Project description:Doping hematite with different elements is a common strategy to improve the electrocatalytic activity towards the water oxidation reaction, although the exact effect of these external agents is not yet clearly understood. Using a feasible electrophoretic procedure, we prepared modified hematite films by introducing in the deposition solution Ti(IV) butoxide. Photoelectrochemical performances of all the modified electrodes were superior to the unmodified one, with a 4-fold increase in the photocurrent at 0.65 V vs. SCE in 0.1 M NaOH (pH 13.3) for the 5% Ti-modified electrode, which was the best performing electrode. Subsequent functionalization with an iron-based catalyst led, at the same potential, to a photocurrent of ca. 1.5 mA·cm(-2), one of the highest achieved with materials based on solution processing in the absence of precious elements. AFM, XPS, TEM and XANES analyses revealed the formation of different Ti(IV) oxide phases on the hematite surface, that can reduce surface state recombination and enhance hole injection through local surface field effects, as confirmed by electrochemical impedance analysis.
Project description:Photoelectrochemical oxidation of methylene blue is investigated, with particular focus on the difference in kinetics and thermodynamics of decoloration and mineralization employing photoinduced absorption spectroscopy. Hematite and titania photoanodes are used for the comparison of both reactions, which is determined to be associated with the depth of the valence band (3.2 vs 2.5 V for titania and hematite, respectively). Methylene blue is mineralized by the titania photoanode, however it is only oxidized to small fragments by hematite. Such difference is related to the valence band potential that provides the thermodynamic driving force for photogenerated holes in both materials. In addition, the kinetic competition of water oxidation is found to occur on titania by controlling the pH of the electrolyte. In the pH 14 electrolyte, mineralization of methylene blue is suppressed due to the faster and dominant kinetics of water oxidation, in contrast to the complete mineralization in the near neutral electrolyte where water oxidation kinetics are modest. These results clearly address the importance considering both thermodynamic and kinetic challenges of methylene blue oxidation, which has been thought to be an easy molecule to oxidize, as the model reaction in the application of photo(electro)catalysis using metal oxides.
Project description:Microplastic (MP) accumulation in the environment is accelerating rapidly, which has led to their effects on both the ecosystem and human life garnering much attention. This study is the first to examine the degradation of high-density polyethylene (HDPE) MPs via photoelectrocatalysis (PEC) using a TiO2-modified boron-doped diamond (BDD/TiO2) photoanode. This study was divided into three stages: (i) preparation of the photoanode through electrophoretic deposition of synthetic TiO2 nanoparticles on a BDD electrode; (ii) characterization of the modified photoanode using electrochemical, structural, and optical techniques; and (iii) degradation of HDPE MPs by electrochemical oxidation and photoelectrocatalysis on bare and modified BDD electrodes under dark and UV light conditions. The results indicate that the PEC technique degraded 89.91 ± 0.08% of HDPE MPs in a 10-h reaction and was more efficient at a lower current density (6.89 mA cm-1) with the BDD/TiO2 photoanode compared to electrochemical oxidation on bare BDD.
Project description:Non-modified (ZnO) and modified (Fe2O3@ZnO and CuO@ZnO) structured films are deposited via aerosol assisted chemical vapor deposition. The surface modification of ZnO with iron or copper oxides is achieved in a second aerosol assisted chemical vapor deposition step and the characterization of morphology, structure, and surface of these new structured films is discussed. X-ray photoelectron spectrometry and X-ray diffraction corroborate the formation of ZnO, Fe2O3, and CuO and the electron microscopy images show the morphological and crystalline characteristics of these structured films. Static water contact angle measurements for these structured films indicate hydrophobic behavior with the modified structures showing higher contact angles compared to the non-modified films. Overall, results show that the modification of ZnO with iron or copper oxides enhances the hydrophobic behavior of the surface, increasing the contact angle of the water drops at the non-modified ZnO structures from 122 to 135 and 145 for Fe2O3@ZnO and CuO@ZnO, respectively. This is attributed to the different surface properties of the films including the morphology and chemical composition.
Project description:Advanced oxidation processes driven by renewable energy sources are gaining attention in degrading organic pollutants in waste waters in an efficient and sustainable way. The present work is focused on a study of TiO₂ nanotubes as photocatalysts for photoelectrocatalytic (PEC) degradation of acetaminophen (AMP) at different pH (3, 7, and 9). In particular, different TiO₂ photocatalysts were synthetized by stirring the electrode at different Reynolds numbers (Res) during electrochemical anodization. The morphology of the photocatalysts and their crystalline structure were evaluated by field emission scanning electron microscopy (FESEM) and Raman confocal laser microscopy (RCLM). These analyses revealed that anatase TiO₂ nanotubes were obtained after anodization. In addition, photocurrent densities versus potential curves were performed in order to characterize the electrochemical properties of the photocatalysts. These results showed that increasing the Re during anodization led to an enhancement in the obtained photocurrents, since under hydrodynamic conditions part of the initiation layer formed over the tubes was removed. PEC degradation of acetaminophen was followed by ultraviolet-visible absorbance measurements and chemical oxygen demand tests. As drug mineralization was the most important issue, total organic carbon measurements were also carried out. The statistical significance analysis established that acetaminophen PEC degradation improved as hydrodynamic conditions linearly increased in the studied range (Re from 0 to 600). Additionally, acetaminophen conversion had a quadratic behavior with respect to the reaction pH, where the maximum conversion value was reached at pH 3. However, in this case, the diversity of the byproducts increased due to a different PEC degradation mechanism.
