Solid-phase reaction synthesis of mesostructured tungsten disulfide material with a high specific surface area

A mesostructured tungsten disulfide (WS₂) material was prepared through a solid-phase reaction utilizing ammonium tetrathiotungstate as the precursor and n-octadecylamine as the template. The as-synthesized WS₂ material was characterized by X-ray powder Diffraction (XRD), Low-temperature N₂ Adsorption (BET method), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM). The characterization results indicate that the WS₂ material has the typical mesopore structure (3.7 nm) with a high specific surface area (145.9 m²/g), and large pore volume (0.18 cm³/g). This approach is novel, green and convenient. The plausible mechanism for the formation of the mesostructured WS₂ material is discussed herein.     

Synthesis,characterization and catalytic activity of acid–base bifunctional materials through protection of amino groups

Acid–base bifunctional mesoporous material SO₃H-SBA-15-NH₂ was successfully synthesized under low acidic medium through protection of amino groups. X-ray diffraction (XRD), N₂ adsorption–desorption, transmission electron micrographs (TEM), back titration, ¹³C magic-angle spinning (MAS) NMR and ²⁹Si magic-angle spinning (MAS) NMR were employed to characterize the synthesized materials. The obtained bifunctional material was tested for aldol condensation reaction between acetone and 4-nitrobenzaldehyde. Compared with monofunctional catalysts of SO₃H-SBA-15 and SBA-15-NH₂, the bifunctional sample of SO₃H-SBA-15-NH₂ containing amine and sulfonic acid groups exhibited excellent acid–basic properties, which make it possess high activity for the aldol condensation.     

Hydrothermally grown ZnO nanoflowers for environmental remediation and clean energy applications

Well-crystalline flower-shaped ZnO nanostructures were synthesized by simple hydrothermal process at low-temperature of 145 °C and utilized as a photocatalyst and photo-anode material for photocatalytic degradation and dye-sensitized solar cell applications, respectively. The detailed morphological and the structural characterizations revealed that the synthesized products were flower-shaped, grown in very high-density, and possessed well-crystalline wurtzite hexagonal phase. The chemical composition confirmed the pure phase and good optical properties of as-synthesized ZnO flowers. The as-synthesized ZnO flowers were used as an efficient photocatalyst for the photocatalytic degradation of Rhodamine B which exhibit ～84% degradation within 140 min. Moreover, the as-synthesized ZnO flowers were utilized as photo-anode material for the fabrication of dye-sensitized solar cells (DSSCs) which exhibited overall light-to-electricity conversion efficiency of ～1.38%, open-circuit current (V_OC) of 0.621 V, short-circuit current (J_SC) of ～3.52 mA/cm² and fill factor (FF) of 0.64.     

Dinitrogen Reduction Coupled with Methanol Oxidation for Low Overpotential Electrochemical NH3 Synthesis Over Cobalt Pyrophosphate as Bifunctional Catalyst

Electrochemical dinitrogen (N₂) reduction to ammonia (NH₃) coupled with methanol electro-oxidation is presented in the current work. Here, methanol oxidation reaction (MOR) is proposed as an alternative anode reaction to oxygen evolution reaction (OER) to accomplish electrons-induced reduction of N₂ to NH₃ at cathode and oxidation of methanol at anode in alkaline media thereby reducing the overall cell voltage for ammonia production. Cobalt pyrophosphate micro-flowers assembled by nanosheets are synthesized via a surfactant-assisted sonochemical approach. By virtue of structural and morphological advantages, the maximum Faradaic efficiency of 43.37% and NH₃ yield rate of 159.6 µg h⁻¹ mg_ca⁻¹ is achieved at a potential of −0.2 V versus RHE. The proposed catalyst is shown to also exhibit a very high activity (100 mA mg⁻¹ at 1.48 V), durability (2 h) and production of value-added formic acid at anode (2.78 µmol h⁻¹ mg_cat⁻¹ and F.E. of 59.2%). The overall NH₃ synthesis is achieved at a reduced cell voltage of 1.6 V (200 mV less than NRR-OER coupled NH₃ synthesis) when OER at anode is replaced with MOR and a high NH₃ yield rate of 95.2 µg h⁻¹ mg_cat⁻¹ and HCOOH formation rate of 2.53 µmol h⁻¹ mg⁻¹ are witnessed under full-cell conditions.     

