High-resolution X-ray Photoelectron Spectroscopy Research Articles

Construction of 2D/2D Mesoporous WO3/CeO2 Laminated Heterojunctions for Optimized Photocatalytic Performance.

Photocatalytic elimination of antibiotics from the environment and drinking water is of great significance for human health. However, the efficiency of photoremoval of antibiotics such as tetracycline is severely limited by the prompt recombination of electron holes and slow charge migration efficacy. Fabrication of low-dimensional heterojunction composites is an efficient method for shortening charge carrier migration distance and enhancing charge transfer efficiency. Herein, 2D/2D mesoporous WO3/CeO2 laminated Z-scheme heterojunctions were successfully prepared using a two-step hydrothermal process. The mesoporous structure of the composites was proved by nitrogen sorption isotherms, in which sorption-desorption hysteresis was observed. The intimate contact and charge transfer mechanism between WO3 nanoplates and CeO2 nanosheets was investigated using high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy measurements, respectively. Photocatalytic tetracycline degradation efficiency was noticeably promoted by the formation of 2D/2D laminated heterojunctions. The improved photocatalytic activity could be attributed to the formation of Z-scheme laminated heterostructure and 2D morphology favoring spatial charge separation, confirmed by various characterizations. The optimized 5WO3/CeO2 (5 wt.% WO3) composites can degrade more than 99% of tetracycline in 80 min, achieving a peak TC photodegradation efficiency of 0.0482 min-1, which is approximately 3.4 times that of pristine CeO2. A Z-scheme mechanism is proposed for photocatalytic tetracycline by from WO3/CeO2 Z-scheme laminated heterojunctions based on the experimental results.

Synthesis and catalytic performance of nanoflower-like Ru@CoAl-LDH composite catalyst for NaBH4 hydrolysis

Sodium borohydride (NaBH4) has been widely regarded as the one of most promising future hydrogen (H2)-generated materials. Therefore, it is necessary to find a catalyst with higher catalytic performance to promote the on-demand H2 release of NaBH4 hydrolysis. In this study, a [email protected] catalyst was developed by immobilizing Ru nanoparticles (Ru NPs) on the surface of Co Al Layered Double Hydroxide (CoAl-LDH) nanocurds. The Ru NPs were prepared by H2 reduction, and nanoflower-like CoAl-LDH was synthesized through a one-step solvothermal method. The microstructure and composition of the catalysts were investigated through scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results showed that [email protected] exhibited good catalytic performance toward the NaBH4 hydrolysis. At 30 °C, the hydrogen generation rate of the hydrolysis reaction was 44.34 L·min−1·gRu−1, and the reaction activation energy was 38.83 kJ·mol−1, and superior to many catalysts of the same type. Because of its high activity, low activation energy and excellent economic performance, this catalyst has high potential for applications in NaBH4 hydrolysis.

Construction of tight ultrafiltration membrane for efficient dye/salt separation with physical and chemical self-healing property

This work developed a novel self-healing tight UF membrane based on damages to membrane during operation and cleaning via blending AMPS-PANI into the membrane matrix, which can not only endow the membrane with physical and chemical self-healing properties, but also enable the membrane to obtain effective separation performance of inorganic salt and dyes. Taking AMPS-PANI membrane (M4) as an example, the self-healing test showed that the dye/salt rejection rates of M4 membrane recovered to near pre-damage levels (more than 98%) for the physical damage. As for chemical damage, the high-resolution XPS spectra of S 2p of M4 membrane after damage displayed a larger S-C-C peak area than that before damage. The above results prove that the membrane has self-healing ability after physical and chemical damage. The observed physical self-healing property is ascribed to the swelling behavior of AMPS hydrogels, the fluidity of hydrogel chains and strong hydrogen bonding, and owing the chemical self-healing property to the Michael addition reaction between carbon–carbon double bonds and free radicals. The pure water flux, dye/salt rejection rate, structure, mechanical properties and porosity of the self-healing tight UF membrane were systematically investigated to evaluate its feasibility as an actual filtration membrane for textile wastewater. The results of the research indicate that membrane including both physical and chemical self-healing is a promising way to improve water filtration membrane with self-healing ability.

