Enhanced Visible-Light Photocatalytic Activity of Bismuth Ferrite Hollow Spheres Synthesized via Evaporation-Induced Self-Assembly.

Semiconductor hollow spheres have garnered significant attention in recent years due to their unique structural properties and enhanced surface area, which are advantageous for various applications in catalysis, energy storage, and sensing. The present study explores the surfactant-assisted synthesis of bismuth ferrite (BiFeO3) hollow spheres, emphasizing their enhanced visible-light photocatalytic activity. Utilizing a novel, facile, two-step evaporation-induced self-assembly (EISA) approach, monodisperse BiFeO3 hollow spheres were synthesized with a narrow particle size distribution. The synthesis involved Bi/Fe citrate complexes as precursors and the triblock copolymer Pluronic P123 as a soft template. The BiFeO3 hollow spheres demonstrated outstanding photocatalytic performance in degrading the emerging pollutants Rhodamine B and metronidazole under visible-light irradiation (100% degradation of Rhodamine B in <140 min and of metronidazole in 240 min). The active species in the photocatalytic process were identified through trapping experiments, providing crucial insights into the mechanisms and efficiency of semiconductor hollow spheres. The findings suggest that the unique structural features of BiFeO3 hollow spheres, combined with their excellent optical properties, make them promising candidates for photocatalytic applications.

Advances on chalcogenide quantum dots-based sensors for environmental pollutants monitoring.

Water contamination represents a significant ecological impact with global consequences, contributing to water scarcity worldwide. The presence of several pollutants, including heavy metals, pharmaceuticals, pesticides, and pathogens, in water resources underscores a pressing global concern, prompting the European Union (EU) to establish a Water Watch List to monitor the level of these substances. Nowadays, the standard methods used to detect and quantify these contaminants are mainly liquid or gas chromatography coupled with mass spectrometry (LC/GC-MS). While these methodologies offer precision and accuracy, they require expensive equipment and experienced technicians, and cannot be used on the field. In this context, chalcogenide quantum dots (QDs)-based sensors have emerged as promising, user-friendly, practical, and portable tools for environmental monitoring. QDs are semiconductor nanocrystals that possess excellent properties, and have demonstrated versatility across various sensor types, such as fluorescent, electrochemical, plasmonic, and colorimetric ones. This review summarizes recent advances (2019-2023) in the use of chalcogenide QDs for environmental sensing, highlighting the development of sensors capable of detect efficiently heavy metals, anions, pharmaceuticals, pesticides, endocrine disrupting compounds, organic dyes, toxic gases, nitroaromatics, and pathogens.

Scanning Tunneling Spectroscopy Method for the Prediction of Semiconductor Heterojunction Performance as a Prequel for Device Development.

The prediction of semiconductor device performance is a persistent challenge in materials science, and the ability to anticipate useful specifications prior to construction is crucial for enhancing the overall efficiency. In this study, we investigate the constituents of a solar cell by employing scanning tunneling microscopy (STM) and spectroscopy (STS). Through our observations, we identify a spatial distribution of the dopant type in thin films of materials that were designed to present major p-doping for germanium sulfide (GeS) and dominant n-doping for tin disulfide (SnS2). By generating separate STS maps for each semiconductor film and conducting a statistical analysis of the gap and doping distribution, we determine intrinsic limitations for the solar cell efficiency that must be understood prior to processing. Subsequently, we fabricate a solar cell utilizing these materials (GeS and SnS2) via vapor phase deposition and carry out a characterization using standard J-V curves under both dark/illuminated irradiance conditions. Our devices corroborate the expected reduced efficiency due to doping fluctuation but exhibit stable photocurrent responses. As originally planned, quantum efficiency measurements reveal that the peak efficiency of our solar cell coincides with the range where the standard silicon solar cells sharply decline. Our STS method is suggested as a prequel to device development in novel material junctions or deposition processes where fluctuations of doping levels are retrieved due to intrinsic material characteristics such as the occurrence of defects, roughness, local chemical segregation, and faceting or step bunching.

Detection of Water Contaminants by Organic Transistors as Gas Sensors in a Bottom-Gate/Bottom-Contact Cross-Linked Structure.

