta2O5/FeTaO4, manifested an exemplary photocatalytic hydrogen evolution capacity, registering at 51.24 µmol/g, which eclipses its counterpart, 1100-1 (Ta2O5/FeTaO4), by an impressive margin. Such revelations amplify the prospective utility of these tantalum iron matrices, endorsing their candidacy as potent agents for sustainable hydrogen production via photocatalysis.

Synergistic Photoelectrochemical and Photocatalytic Properties of the Cobalt Nanoparticles-Embedded TiVO4 Thin Film.

To optimize the semiconductor properties of TiVO4 thin films and enhance their performance, we incorporated cobalt nanoparticles as an effective co-catalyst consisting of a non-noble metal. Through an investigation into the impact of cobalt loading on spray pyrolyzed TiVO4 thin films, we observed a significant enhancement in the photoelectrochemical (PEC) performance. This was accomplished by carefully optimizing the concentrations of Co2+ (3 mM) to fabricate a composite electrode, resulting in a higher photocurrent density for the TiVO4:Co photoanode. When an applied potential of 1.23 V (vs RHE) was used, the photocurrent density reached 450 µA/cm2, approximately 5 times higher than that of bare TiVO4. We conducted a thorough characterization of the composite structure and optical properties. Additionally, electrochemical impedance spectroscopy analysis indicated that the TiVO4/Co thin film exhibited a smaller semicircle, indicating a significant improvement in charge transfer at the interface. In comparison to bare TiVO4, the TiVO4/Co composite exhibited a notable improvement in photocatalytic activity when degrading methylene blue (MB) dye, a widely employed model dye. Under light illumination, a TiVO4/Co thin film exhibited a notable dye degradation rate of 97% within a 45 min duration. The scalability of our fabrication method makes it suitable for large-area devices intended for sunlight-driven PEC seawater splitting studies.

Fabrication of TiVO4 photoelectrode for photoelectrochemical application.

Photoelectrochemical (PEC) water splitting is one of the promising, environmentally friendly, carbon emission-free strategies for the cost-effective production of hydrogen. The interest in developing effective approaches for solar-to-hydrogen production with stable and visible light active semiconductors directed many researchers to develop stable and efficient materials. For the first time, a nanostructured TiVO4 photoanode was fabricated at a substrate temperature of 250 °C and further annealed at 600 °C using the spray pyrolysis technique and it obtained an optical band gap of ∼2.18 eV. The photoanode underwent photoelectrochemical testing, where it exhibited a high photocurrent density of 0.080 mA cm-2 at 1.23 V (vs. reversible hydrogen electrode), which can be stable up to 110 min. Further, various physicochemical characterizations were employed to understand the phase purity and thin film growth mechanism. A systematic substrate and annealed temperatures were monitored during the fabrication process. The transmission electron microscopy (TEM) studies revealed agglomeration of TiVO4 nanoparticles with an average size of ∼100 nm accompanying dendritic orientation at the outer edge. This study envisages the design and development of a novel photocatalyst for water splitting under visible light irradiation, an ideal route to a cost-effective, large-scale, sustainable route for hydrogen production.