Irradiation-enhanced Interactions at UO2/Al2O3/Al Interfaces

Combustion synthesis is used to prepare thin UO2 films on aluminum alloy substrates. This simple preparation method involves electrospraying uranyl nitrate + acetylacetone + 2-methoxyethanol solution on the substrate, followed by a short annealing at 350 or 550 °C. The irradiation of films with a 40Ar2+ ion beam (energy of 1.7 MeV and fluences of 7.7 × 1016 and 1.3 × 1017 ions/cm2) is conducted to investigate irradiation-induced restructuring processes. High-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) investigations show that the annealing temperature significantly influences the crystallinity and stability of materials during irradiation. A small amount of Mg in the alloy substrate diffuses into the amorphous Al2O3 interfacial layer between the film and the substrate. Local thermal spikes from the incoming ions facilitate the irradiation-induced mixing of immiscible Al2O3 and UO2 for the materials prepared at 350 °C. This mass diffusion produces relatively large cavities at the interface. Selective diffusion of a more significant amount of Mg for the materials prepared at 550 °C suppresses the mixing of the Al2O3 interlayer with the film but forms MgyU1–yO2±x solid solutions during irradiation. Local thermal heating triggers the precipitation of a discontinuous crystalline MgO layer close to the film surface. The enhanced and selective diffusion of Mg into the film makes the materials prepared at 550 °C more robust and mechanically stable than those prepared at 350 °C.

α-In2Se3 Nanostructure-Based Photodetectors for Tunable and Broadband Response

The strong thickness-dependent narrow direct band gap of few-layer α-In2Se3 makes it a promising candidate for high-performance photodetectors. However, few researchers focus on the relationship between thickness and optoelectronic characteristics, and most results are based on the mechanically exfoliated α-In2Se3 nanoflakes. Herein, a reliable physical vapor deposition strategy to grow α-In2Se3 nanosheets with tunable thickness and submillimeter scale is reported. High-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) studies confirmed the high-quality growth of α-In2Se3 nanosheets. The back-gate field-effect transistors on SiO2 substrates display n-type semiconductor behavior. A systematical investigation of the optoelectronic properties reveals a thickness-dependent broadband response from visible (447 nm) to near-infrared (1550 nm) wavelengths with better and excellent performance obtained in thicker α-In2Se3 nanosheets than that in thinner devices. More importantly, a great improvement of the responsivity, detectivity, and external quantum efficiency (EQE) can be achieved by changing the thickness of In2Se3. The photodetector exhibits an outstanding photoresponsivity of 347.6 A/W, an ultrahigh detectivity of 1.5 × 1013 Jones, and an external quantum efficiency of 8.3 × 104%, which is superior to several α-In2Se3 nanostructure- or other two-dimensional (2D)-based photodetectors. The thickness-dependent broadband response characteristics make the α-In2Se3 nanostructure a promising candidate for multifunctional optoelectronic device applications.

Nanoarchitecture of a Ti3C2@TiO2 Hybrid for Photocatalytic Antibiotic Degradation and Hydrogen Evolution: Stability, Kinetics, and Mechanistic Insights.