Detecting volatile organic compounds is a fundamental step in water quality analysis. Methylisoborneol (MIB) provides a lousy odor to water, whereas geosmin (GEO) is responsible for its sour taste. A widely-used technique for their detection is gas-phase chromatography. On the other hand, an electronic nose from organic thin-film transistors is a cheaper and faster alternative. Poly(2,5-bis(3-tetradecyl-thiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-C14) features semiconducting properties suitable for organic electronics. However, in order to expose the active layer in a bottom-gate transistor structure with photolithographically patterned electrodes, a cross-linked dielectric such as poly(4-vinyl phenol) (PVP) is necessary. In this work, the cross-linking was demonstrated using FTIR and Raman spectroscopies, as well as high-k capacitors with a dielectric constant of 5.3. The presence of enhanced crystallinity with terrace formation in the semiconducting film was confirmed with UV-visible spectrophotometry, atomic force microscopy, and X-ray diffraction. Finally, for the first time, a PBTTT-C14 transistor on cross-linked PVP was shown to respond to isoborneol with a sensitivity of up to 6% change in mobility per ppm. Due to its similarity to MIB, a system comprising these sensors must be investigated in the future as a tool for sanitation companies in real-time water quality monitoring.

Effect of the tri-sodium citrate as a complexing agent in the deposition of ZnS by SILAR.

Using the SILAR method Zinc sulfide coatings were deposited on glass slices. The physical properties and the chemical mechanism throughout the variation in concentration of tri-sodium citrate (TSC) as a chelating agent in the synthesis of thin films were investigated. Results shows that ZnS thin films exhibit an average transmittance of 16% in visible light spectra region and a zinc blende structure. The ZnS films synthesized using TSC as a complexing agent, present a smaller average particle size, an average transmittance of 85%, and an adsorption edge at 300-340 nm. Based on our experimental data and analysis, we conclude that the contribution of the oxychloride species, a subproduct in the chemical deposition, is suggested to be related as an impurity level former in the synthesis of ZnS thin films. TSC as a complexing agent in the SILAR technique is a non-toxic option to reduce the generation of the oxychloride species and synthesize a wide band gap semiconductor. Moreover, the use of complexing agents could be extended to other types of semiconductors deposited by SILAR.

New Benzotrithiophene-Based Molecules as Organic P-Type Semiconductor for Small-Molecule Organic Solar Cells.

A new benzotrithiophene-based small molecule, namely 2,5,8-Tris[5-(2,2-dicyanovinyl)-2-thienyl]-benzo[1,2-b:3,4-b':6,5-b″]-trithiophene (DCVT-BTT), was successfully synthesized and subsequently characterized. This compound was found to present an intense absorption band at a wavelength position of ∼544 nm and displayed potentially relevant optoelectronic properties for photovoltaic devices. Theoretical studies demonstrated an interesting behavior of charge transport as electron donor (hole-transporting) active material for heterojunction cells. A preliminary study of small-molecule organic solar cells based on DCVT-BTT (as the P-type organic semiconductor) and phenyl-C61-butyric acid methyl ester (as the N-type organic semiconductor) exhibited a power conversion efficiency of 2.04% at a donor: acceptor weight ratio of 1:1.

Obtaining of Mg-Zn Co-Doped GaN Powders via Nitridation of the Ga-Mg-Zn Metallic Solution and Their Structural and Optical Properties.

Mg-Zn co-dopedGaN powders via the nitridation of a Ga-Mg-Zn metallic solution at 1000 °C for 2 h in ammonia flow were obtained. XRD patterns for the Mg-Zn co-dopedGaN powders showed a crystal size average of 46.88 nm. Scanning electron microscopy micrographs had an irregular shape, with a ribbon-like structure and a length of 8.63 µm. Energy-dispersive spectroscopy showed the incorporation of Zn (Lα 1.012 eV) and Mg (Kα 1.253 eV), while XPS measurements showed the elemental contributions of magnesium and zinc as co-dopant elements quantified in 49.31 eV and 1019.49 eV, respectively. The photoluminescence spectrum showed a fundamental emission located at 3.40 eV(364.70 nm), which was related to band-to-band transition, besides a second emission found in a range from 2.80 eV to 2.90 eV (442.85-427.58 nm), which was related to a characteristic of Mg-doped GaN and Zn-doped GaN powders. Furthermore, Raman scattering demonstrated a shoulder at 648.05 cm-1, which could indicate the incorporation of the Mg and Zn co-dopants atoms into the GaN structure. It is expected that one of the main applications of Mg-Zn co-doped GaN powders is in obtaining thin films for SARS-CoV-2 biosensors.

