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.

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.

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.

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.

Vertically Aligned CdO-Decked α-Fe2O3 Nanorod Arrays by a Radio Frequency Sputtering Method for Enhanced Photocatalytic Applications.

Green hydrogen production is one of the most desirable sustainable goals of the United Nations. Thus, for that purpose, we developed hematite (α-Fe2O3), an n-type semiconductor, a desirable candidate for photoelectrochemical (PEC) water splitting, enabling hydrogen evolution. High recombination losses, low efficiency, and large-scale production hinder its potential. To address these issues, we have fabricated optimized bare and cadmium oxide (CdO)-decorated hematite thin film nanorod arrays using a throughput radio frequency (RF) sputtering with efficient water splitting behavior. To the best of our knowledge, no work has been done so far on the synthesis of CdO/α-Fe2O3 via RF sputtering for PEC application. Bare α-Fe2O3 samples, with a morphology of vertically aligned nanorods, were fabricated with optimized parameters such as as-deposited 70 nm of Fe, an angle of deposition of 70°, and an annealing temperature of 600 °C, which showed a photocurrent density of 0.38 mA/cm2 at 1.65 V vs reversible hydrogen electrode (RHE). Characterizations depicted that this unique morphology with high crystallinity directly enhanced the performance of hematite photoanodes. Further, deposition of 30 nm of cadmium (CdO) on the α-Fe2O3 nanorods produced a corn-like morphology with CdO nanoparticles (∼2 nm), resulting in 4-times enhancement of the PEC performance (1.2 mA/cm2 at 1.65 V vs RHE). CdO acted as a co-catalyst, responsible for satisfactory suppression of recombination and facilitating the hole transfer, directly enhancing the overall photocurrent density. This photoanode showed an extremely stable behavior over a period of 26 h when kept under constant illumination. Furthermore, the CdO-modified photoanode showed a better dye degradation (98% in 40 min) than the bare hematite (60% in 40 min), proving to be an efficient photoanode.