Characterization and optical properties of m-Li2ZrO3 prepared by optimized solid-state reaction

m-Li₂ZrO₃ powders were successfully prepared by solid-state reaction method using Li₂CO₃ and ZrO₂ as raw materials. The synthesis was optimized by varying the ball-milling time (0–96 h); Li₂CO₃ excess (0 or 5 wt%), reaction temperature (700, 800, 900 or 1000 °C), and reaction time (3, 6, 9 or 12 h). The structural, morphological and optical properties of m-Li₂ZrO₃ powders were examined by X-Ray Diffraction, Thermogravimetric and Differential-Thermal analysis, Scanning Electron Microscopy, High-Resolution Transmission Electron Microscopy, Laser Diffraction, Dynamic Light Scattering and UV–Vis Diffuse Reflectance Spectroscopy. The results show that precursors suitable for the synthesis of fine powders require ball-milling times longer than or equal to 6 h. Highly crystalline m-Li₂ZrO₃ was synthesized under two distinctive calcination conditions as follows: 900 °C/6h without Li₂CO₃ excess or 1000 °C/12 h using 5 wt% of Li₂CO₃ excess. Particle size of as-synthesized powders was found to be in the range from 200 nm to 1 µm. m-Li₂ZrO₃ was found to be a wide band gap material with apparent optical band gap of 5.5 eV (direct) and 5.1 eV (indirect), which can be used in UV-C applications.     

Identification of thaumasite in concrete by Raman chemical imaging

Identification of thaumasite (CaSiO₃·CaO₃·CaSO₄·15H₂O) in concrete undergoing external sulfate attack by X-ray powder diffraction or by microscopic techniques is difficult due to its crystallographic and morphological similarity with ettringite. Widefield Raman chemical imaging via liquid crystal tunable filter (LCTF) technology has been used in a preliminary study to determine the presence of thaumasite in association with ettringite (3CaO·Al₂O₃·3CaSO₄·32H₂O) and gypsum (CaSO₄·2H₂O). Raman chemical imaging combines Raman spectroscopy with optical microscopy and digital imaging to provide images with molecular-based contrast. Thaumasite has three major peaks at 658, 990, 1076 cm⁻¹ and three minor peaks at 417, 453, 479 cm⁻¹. Ettringite has major peaks at 990, 1088 cm⁻¹. Gypsum has a major peak at 1009 cm⁻¹ and minor peaks at 417, 496, 621, 673, 1137 cm⁻¹. When these minerals are presented together, Raman chemical imaging provides an excellent way to determine their molecular composition and spatial distribution within the sample.     

High resolution electron energy loss spectroscopy of manganese oxides: Application to Mn3O4 nanoparticles

Manganese oxides particularly Mn₃O₄ Hausmannite are currently used in many industrial applications such as catalysis, magnetism, electrochemistry or air contamination. The downsizing of the particle size of such material permits an improvement of its intrinsic properties and a consequent increase in its performances compared to a classical micron-sized material. Here, we report a novel synthesis of hydrophilic nano-sized Mn₃O₄, a bivalent oxide, for which a precise characterization is necessary and for which the determination of the valency proves to be essential. X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and particularly High Resolution Electron Energy Loss Spectroscopy (HREELS) allow us to perform these measurements on the nanometer scale. Well crystallized 10–20 nm sized Mn₃O₄ particles with sphere-shaped morphology were thus successfully synthesized. Meticulous EELS investigations allowed the determination of a Mn³⁺/Mn²⁺ ratio of 1.5, i.e. slightly lower than the theoretical value of 2 for the bulk Hausmannite manganese oxide. This result emphasizes the presence of vacancies on the tetrahedral sites in the structure of the as-synthesized nanomaterial.     

Highly Enhancing CO2 Photoreduction by Metallization of an Imidazole-linked Robust Covalent Organic Framework

Converting CO₂ into value-added chemicals to solve the issues caused by carbon emission is promising but challenging. Herein, by embedding metal ions (Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) into an imidazole-linked robust photosensitive covalent organic framework (PyPor-COF), effective photocatalysts for CO₂ conversion are rationally designed and constructed. Characterizations display that all of the metallized PyPor-COFs (M-PyPor-COFs) display remarkably high enhancement in their photochemical properties. Photocatalysis reactions reveal that the Co-metallized PyPor-COF (Co-PyPor-COF) achieves a CO production rate as high as up to 9645 µmol g⁻¹ h⁻¹ with a selectivity of 96.7% under light irradiation, which is more than 45 times higher than that of the metal-free PyPor-COF, while Ni-metallized PyPor-COF (Ni-PyPor-COF) can further tandem catalyze the generated CO to CH₄ with a production rate of 463.2 µmol g⁻¹ h⁻¹. Experimental analyses and theory calculations reveal that their remarkable performance enhancement on CO₂ photoreduction should be attributed to the incorporated metal sites in the COF skeleton, which promotes the adsorption and activation of CO₂ and the desorption of generated CO and even reduces the reaction energy barrier for the formation of different intermediates. This work demonstrates that by metallizing photoactive COFs, effective photocatalysts for CO₂ conversion can be achieved.     