The role of defects in the persistent photoconductivity of BaSnO3thin films.

Time-dependent photoconductivity (PC) and PC spectra have been studied in oxygen deficient BaSnO3thin films grown on different substrates. X-ray spectroscopy measurements show that the films have epitaxially grown on MgO and SrTiO3substrates. While on MgO the films are nearly unstrained, on SrTiO3the resulting film is compressive strained in the plane. Electrical conductivity in dark is increased in one order of magnitude for the films on SrTiO3in comparison to the one on MgO. This leads to an increase of PC in the latter film in at least one order of magnitude. PC spectra show a direct gap with a value ofEG=3.9eV for the film grown on MgO while on SrTiO3EG=3.36eV. For both type of films, time-dependent PC curves show a persistent behavior after illumination is removed. These curves have been fitted employing an analytical procedure based on the frame of PC as a transmission phenomenon showing the relevant role of donor and acceptor defects as carrier traps and as a source of carriers. This model also suggests that in the BaSnO3film on SrTiO3more defects are created probably due to strain. This latter effect can also explain the different transition values obtained for both type of films.

Poly(butylene adipate-co-terephthalate)/Poly(lactic acid) Polymeric Blends Electrospun with TiO2-R/Fe3O4 for Pollutant Photodegradation.

This work aimed to use the electrospinning technique to obtain PBAT/PLA polymer fibers, with the semiconductors rutile titanium dioxide (TiO2-R) and magnetite iron oxide (Fe3O4), in order to promote the photocatalytic degradation of environmental contaminants. The parameters used in the electrospinning process to obtain the fibers were distance from the needle to the collecting target of 12 cm, flow of 1 mL h-1 and voltage of 14 kV. The best mass ratio of semiconductors in the polymeric fiber was defined from a 22 experimental design, and the values obtained were 10% TiO2-R, 1% Fe3O4 at pH 7.0. Polymer fibers were characterized by Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD), Thermogravimetric Analysis (TGA) and Fourier Transform Infrared (FTIR) techniques. SEM measurements indicated a reduction in fiber diameter after the incorporation of semiconductors; for the PBAT/PLA fiber, the average diameter was 0.9466 ± 0.2490 µm, and for the fiber with TiO2-R and Fe3O4 was 0.6706 ± 0.1447 µm. In the DSC, DRX, TGA and FTIR analyses, it was possible to identify the presence of TiO2-R and Fe3O4 in the fibers, as well as their interactions with polymers, demonstrating changes in the crystallinity and degradation temperature of the material. These fibers were tested against Reactive Red 195 dye, showing an efficiency of 64.0% within 24 h, showing promise for photocatalytic degradation of environmental contaminants.

ZnO recovered from spent alkaline batteries as antimicrobial additive for waterborne paints.

Biocides are employed to prevent biodeterioration in waterborne paints. In the present study, we used zinc oxide nanoparticles (obtained from spent alkaline batteries) as biocide for indoor waterborne paint at 1.5% of the total solid content in paint. Two different zinc oxides synthesized from spent alkaline batteries, which showed photocatalyst activity, were employed as an antimicrobial agents. After leaching the anode of alkaline batteries, zinc was precipitated from the leachate liquor by introducing oxalic acid (O-ZnO) or sodium carbonate (C-ZnO). The antimicrobial properties of the prepared oxides were tested against Staphylococcus aureus (bacteria), Chaetomium globosum, and Aspergillus fumigatus (fungi) using agar well diffusion method. C-ZnO inhibited the growth of all the strains studied and presented enhanced activity than O-ZnO. The better performance as antimicrobial agent of C-ZnO compared to O-ZnO was attributed to its lower crystallite size, higher amount of oxygen monovacancies, and to its lower band gap energy. The oxide with the best performance in antimicrobial activity, C-ZnO, was employed for the formulation of waterborne acrylic paints. It was observed that 1.5% C-ZnO improved the antifungal properties and antibacterial properties compared to the control sample.