Designing of a visible-light-driven semiconductor-based heterojunction with suitable band alignment and well-defined interfacial contact is considered to be an effective strategy for the transformation of solar-to-chemical energy and environmental remediation. In this context, MXenes have received tremendous attention in the research community due to their merits of abundant derivatives, elemental composition, excellent metallic conductivity, and surface termination groups. Meanwhile, a facile synthetic strategy for MXene-derived TiO2 nanocomposites with stable framework and higher photocatalytic activity under visible-light irradiation still remains a challenge for researchers. Herein, we report a novel synthetic strategy of preparing a two-dimensional Ti3C2@TiO2 nanohybrid by a facile reflux method under acidic conditions. In this oxidation reaction, protonation of the hydroxyl terminal group of MXene creates Ti more electrophilic and susceptible to an oxidative nucleophilic addition reaction with the presence of both water and oxygen. The physicochemical properties of the nanohybrid Ti3C2@TiO2 were verified by varieties of characterization techniques. High-resolution transmission electron microscopy and X-ray photoelectron spectroscopy analysis specifically elucidated the intimate interfacial interaction between Ti3C2 and TiO2. The optimized Ti3C2@TiO2-48 h photocatalyst exhibited the highest tetracycline hydrochloride (TCH, 90% in 90 min) degradation efficiency in comparison to pristine TiO2 with a rate constant (k) of 0.02463 min-1. The major contribution of •O2- and •OH radicals throughout photocatalytic TCH degradation was confirmed by the trapping experiment. Moreover, the photocatalyst showed the highest hydrogen generation rate of 140.8 μmol h-1 along with an apparent conversion efficiency of 2.2%. The excellent photocatalytic activity of Ti3C2@TiO2 originated from the superior electrical conductivity of cocatalyst Ti3C2, which facilitated spatial photogenerated e-/h+ separation and transfer at the Ti3C2 MXene@TiO2 interface. Overall, this research work will describe a promising protocol of designing MXene-derived photocatalysts toward efficient environmental remediation and wastewater treatment applications.

Trimetallic Oxide Foam as an Efficient Catalyst for Fixation of CO2 into Oxazolidinone: An Experimental and Theoretical Approach

The excess anthropogenic CO2 depletion via the catalytic approach to produce valuable chemicals is an industrially challenging, demanding, and encouraging strategy for CO2 fixation. Herein, we demonstrate a selective one-pot strategy for CO2 fixation into "oxazolidinone" by employing stable porous trimetallic oxide foam (PTOF) as a new catalyst. The PTOF catalyst was synthesized by a solution combustion method using transition metals Cu, Co, and Ni and systematically characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), N2 sorption, temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS) analysis. Due to the distinctive synthesis method and unique combination of metal oxides and their percentage, the PTOF catalyst displayed highly interconnected porous channels along with uniformly distributed active sites on its surface. Well ahead, the PTOF catalyst was screened for the fixation of CO2 into oxazolidinone. The screened and optimized reaction parameters revealed that the PTOF catalyst showed highly efficient and selective activity with 100% conversion of aniline along with 96% selectivity and yield toward the oxazolidinone product at mild and solvent-free reaction conditions. The superiority of the catalytic performance could be due to the presence of surface active sites and acid-base cooperative synergistic properties of the mixed metal oxides. A doubly synergistic plausible reaction mechanism was proposed for the oxazolidinone synthesis experimentally with the support of DFT calculations along with bond lengths, bond angles, and binding energies. In addition, stepwise intermediate formations with the free energy profile were also proposed. Also, the PTOF catalyst displayed good tolerance toward substituted aromatic amines and terminal epoxides for the fixation of CO2 into oxazolidinones. Very interestingly, the PTOF catalyst could be significantly reused for up to 15 consecutive cycles with stable activity and retention in physicochemical properties.

On the surface oxidation and band alignment of ferroelectric Sc0.18Al0.82N/GaN heterostructures

Ferroelectric scandium aluminum nitride (ScAlN), owing to its unique properties and seamless integration with the mainstream GaN technology, has attracted considerable attention as one of the most promising materials for next-generation multifunctional electronics. To date, however, a detailed understanding of the fundamental surface properties and the band alignment of ScAlN/III-nitride heterostructure has remained elusive. In this work, with the use of high-resolution X-ray photoelectron spectroscopy measurements, we demonstrate the existence of a considerable oxidation layer on ScAlN when it is exposed to air, which shows a significant impact on the material characterization and electronic structure evaluation. By excluding the possible impact from the surface oxide layer, the band alignment of Sc0.18Al0.82N/GaN can be correctly determined. Simulation results further showed that the Sc0.18Al0.82N barrier layer could offer excellent charge carrier confinement and a high density of two-dimensional electron gas (2DEG) at the heterostructure interface, which is needed for GaN-based high electron mobility transistors (HEMTs) with enhanced performance. This work not only identifies the band alignment between Sc0.18Al0.82N and GaN for future novel ScAlN/III-nitride device applications but also highlights the importance of considering the prevalent surface oxidation issue in the emerging ferroelectric nitride family.

