Controlling crystallites orientation and facet exposure for enhanced electrochemical properties of polycrystalline MoO3 films.

This study focuses on the development and optimization of MoO3 films on commercially available FTO substrates using the pulsed laser deposition (PLD) technique. By carefully selecting deposition conditions and implementing post-treatment procedures, precise control over crystallite orientation relative to the substrate is achieved. Deposition at 450 °C in O2 atmosphere results in random crystallite arrangement, while introducing argon instead of oxygen to the PLD chamber during the initial stage of sputtering exposes the (102) and (011) facets. On the other hand, room temperature deposition leads to the formation of amorphous film, but after appropriate post-annealing treatment, the (00k) facets were exposed. The deposited films are studied using SEM and XRD techniques. Moreover, electrochemical properties of FTO/MoO3 electrodes immersed in 1 M AlCl3 aqueous solution are evaluated using cyclic voltammetry and electrochemical impedance spectroscopy. The results demonstrate that different electrochemical processes are promoted based on the orientation of crystallites. When the (102) and (011) facets are exposed, the Al3+ ions intercalation induced by polarization is facilitated, while the (00k) planes exposure leads to the diminished hydrogen evolution reaction overpotential.

Insight into Potassium Vanadates as Visible-Light-Driven Photocatalysts: Synthesis of V(IV)-Rich Nano/Microstructures for the Photodegradation of Methylene Blue.

Photocatalysis is regarded as a promising tool for wastewater remediation. In recent years, many studies have focused on investigating novel photocatalysts driven by visible light. In this study, K2V6O16·nH2O nanobelts and KV3O8 microplatelets were synthesized and investigated as photocatalysts. Samples were obtained via the facile method based on liquid-phase exfoliation with ion exchange. By changing the synthesis temperature (20-80 °C), different compositions, morphologies, and V4+/V5+ ratios were obtained and investigated as photocatalysts for organic dye degradation. Potassium vanadates' structural, morphological, and optical properties were characterized using X-ray diffraction(XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Physical Property Measurement System (PPMS), thermogravimetric analysis (TGA) with mass spectrometry (MS), N2 adsorption, scanning electron microscopy (SEM), photoluminescence (PL), and UV-vis diffuse reflectance spectroscopy (DRS). Synthesized K2V6O16·nH2O and KV3O8 showed an efficient absorption in the visible wavelength region with a narrow band gap energy of 1.80 and 1.91 eV, respectively. Their photocatalytic activity was evaluated by the degradation of methylene blue (MB) under simulated solar light illumination. The KV3O8 microplatelets exhibited the greatest photocatalytic activity, resulting in more than 90% degradation of the dye within the first 30 min. It is suggested that the observed excellent photocatalytic performance is attributed to the high content of V4+ species. Furthermore, the influence of active species was investigated, and the mechanism responsible for the photodegradation of the MB dye was discussed for the first time for potassium vanadates.

Scaling Up the Process of Titanium Dioxide Nanotube Synthesis and Its Effect on Photoelectrochemical Properties.

In this work, for the first time, the influence of scaling up the process of titanium dioxide nanotube (TiO2NT) synthesis on the photoelectrochemical properties of TiO2 nanotubes is presented. Titanium dioxide nanotubes were obtained on substrates of various sizes: 2 × 2, 4 × 4, 5 × 5, 6 × 6, and 8 × 8 cm2. The electrode material was characterized using scanning electron microscopy as well as Raman and UV-vis spectroscopy in order to investigate their morphology, crystallinity, and absorbance ability, respectively. The obtained electrodes were used as photoanodes for the photoelectrochemical water splitting. The surface analysis was performed, and photocurrent values were determined depending on their place on the sample. Interestingly, the values of the obtained photocurrent densities in the center of each sample were similar and were about 80 µA·cm2. The results of our work show evidence of a significant contribution to wider applications of materials based on TiO2 nanotubes not only in photoelectrochemistry but also in medicine, supercapacitors, and sensors.