Project description:A novel type of TiO₂ nanotubes (NTs)/Ag/MoS₂ meshy photoelectrode was fabricated with highly oriented TiO₂ nanotube arrays grown from a Ti mesh supporting Ag nanoparticles and three-dimensional MoS₂ nanosheets. In this structure, Ag nanoparticles act as bridges to connect MoS₂ and TiO₂ and pathways for electron transfer, ensuring the abundant production of active electrons, which are the source of •O₂-. The TiO₂ NTs/Ag/MoS₂ mesh can be used as both photocatalyst and electrode, exhibiting enhanced photoelectrocatalytic efficiency in degrading tetracycline hydrochloride under visible light irradiation (λ ≥ 420 nm). Compared to unmodified TiO₂ NTs, the improved photoelectrocatalytic activity of the TiO₂ NTs/Ag/MoS₂ arise from the formation of Z-scheme heterojunctions, which facilitate the efficient separation of photogenerated electron-hole pairs through the Schottky barriers at the interfaces of TiO₂ NTs⁻Ag and Ag⁻MoS₂.
Project description:Zinc oxide (ZnO) is one of the most promising metal oxide semiconductor materials, particularly for optical and gas sensing applications. The influence of thickness and solvent on various features of ZnO thin films deposited at ambient temperature and barometric pressure by the sequential ionic layer adsorption and reaction method (SILAR) was carefully studied in this work. Ethanol and distilled water (DW) were alternatively used as a solvent for preparation of ZnO precursor solution. Superficial morphology, crystallite structure, optical and electrical characteristics of the thin films of various thickness are examined applying X-ray diffraction (XRD) system, scanning electron microscopy, the atomic force microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible spectroscopy, photoluminescence spectroscopy, Hall effect measurement analysis and UV response study. XRD analysis confirmed that thin films fabricated using ethanol or DW precursor solvents are hexagonal wurtzite ZnO with a preferred growth orientation (002). Furthermore, it was found that thin films made using ethanol are as highly crystalline as thin films made using DW. ZnO thin films prepared using aqueous solutions possess high optical band gaps. However, films prepared with ethanol solvent have low resistivity (10-2 Ω cm) and high electron mobility (750 cm2/Vs). The ethanol solvent-based SILAR method opens opportunities to synthase high quality ZnO thin films for various potential applications.
Project description:Co-doping represents a valid approach to maximize the performance of photocatalytic and photoelectrocatalytic semiconductors. Albeit theoretical predictions in hematite suggesting a bulk n-type doping and a surface p-type doping would deliver best results, hematite co-doping with coupled cations possessing low and high oxidation states has shown promising results. Herein, we report, for the first time, Sb and Li co-doping of hematite photoanodes. Particularly, this is also a seminal work for the introduction of the highly reactive Sb5+ directly into the hematite thin films. Upon co-doping, we have a synergistic effect on the current densities with a 67-fold improvement over the standard. Via a combined investigation with profuse photoelectrochemical measurements, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman analyses, we confirm the two doping roles of Sb5+ and Li+ as the substitutional and interstitial dopant, respectively. The improvements are attributed to a higher charge carrier concentration along with a lower charge transfer resistance at the surface.
Project description:Hydrophobically modified poly(vinyl alcohol) (hm-PVA) films with various alkyl chain lengths were prepared. Their surface/mechanical properties, cytocompatibility, and porcine skin adhesion strength were evaluated. hm-PVAs had 10 °C higher glass transition temperature than poly(vinyl alcohol) (PVA) (33.4 ± 2.5 °C). The water contact angle of the hm-PVA films increased with alkyl chain length and/or hydrophobic group modification ratio. The tensile strength of the hm-PVA films decreased with increasing alkyl chain length and/or hydrophobic group modification ratio. hm-PVA with short chain lengths (4 mol % propanal-modified PVA; 4C3-PVA) had low cytotoxicity compared with long alkyl chain length hm-PVAs (4 mol % hexanal and nonanal-modified PVA; 4C6-PVA and 4C9-PVA). The 4C3-PVA film had the highest porcine skin adhesion strength. Thus, the 4C3-PVA film is promising as an adhesive for wearable medical devices.