Cu(C3H3N3S3)3 Adsorption onto ZnTiO3/TiO2 for Coordination-Complex Sensitized Photochemical Applications.

Currently, the design of highly efficient materials for photochemical applications remains a challenge. In this study, an efficient semiconductor was prepared, based on a coordination complex (Cu-TTC) of Cu(I) and trithiocyanuric acid on ZnTiO3/TiO2 (ZTO/TO). The Cu-TTC/ZTO/TO composite was prepared by the solvothermal method at room temperature. The structural, optical, and electrochemical characteristics, as well as the photocatalytic performance of the composite, were experimentally and computationally studied. The results show that the Cu-TTC/ZTO/TO composite efficiently extended its photoresponse in the visible region of the electromagnetic spectrum. The electrochemistry of the proposed tautomeric architecture (s-Cu-TTC) clearly reveals the presence of metal-ligand charge-transfer (MLCT) and π → π* excitations. The maximum methylene blue (MB) dye photodegradation efficiency of 95% in aqueous solutions was achieved under the illumination of simulated solar light. Finally, computational calculations based on the Density Functional Theory (DFT) method were performed to determine the electronic properties of the s-Cu-TTC tautomeric structure and clarify the adsorption mechanism of this complex on the surface (101) of both ZnTiO3 and TiO2 oxides. The results obtained allow us to suggest that the Cu-TTC complex is an effective charge carrier and that the Cu-TTC/ZTO/TO composite can be used efficiently for photochemical applications.

Clinical and histopathological features of congenital epulis in a newborn submitted to laser surgery.

Congenital epulis (CE) is a rare condition in newborns, whose histogenesis remains unclear. It mostly presents as a circumscribed mass in the maxilla alveolar ridge of female neonates and can interfere with their normal breathing and breastfeeding. This benign oral lesion usually appears as a pedunculated nodule covered with normal mucosa that extends from the anterior vestibular alveolar ridge up to the posterior region. There are some pathological conditions that show clinical and histopathological features similar to those of CE, such as granular cell tumor, gingival cyst of the newborn, vascular malformations and others. This case report aimed to describe the clinical and pathological features of a newborn patient with a clinical and histopathological diagnosis of CE on the right side of the maxillary alveolar ridge, treated with excision by laser surgery, with a follow-up of 5 months without any sign of recurrence.

Two-Dimensional Titanium Dioxide-Surfactant Photoactive Supramolecular Networks: Synthesis, Properties, and Applications for the Conversion of Light Energy.

The desire to harness solar energy to address current global environmental problems led us to investigate two-dimensional (2D) core-shell hybrid photocatalysts in the form of a 2D-TiO2-surfactant, mainly composed of fatty acids. The bulk products, prepared by two slightly different methods, consist of stacked host-guest hybrid sheets held together by van der Waals forces between alkyl carboxylate moieties, favoring the synergistic conjugation of the photophysical properties of the core and the hydrophobicity of the self-assembled surfactant monolayer of the shell. X-ray diffraction and the vibrational characteristics of the products revealed the influence of synthesis strategies on two types of supramolecular aggregates that differ in the core chemical structure, guest conformers of alkyl surfactant tails and type, and the bilayer and monolayer of the structure of nanocomposites. The singular ability of the TiO2 core to anchor carboxylate leads to commensurate hybrids, in contrast to both layered clay and layered double-hydroxide-based ion exchangers which have been previously reported, making them potentially interesting for modeling the role of fatty acids and lipids in bio-systems. The optical properties and photocatalytic activity of the products, mainly in composites with smaller bandgap semiconductors, are qualitatively similar to those of nanostructured TiO2 but improve their photoresponse due to bandgap shifts and the extreme aspect-ratio characteristics of two-dimensional TiO2 confinement. These results could be seen as a proof-of-concept of the potential of these materials to create custom-designed 2D-TiO2-surfactant supramolecular photocatalysts.