Effect of Temperature on the Tribological Properties of Hafnium Carbonitrides Coatings

For industrial processes in which refractory metals are necessary, hafnium carbonitride exhibits excellent performance due to its high thermal conductivity and resistance to oxidation. In this study, hafnium carbonitride was deposited on Inconel 718 steel and silicon (100) substrates. The objective was to characterize the wear properties as a function of temperature. The layers were deposited by physical vapor deposition (PVD) in an R.F. sputtering magnetron system from carbon targets and high-purity hafnium (99.99%). The wear tests were carried out at temperatures of 100 °C, 200 °C, 400 °C, and 800 °C in non-lubricated conditions. The coefficient of friction (COF) was recorded in situ. The heat treatment temperature on coatings is essential in determining anti-wear efficiency. It was determined that high temperatures (800 °C) improve resistance to wear. High-resolution XPS spectra were used to detect the chemical states of Hf 4f5/2 and Hf 4f7/2. The 4f5/2 and 4f7/2 binding energy indicates the presence of HfN and HfC. Using the TEM technique in bright field mode allowed us to know the orientation, crystallographic structure and interplanar distances of the HfCN. The topography of the coatings, by AFM, shows uniform grains and very small characteristics that determine the low surface roughness value. The SEM image of the cross-section of the HfCN coating shows homogeneity of the layer; no cracks or deformations are observed.

Ecofriendly sol-gel-derived dye-sensitized solar cells with aluminium-doped tin oxide photoanode.

The manuscript reports the fabrication of an eco-friendly sol gel dye-sensitized solar cell (DSSC) based on aluminium (Al)-doped tin oxide nanoparticles with different concentrations (0.5, 1, and 5 mol%) of Al providing enhanced optical and electrical properties than its bare counterparts. The physical, chemical, optical, and electrical properties of the as-synthesized nanoparticles were studied using different analytical tools. X-ray diffraction (XRD) study reveals the crystal structure of the prepared samples ascribed to SnO2 nanoparticles uniformly with reduced crystallite size for Al-doped SnO2 nanoparticles. Field emission scanning electron microscope (FESEM) analysis reveals narrowing of particle size on doping with the Al, substantially enhancing the optical and surface characteristic features of the SnO2 nanoparticles. Photoconductivity studies indicate that all the samples have a good linear response with the increment of electric field in dark and photocurrent attributing to better photoconversion capability of the samples. Further, the optimized Al-doped SnO2 and bare SnO2 nanoparticles were subjected to sophisticated analytical studies such as high-resolution transmission electron microscope (HR-TEM) and X-ray photoelectron spectroscopy (XPS) for the better insight into their properties. The as-prepared Al-doped SnO2 nanoparticles in the present study record good optical, surface, and electrical properties which enhance their compatibility for possible photovoltaic applications especially in dye-sensitized solar cells as an environmentally safe alternate energy solution. Further, the current density-voltage (J-V) characteristics of the optimized Al-SnO2 and bare SnO2 photoanode component were probed for their suitability in DSSCs which disclosed enriched efficiency upon doping with aluminium nanoparticles.

Nanocomposites with ZrO2@S-Doped g-C3N4 as an Enhanced Binder-Free Sensor: Synthesis and Characterization.