Tin Oxide Encapsulated into Pyrolyzed Chitosan as a Negative Electrode for Lithium Ion Batteries.

Tin oxide is one of the most promising electrode materials as a negative electrode for lithium-ion batteries due to its higher theoretical specific capacity than graphite. However, it suffers lack of stability due to volume changes and low electrical conductivity while cycling. To overcome these issues, a new composite consisting of SnO2 and carbonaceous matrix was fabricated. Naturally abundant and renewable chitosan was chosen as a carbon source. The electrode material exhibiting 467 mAh g-1 at the current density of 18 mA g-1 and a capacity fade of only 2% after 70 cycles is a potential candidate for graphite replacement. Such good electrochemical performance is due to strong interaction between amine groups from chitosan and surface hydroxyl groups of SnO2 at the preparation stage. However, the charge storage is mainly contributed by a diffusion-controlled process showing that the best results might be obtained for low current rates.

Improving the Performance of a Graphite Foil/Polyaniline Electrode Material by a Thin PEDOT:PSS Layer for Application in Flexible, High Power Supercapacitors.

In this study, we present a novel strategy for enhancing polyaniline stability and thus obtaining an electrode material with practical application in supercapacitors. A promising (graphite foil/polyaniline/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) GF/PANI/PEDOT:PSS) electrode material was characterized and used in the construction of a symmetric supercapacitor that provides an outstanding high power density. For this purpose, the electropolymerization of PANI was carried out on a graphite foil and then a thin protective layer of PEDOT:PSS was deposited. The presence of the nanometer PEDOT:PSS layer made it possible to widen the electroactivity potential range of the electrode material. Moreover, the synergy between materials positively affected the amount of accumulated charge, and thus the thin PEDOT:PSS layer contributed to enhancing the specific capacity of the electrode material. The electrochemical performance of the GF/PANI/PEDOT:PSS electrode, as well as the symmetrical supercapacitor, was investigated by cyclic voltammetry and galvanostatic charge/discharge cycles in 1 M H2SO4 at room temperature. The fabricated electrode material shows a high specific capacitance (Csp) of 557.4 Fg-1 and areal capacitance (Careal) of 2600 mF·cm-2 in 1 M H2SO4 at a current density of 200 mA·cm-2 (~4 A·g-1). The supercapacitor performance was studied and the results show that a thin PEDOT:PSS layer enables cycling stability improvement of the device from 54% to 67% after 10,000 cycles, and provides a high specific capacity (159.8 F·g-1) and a maximum specific power (18,043 W·kg-1) for practical applications.

An Aqueous Exfoliation of WO3 as a Route for Counterions Fabrication-Improved Photocatalyticand Capacitive Properties of Polyaniline/WO3Composite.

In this paper, we demonstrate a novel, electrochemical route of polyaniline/tungsten oxide (PANI)/WO3) film preparation. Polyaniline composite film was electrodeposited on the FTO (fluorine-doped tin oxide) substrate from the aqueous electrolyte that contained aniline (monomer) and exfoliated WO3 as a source of counter ions. The chemical nature of WO3 incorporated in the polyaniline matrix was investigated using X-ray photoelectron spectroscopy. SEM (scanning electron microscopy) showed the impact of WO3 presence on the morphology of polyaniline film. PANI/WO3 film was tested as an electrode material in an acidic electrolyte. Performed measurements showed the electroactivity of both components and enhanced electrochemical stability of PANI/WO3 in comparison with PANI/Cl. Thus, PANI/WO3 electrodes were utilized to construct the symmetric supercapacitors. The impact of capacitive and diffusion-controlled processes on the mechanism of electrical energy storage was quantitatively determined. Devices exhibited high electrochemical capacity of 135 mF cm-2 (180 F g-1) and satisfactory retention rate of 70% after 10,000 cycles. The electrochemical energy storage device exhibited 1075.6 W kg-1 of power density and 12.25 Wh kg-1 of energy density. We also investigated the photocatalytic performance of the deposited film. Photodegradation efficiencies of methylene blue and methyl orange using PANI/WO3 and PANI/Cl were compared. The mechanism of dye degradation using WO3-containing films was investigated in the presence of scavengers. Significantly higher efficiency of photodecomposition of dyes was achieved for composite films (84% and 86%) in comparison with PANI/Cl (32% and 39%) for methylene blue and methyl orange, respectively.