Novel Semiconductor Cu(C3H3N3S3)3/ZnTiO3/TiO2 for the Photoinactivation of E. coli and S. aureus under Solar Light.

The use of semiconductors for bacterial photoinactivation is a promising approach that has attracted great interest in wastewater remediation. The photoinactivator Cu-TTC/ZTO/TO was synthesized by the solvothermal method from the coordination complex Cu(C3H3N3S3)3 (Cu-TTC) and the hybrid semiconductor ZnTiO3/TiO2 (ZTO/TO). In this study, the effect of photocatalyst composition/concentration as well as radiation intensity on the photoinactivation of the gram-negative bacteria Escherichia coli and the gram-positive bacteria Staphylococcus aureus in aqueous solutions was investigated. The results revealed that 25 mg/mL of photoinactivator, in a Cu-TTC:ZTO/TO molar ratio of 1:2 (w/w%) presents a higher rate of bacterial photoinactivation under simulated solar light (λ = 300-800 nm) in comparison to the individual components. The evidence of this study suggests that the presence of the Cu(C3H3N3S3)3 coordination complex in the ZnTiO3/TiO2 hybrid semiconductor would contribute to the generation of reactive oxygen species (ROS) that are essential to initiate the bacterial photoinactivation process. Finally, the results obtained allow us to predict that the Cu-TTC/ZTO/TO photocatalyst could be used for effective bacterial inactivation of E. coli and S. aureus in aqueous systems under simulated solar light.

Alkylated Benzodithienoquinolizinium Salts as Possible Non-Fullerene Organic N-Type Semiconductors: An Experimental and Theoretical Study.

Three photobicyclized benzodithienoquinolizinium tetrafluoroborates (BPDTQBF4) were prepared and evaluated by UV-Vis and fluorescence spectral, electrochemical analysis, and by theoretical calculations as possible organic n-type semiconductors. Evaluation and comparison of their LUMO levels, HOMO-LUMO energy gaps as monomeric and π-stacked dimers with those of other materials, suggest their potential as organic n-type semiconductors. Calculations of their relative charge carrier mobilities confirmed this potential for one derivative with a long (C-14) alkyl chain appended to the polycyclic planar π-system.

Improved photocatalytic oxidation of arsenic (III) with WO3/TiO2 nanomaterials synthesized by the sol-gel method.

Photocatalytic oxidation of arsenite (As(III)) to arsenate (As(V)) was studied in aqueous solution using a series of WO3/TiO2 semiconductors readily synthesized through sol-gel method with WO3 content in the range of 1-5 wt%. The resulting materials showed enhanced photocatalytic activity towards As(III) photo-oxidation compared to their individual counterparts under UV radiation. The amount of As(III) and As(V) species in the irradiated solution was determined using the molybdenum blue method. The efficiency of photoinduced carriers separation was further affirmed by electrical impedance spectroscopy (EIS) and photocurrent tests. The maximum catalytic efficiency was observed when the binary oxide 3%WO3/TiO2 (TW3) was used, reaching a 99% conversion of As(III) to As(V) within the first 25 min under UV irradiation. The enhanced photocatalytic performance of the heterostructures could be explained as consequent to an improved charge separation due to the migration of photoproduced holes in TW3 photocatalyst. Based on the electric band structure of WO3 and TiO2, a reasonable mechanism for the photo-oxidation of As(III) over TW3 novel catalyst has been proposed.

LED irradiated photo-Fenton for the removal of estrogenic activity and endocrine disruptors from wastewater treatment plant effluent.