This study describes new electrocatalyst materials that can detect and reduce environmental pollutants. The synthesis and characterization of semiconductor nanocomposites (NCs) made from active ZrO2@S-doped g-C3N4 is presented. Electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) measurements were used to examine electron transfer characteristics of the synthesized samples. Using X-ray diffraction (XRD) and high-resolution scanning electron microscopy (HR-SEM) techniques, inclusion of monoclinic ZrO2 on flower-shaped S-doped-g-C3N4 was visualized. High-resolution X-ray photoelectron spectroscopy (XPS) revealed successful doping of ZrO2 into the lattice of S-doped g-C3N4. The electron transport mechanism between the electrolyte and the fluorine tin-oxide electrode (FTOE) was enhanced by the synergistic interaction between ZrO2 and S-doped g-C3N4 as co-modifiers. Development of a platform with improved conductivity based on an FTOE modified with ZrO2@S-doped g-C3N4 NCs resulted in an ideal platform for the detection of 4-nitrophenol (4-NP) in water. The electrocatalytic activity of the modified electrode was evaluated through determination of 4-NP by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) under optimum conditions (pH 5). ZrO2@S-doped g-C3N4 (20%)/FTOE exhibited good electrocatalytic activity with a linear range from 10 to 100 μM and a low limit of detection (LOD) of 6.65 μM. Typical p-type semiconductor ZrO2@S-doped g-C3N4 NCs significantly impact the superior detection of 4-NP due to its size, shape, optical properties, specific surface area and effective separation of electron-hole pairs. We conclude that the superior electrochemical sensor behavior of the ZrO2@S-doped g-C3N4 (20%)/FTOE surfaces results from the synergistic interaction between S-doped g-C3N4 and ZrO2 surfaces that produce an active NC interface.

Efficient activation of persulfate by Ti3C2 MXene QDs modified ZnFe2O4 for the rapid degradation of tetracycline

Mxene-based catalysts with specific interfacial characteristics are beneficial for photocatalytic applications. Herein, Ti3C2 MXene modified ZnFe2O4 nanocomposite materials were prepared for photocatalysis. The morphology and structure of the nanocmposites were characterized by scanning electron microscopy (SEM), High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), which revealed that Ti3C2 MXene as quantum dots (QDs) was uniformly distributed on the ZnFe2O4 surface. The Ti3C2 QDs modified ZnFe2O4 catalyst (ZnFe2O4/MXene-15%) under visible light achieved 87% degradation efficiency of tetracycline within 60 min when coupled with persulfate (PS) system. The initial solution pH, PS dosage and co-existing ions were found to be the main factors affecting the heterogeneous oxidation process, while quenching experiments showed that O2•- is the main oxidizing species in the removal of tetracycline in ZnFe2O4/MXene-PS system. In addition, the cyclic experiments suggested that ZnFe2O4/MXene had good stability and thus it may have practical applications in industry.

The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters

Size-selected iron oxide nanoclusters are outstanding candidates for technological-oriented applications due to their high efficiency-to-cost ratio. However, despite many theoretical studies, experimental works on their oxidation mechanism are still limited to gas-phase clusters. Herein we investigate the oxidation of graphene-supported size-selected Fen clusters by means of high-resolution X-ray Photoelectron Spectroscopy. We show a dependency of the core electron Fe 2p3/2 binding energy of metallic and oxidized clusters on the cluster size. Binding energies are also linked to chemical reactivity through the asymmetry parameter which is related to electron density of states at the Fermi energy. Upon oxidation, iron atoms in clusters reach the oxidation state Fe(II) and the absence of other oxidation states indicates a Fe-to-O ratio close to 1:1, in agreement with previous theoretical calculations and gas-phase experiments. Such knowledge can provide a basis for a better understanding of the behavior of iron oxide nanoclusters as supported catalysts.

Decoration of 1,3 oxazole modified g- C3N4 by Bio-synthesized Ag nanoparticle for the photodegradation of pharmaceutical effluent: Clotrimazole

The current work demonstrates the fabrication of Ag nanoparticle (Ag nps) loaded oxazole modified g- C3N4(COA) photo catalysts. A novel green method was opted to synthesize silver nanoparticles using seed extract of Nigella sativa. The photo catalyst was comprehensively characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS), High-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). The optical activities were analysed by double beam UV–Vis and photoluminescence. The catalytic potential of synthesized COA have been tested for degradation of Clotrimazole (CTZ) pharmaceutical effluent as model pollutant. The photo degradation results have shown that about 94.5 % of CTZ get degraded over the duration of 120 min. To explore the real scale application, the effect of catalysts dosage and pH have been studied. The major active radical species responsible for the degradation have been identified by radical scavenging experiments.