An Easy and Ecological Method of Obtaining Hydrated and Non-Crystalline WO3-x for Application in Supercapacitors.

In this work, we report the synthesis of hydrated and non-crystalline WO3 flakes (WO3-x) via an environmentally friendly and facile water-based strategy. This method is described, in the literature, as exfoliation, however, based on the results obtained, we cannot say unequivocally that we have obtained an exfoliated material. Nevertheless, the proposed modification procedure clearly affects the morphology of WO3 and leads to loss of crystallinity of the material. TEM techniques confirmed that the process leads to the formation of WO3 flakes of a few nanometers in thickness. X-ray diffractograms affirmed the poor crystallinity of the flakes, while spectroscopic methods showed that the materials after exfoliation were abundant with the surface groups. The thin film of hydrated and non-crystalline WO3 exhibits a seven times higher specific capacitance (Cs) in an aqueous electrolyte than bulk WO3 and shows an outstanding long-term cycling stability with a capacitance retention of 92% after 1000 chronopotentiometric cycles in the three-electrode system. In the two-electrode system, hydrated WO3-x shows a Cs of 122 F g-1 at a current density of 0.5 A g-1. The developed supercapacitor shows an energy density of 60 Whkg-1 and power density of 803 Wkg-1 with a decrease of 16% in Csp after 10,000 cycles. On the other hand, WO3-x is characterized by inferior properties as an anode material in lithium-ion batteries compared to bulk WO3. Lithium ions intercalate into a WO3 crystal framework and occupy trigonal cavity sites during the electrochemical polarization. If there is no regular layer structure, as in the case of the hydrated and non-crystalline WO3, the insertion of lithium ions between WO3 layers is not possible. Thus, in the case of a non-aqueous electrolyte, the specific capacity of the hydrated and non-crystalline WO3 electrode material is much lower in comparison with the specific capacity of the bulk WO3-based anode material.

Diatoms Biomass as a Joint Source of Biosilica and Carbon for Lithium-Ion Battery Anodes.

The biomass of one type cultivated diatoms (Pseudostaurosira trainorii), being a source of 3D-stuctured biosilica and organic matter-the source of carbon, was thermally processed to become an electroactive material in a potential range adequate to become an anode in lithium ion batteries. Carbonized material was characterized by means of selected solid-state physics techniques (XRD, Raman, TGA). It was shown that the pyrolysis temperature (600 °C, 800 °C, 1000 °C) affected structural and electrochemical properties of the electrode material. Biomass carbonized at 600 °C exhibited the best electrochemical properties reaching a specific discharge capacity of 460 mAh g-1 for the 70th cycle. Such a value indicates the possibility of usage of biosilica as an electrode material in energy storage applications.

Pulsed Laser Deposition of Bismuth Vanadate Thin Films-The Effect of Oxygen Pressure on the Morphology, Composition, and Photoelectrochemical Performance.