The goal of this work was to evaluate the performance of the LED irradiated photo-Fenton process on the removal of (i) estrogenic activity and (ii) seven endocrine disruptors (EDs) (4-octylphenol, 4-nonylphenol, bisphenol A, estrone, 17ß-estradiol, 17α-ethinylestradiol, and estriol) from real wastewater treatment plant effluent (WWTPE). EDs are a group of contaminants of emerging concern present in WWTPE and which may be recognized by hormone receptors, thus harming animal and human health. The yeast estrogenic screen test (YES) was used to quantify estrogenic activity promoted by EDs in WWTPE samples before and after photo-Fenton treatment. Tests were performed following a factorial design with different iron (20, 40, and 60 mg L-1) and hydrogen peroxide (100, 200, and 300 mg L-1) concentrations in a laboratory scale LED photoreactor (λ = 455 nm, 1.5 L, 1.6 × 10-6 Einstein s-1). EDs were analyzed by gas chromatography coupled to a mass spectrometer. Control experiments consisted of Fenton process, iron only, LED irradiation only, and H2O2 only. Optimum experimental conditions for LED photo-Fenton resulted in 62% removal of estrogenic activity and 59% mineralization. In addition, treated WWTPE was not toxic to Aliivibrio fischeri and more than 80% of EDs were removed during LED irradiated photo-Fenton. Although Fenton process showed similar efficiency to that obtained by LED photo-Fenton, a higher volume of sludge was generated in the dark. Finally, results obtained in this study confirm the applicability of LED irradiated photo-Fenton process for improving the quality of WWTPE as an alternative to solar photo-Fenton in case solar radiation is not available, thus reducing hazards associated to WWTPE reuse or discharge.

Organic Thin-Film Transistors as Gas Sensors: A Review.

Organic thin-film transistors (OTFTs) are miniaturized devices based upon the electronic responses of organic semiconductors. In comparison to their conventional inorganic counterparts, organic semiconductors are cheaper, can undergo reversible doping processes and may have electronic properties chiefly modulated by molecular engineering approaches. More recently, OTFTs have been designed as gas sensor devices, displaying remarkable performance for the detection of important target analytes, such as ammonia, nitrogen dioxide, hydrogen sulfide and volatile organic compounds (VOCs). The present manuscript provides a comprehensive review on the working principle of OTFTs for gas sensing, with concise descriptions of devices' architectures and parameter extraction based upon a constant charge carrier mobility model. Then, it moves on with methods of device fabrication and physicochemical descriptions of the main organic semiconductors recently applied to gas sensors (i.e., since 2015 but emphasizing even more recent results). Finally, it describes the achievements of OTFTs in the detection of important gas pollutants alongside an outlook toward the future of this exciting technology.

Sugar-Mediated Green Synthesis of Silver Selenide Semiconductor Nanocrystals under Ultrasound Irradiation.

Silver selenide (Ag2Se) is a promising nanomaterial due to its outstanding optoelectronic properties and countless bio-applications. To the best of our knowledge, we report, for the first time, a simple and easy method for the ultrasound-assisted synthesis of Ag2Se nanoparticles (NPs) by mixing aqueous solutions of silver nitrate (AgNO3) and selenous acid (H2SeO3) that act as Ag and Se sources, respectively, in the presence of dissolved fructose and starch that act as reducing and stabilizing agents, respectively. The concentrations of mono- and polysaccharides were screened to determine their effect on the size, shape and colloidal stability of the as-synthesized Ag2Se NPs which, in turn, impact the optical properties of these NPs. The morphology of the as-synthesized Ag2Se NPs was characterized by transmission electron microscopy (TEM) and both α- and ß-phases of Ag2Se were determined by X-ray diffraction (XRD). The optical properties of Ag2Se were studied using UV-Vis spectroscopy and its elemental composition was determined non-destructively using scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS). The biological activity of the Ag2Se NPs was assessed using cytotoxic and bactericidal approaches. Our findings pave the way to the cost-effective, fast and scalable production of valuable Ag2Se NPs that may be utilized in numerous fields.

Modification of the photoconducting properties of ZnO thin films via low-temperature annealing and air exposure.

A simple thermal annealing at 150 °C followed by exposure to air ambient conditions in epitaxial ZnO thin films produces a photoconductivity enhancement and a reduction of the energy gap. The first effect is related to a release of carriers from bulk traps while the second is caused by a gradual adsorption of species on the film surface which increases the band bending, as x-ray photoemission spectroscopy (XPS) shows. An observed drift of the photoconductivity and the energy gap over the days is connected to this adsorption kinetics. These findings have a potential application in ZnO based optoelectronic devices.