Pump-Probe X-ray Photoemission Spectroscopy of Free-Standing Graphane

Free-standing nanoporous graphene was hydrogenated at about 60 at.% H uptake, as determined by the emerging of the sp3 bonding component in the C 1s core level investigated by high-resolution X-ray photoelectron spectroscopy (XPS). Fully unsupported graphane was investigated by XPS under optical excitation at 2.4 eV. At a laser fluence of 1.6 mJ/cm2, a partial irreversible dehydrogenation of the graphane was observed, which could be attributed either to the local temperature increase or to a photo-induced softening of the H-to-C stretching mode. The sub-ns dynamics of the energy shift and peak broadening of the C 1s core level revealed two different decay constants: 210 ps and 130 ps, respectively, the former associated with photovoltage dynamics and the latter with thermal heating on a time scale comparable with the synchrotron temporal resolution.

β-Cyclodextrin Stabilized Nanoceria for Hydrolytic Cleavage of Paraoxon in Aqueous and Cationic Micellar Media.

Beta-cyclodextrin (β-CD) stabilized cerium oxide nanoparticles (β-CD@CeO2 NPs) were synthesized through a hydrothermal route. The electronic properties, surface functional group, surface composition, size, and morphologies of the as-synthesized β-CD@CeO2 NPs were characterized using UV-visible spectroscopy, FTIR analysis, high resolution X-ray photoelectron spectroscopy (HRXPS), high resolution transmission electron microscopy (HRTEM), and field emission scanning electron microscopy (FESEM). The pH-dependent variation of the ζ-potential of β-CD@CeO2 NPs and the catalytic activity of the NPs for the hydrolysis of paraoxon were investigated. The observed pseudo-first-order rate constant (kobs) for the hydrolysis of paraoxon is increased with increasing pH and the ζ-potential of β-CD@CeO2 NPs. The kinetics and mechanism of hydrolysis of paraoxon in the aqueous and cationic micellar media have been discussed.

Insights of keratin geometry from agro-industrial wastes: A comparative computational and experimental assessment

Understanding the structural properties of keratin is of great importance to managing their potential application in keratin-inspired biomaterials and its management of wastes. In this work, the molecular structure of chicken feather keratin 1 was characterized by AlphaFold2 and quantum chemistry calculation. The predicted IR spectrum of the N-terminal region of feather keratin 1, consisting of 28 amino acid residues, was used to assign the Raman frequencies of the extracted keratin. The MW of experimental samples were 6 & 1 kDa while the predicted MW (∼10 kDa) of β-keratin. Experimental analysis shows the magnetic field treatment could affect the functional and surface structural properties of keratin. The particle size distribution curve illustrates the dispersion of particle size concentration, while TEM analysis demonstrates the reduction of particle diameter to 23.71 ± 1.1 nm following treatment. High-resolution XPS analysis confirmed the displacement of molecular elements from their orbital.

Multitarget Reactive Magnetron Sputtering towards the Production of Strontium Molybdate Thin Films

X-ray photoelectron spectroscopy was used to study the direct synthesis of strontium and molybdenum oxide thin films deposited by multitarget reactive magnetron sputtering (MT-RMS). Sr and Mo targets with a purity of 99.9% and 99.5%, respectively, were co-sputtered in an argon-oxygen gas mixture. The chamber was provided with an oxygen background flow plus an additional controlled oxygen supply to each of the targets. We demonstrate that variation in the power applied to the Mo target during MT-RMS enables the production of strontium and molybdenum oxide films with variable concentrations of Mo atoms. Both molybdenum and strontium were found in the oxidized state, and no metallic peaks were detected. The deconvoluted high-resolution XPS spectra of molybdenum revealed the presence of several Mo 3d peaks, which indicates molybdenum bonds in a lower valence state. Contrary to the Mo spectra, the high-resolution strontium Sr 3d spectra for the same samples were very similar, and no additional peaks were detected.