Thin layers of bismuth vanadate were deposited using the pulsed laser deposition technique on commercially available FTO (fluorine-doped tin oxide) substrates. Films were sputtered from a sintered, monoclinic BiVO4 pellet, acting as the target, under various oxygen pressures (from 0.1 to 2 mbar), while the laser beam was perpendicular to the target surface and parallel to the FTO substrate. The oxygen pressure strongly affects the morphology and the composition of films observed as a Bi:V ratio gradient along the layer deposited on the substrate. Despite BiVO4, two other phases were detected using XRD (X-ray diffraction) and Raman spectroscopy-V2O5 and Bi4V2O11. The V-rich region of the samples deposited under low and intermediate oxygen pressures was covered by V2O5 longitudinal structures protruding from BiVO4 film. Higher oxygen pressure leads to the formation of Bi4V2O11@BiVO4 bulk heterojunction. The presented results suggest that the ablation of the target leads to the plasma formation, where Bi and V containing ions can be spatially separated due to the interactions with oxygen molecules. In order to study the phenomenon more thoroughly, laser-induced breakdown spectroscopy measurements were performed. Then, obtained electrodes were used as photoanodes for photoelectrochemical water splitting. The highest photocurrent was achieved for films deposited under 1 mbar O2 pressure and reached 1 mA cm-2 at about 0.8 V vs Ag/AgCl (3 M KCl). It was shown that V2O5 on the top of BiVO4 decreases its photoactivity, while the presence of a bulk Bi4V2O11@BiVO4 heterojunction is beneficial in water photooxidation.

Widening of the electroactivity potential range by composite formation - capacitive properties of TiO2/BiVO4/PEDOT:PSS electrodes in contact with an aqueous electrolyte.

Composites based on the titania nanotubes were tested in aqueous electrolyte as a potential electrode material for energy storage devices. The nanotubular morphology of TiO2 was obtained by Ti anodization. TiO2 nanotubes were covered by a thin layer of bismuth vanadate using pulsed laser deposition. The formation of the TiO2/BiVO4 junction leads to enhancement of pseudocapacitance in the cathodic potential range. The third component, the conjugated polymer PEDOT:PSS, was electrodeposited from an electrolyte containing the monomer EDOT and NaPSS as a source of counter ions. Each stage of modification and deposition affected the overall capacitance and allowed for an expansion of the potential range of electroactivity. Multiple charge/discharge cycles were performed to characterize the electrochemical stability of the inorganic-organic hybrid electrode. Capacitance values higher than 10 mF·cm-2 were maintained even after 10000 galvanostatic cycles (i c = i a = 0.5 mA·cm-2).

UV-Vis-Induced Degradation of Phenol over Magnetic Photocatalysts Modified with Pt, Pd, Cu and Au Nanoparticles.

The combination of TiO2 photocatalyst and magnetic oxide nanoparticles enhances the separation and recoverable properties of nanosized TiO2 photocatalyst. Metal-modified (Me = Pd, Au, Pt, Cu) TiO2/SiO2@Fe3O4 nanocomposites were prepared by an ultrasonic-assisted sol-gel method. All prepared samples were characterized by X-ray powder diffraction (XRD) analysis, Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), Mott-Schottky analysis and photoluminescence spectroscopy (PL). Phenol oxidation pathways of magnetic photocatalysts modified with Pt, Pd, Cu and Au nanoparticles proceeded by generation of reactive oxygen species, which oxidized phenol to benzoquinone, hydroquinone and catechol. Benzoquinone and maleic acid were products, which were determined in the hydroquinone oxidation pathway. The highest mineralization rate was observed for Pd-TiO2/SiO2@Fe3O4 and Cu-TiO2/SiO2@Fe3O4 photocatalysts, which produced the highest concentration of catechol during photocatalytic reaction. For Pt-TiO2/SiO2@Fe3O4 nanocomposite, a lack of catechol after 60 min of irradiation resulted in low mineralization rate (CO2 formation). It is proposed that the enhanced photocatalytic activity of palladium and copper-modified photocatalysts is related to an increase in the amount of adsorption sites and efficient charge carrier separation, whereas the keto-enol tautomeric equilibrium retards the rate of phenol photomineralization on Au-TiO2/SiO2@Fe3O4. The magnetization hysteresis loop indicated that the obtained hybrid photocatalyst showed magnetic properties and therefore could be easily separated after treatment process.