Photoaging of polystyrene microspheres causes oxidative alterations to surface physicochemistry and enhances airway epithelial toxicity.

Microplastics represent an emerging environmental contaminant, with large gaps in our understanding of human health impacts. Furthermore, environmental factors may modify the plastic chemistry, further altering the toxic potency. Ultraviolet (UV) light is one such unavoidable factor for airborne microplastic particulates and a known modifier of polystyrene surface chemistry. As an experimental model, we aged commercially available polystyrene microspheres for 5 weeks with UV radiation, then compared the cellular responses in A549 lung cells with both pristine and irradiated particulates. Photoaging altered the surface morphology of irradiated microspheres and increased the intensities of polar groups on the near-surface region of the particles as indicated by scanning electron microscopy and by fitting of high-resolution X-ray photoelectron spectroscopy C 1s spectra, respectively. Even at low concentrations (1-30 µg/ml), photoaged microspheres at 1 and 5 µm in diameter exerted more pronounced biological responses in the A549 cells than was caused by pristine microspheres. High-content imaging analysis revealed S and G2 cell cycle accumulation and morphological changes, which were also more pronounced in A549 cells treated with photoaged microspheres, and further influenced by the size, dose, and time of exposures. Polystyrene microspheres reducedmonolayer barrier integrity and slowed regrowth in a wound healing assay in a manner dependent on dose, photoaging, and size of the microsphere. UV-photoaging generally enhanced the toxicity of polystyrene microspheres in A549 cells. Understanding the influence of weathering and environmental aging, along with size, shape, and chemistry, on microplastics biocompatibility may be an essential consideration for incorporation of different plastics in products.

Highly active and stable MoS2-TiO2 nanocomposite catalyst for slurry-phase phenanthrene hydrogenation

MoS2-TiO2 nanocomposite catalysts with Janus structure were synthesized via facile one-step solvothermal method. X-ray diffraction, high resolution transmission electron microscope, NO chemisorption and X-ray photoelectron spectroscopy were applied to characterize the composition and nanostructure of the MoS2-TiO2 nanocomposite catalysts. Experimental results revealed that the MoS2-TiO2 nanocomposite catalysts with Janus structure were composed of MoS2 layers (few stacked layers of 1–3 and short slabs of 2–10 nm) and TiO2 nanoparticles (10–15 nm), which have strong MoS2-TiO2 interaction with transferring electrons from TiO2 to MoS2. Catalytic performance of MoS2-TiO2 nanocomposite catalysts for phenanthrene hydrogenation was investigated and compared with that of MoS2 catalyst in an autoclave reactor with high temperature and high pressure. The phenanthrene conversion over the MoS2-TiO2 nanocomposite catalyst with MoS2 content of 15.0 wt% (MoS2-TiO2-15) can reach 91.6%, which was much higher than 50.4% for MoS2 catalyst and 76.8% for conventional supported MoS2/TiO2-15 catalyst. After 7 cycles of phenanthrene hydrogenation reaction, the phenanthrene conversion over MoS2-TiO2-15 nanocatalyst remained at 68.6%, while the phenanthrene conversion over MoS2 catalyst was reduced to only 25.4%. The MoS2-TiO2 nanocomposite catalysts exhibit significantly enhanced catalytic activity and stability for slurry phase hydrogenation. The enhanced catalytic activity originates from the exposure of abundant coordinatively unsaturated Mo atoms. The enhanced stability results from the Janus structure with stable MoS2-TiO2 interaction and Mo–O–Ti bonds, which anchor MoS2 layers on the surface of TiO2 nanoparticles to avoid the curling, folding and agglomeration of MoS2 layers. This is an important finding on slurry phase catalytic hydrogenation performances of MoS2-based nanocomposite catalysts with Janus structure. Shedding light on the research of Janus nanocomposite catalysts in catalytic hydrogenation is significantly crucial for the development of effective and stable hydrogenation catalysts.