Die Ausbildung von Oxidschutzschichten auf verschiedenen Ni-Cr-Fe-Legierungen bei unterschiedlichen Sauerstoffpartialdrucken

The growth of the oxide protective layer on different Ni-Cr-Fe-alloys with variation of oxygen partial pressure High temperature alloys e.g. Incoloy 800 H, Hastelloy X and Ni75Cr25 model alloy are in-situ oxidized with variation potentials oxidation of PO₂ = 4,41 × 10^?19 bar, PO₂ = 4,41 × 10^?17 bar and PO₂ = 176 × 10^?16 bar by temperature, 800°. The behaviour of the scales which are oxidized at different oxidizing atmospheres has been investigated in this work, with deuterium permeation. The test of scales as corrosion barrier had been done in sulfidizing atmospheres with PS₂ = 1,82 × 10^?7 bar. The microstructure of the oxide layers has been investigated with Light Microscopy (LM), Scanning Electron Microscopy (SEM), Analytical Transmission Electron Microscopy (ATEM) and High Resolution Transmission Electron Microscopy (HRTEM). It is found that the deuterium permeation measurement can be correlated as a method for characterization corrosion layer at high temperature alloys. The structure of the oxide layer, the influence of sulfidizing atmospheres, additions of small amounts of reactive elements such as Ti before oxidation, the interface structure between oxide layers and matrix, as well as crystal defects and grain boundaries is explainable.     

Synthesis of CaOSiO2 compounds and their testing as heterogeneous catalysts for transesterification of sunflower oil

The powder mixtures of calcium oxide (CaO) and silica gel (SiO₂) in molar ratios of 1:1, 1.5:1, 2:1 and 3:1 were mechanochemically treated with the addition of water, and were subsequently calcined with a goal of synthesizing CaSiO_3, Ca₃Si₂O₇, Ca₂SiO₄ compounds and CaO/Ca₂SiO₄ two-phase mixture. The prepared materials were characterized by XRD, FTIR, SEM/EDS, particle size laser diffraction (PSLD), UV–vis diffuse reflectance spectroscopy (DRS), N₂ adsorption/desorption isotherms, Hammett indicator for basic strength and volumetric analysis for free CaO content. The catalytic activity of calcium silicates with different Ca/Si ratios was tested in the transesterification of triacylglycerols (sunflower oil) with methanol. Samples obtained with initial composition 2CaO·SiO₂ and 3CaO·SiO₂ calcined at 700?°C, and 3CaO·SiO₂ calcined at 900?°C had high catalytic activity, resulting with triacylglycerols conversion and fatty acids methyl ester formation (FAME or biodiesel) above 96%. The activity of these samples can be attributed to the existence of free CaO defined by CaO/Ca₂SiO₄ complex mixture. The effect of different amount of catalyst used for transesterification (0.2–2?wt%) was analyzed using the most active catalyst i.e. 3CaO·SiO₂ calcined at 700?°C as well as possibility of its reuse for biodiesel synthesis. It was also found that CaSiO₃, Ca₃Si₂O₇ and Ca₂SiO₄, phases did not possess catalytic activity.     

Strain rate sensitivity of glass/epoxy composites with nanofillers

It is understood that small amount of nanoclay in the neat epoxy and fiber reinforced epoxy composite system improves the mechanical properties. The mechanical properties of most of polymer matrix composites are rate sensitive. Most of the researches have concentrated on the behavior of the polymer composites at high strain rates. The present research work is to study the effect of clay on neat epoxy and glass/epoxy composites, at low strain rates. The clay in terms of 1.5, 3 and 5 wt% are dispersed in the epoxy resin using mechanical stirrer followed by sonication process. The glass/epoxy nanocomposites are prepared by impregnating the glass fiber with epoxy–clay mixture by hand lay-up process followed by compression molding. Characterization of the nanoclay is done by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). Tensile stress–strain curves are obtained at strain rates of 10⁻⁴, 10⁻³, 10⁻² and 10⁻¹ s⁻¹ by a servo-hydraulic machine and the variation of modulus, strength and failure strain with strain rate are determined. The results show that, even at low strain rates, the longitudinal strength and stiffness increase as strain rate increases for all clay loadings. It is observed that the tensile modulus increases as the clay loading increases for both epoxy and glass/epoxy nanocomposites. Scanning electron microscopy is used to study the adhesion of composites in fracture surfaces.     

Chemical synthesis of CdS onto TiO2 nanorods for quantum dot sensitized solar cells

A quantum dot sensitized solar cell (QDSSC) is fabricated using hydrothermally grown TiO₂ nanorods and successive ionic layer adsorption and reaction (SILAR) deposited CdS. Surface morphology of the TiO₂ films coated with different SILAR cycles of CdS is examined by Scanning Electron Microscopy which revealed aggregated CdS QDs coverage grow on increasing onto the TiO₂ nanorods with respect to cycle number. Under AM 1.5G illumination, we found the TiO₂/CdS QDSSC photoelectrode shows a power conversion efficiency of 1.75%, in an aqueous polysulfide electrolyte with short-circuit photocurrent density of 4.04 mA/cm² which is higher than that of a bare TiO₂ nanorods array.     

Significantly Stabilizing Hydrogen Evolution Reaction Induced by Nb-Doping Pt/Co(OH)2 Nanosheets

High stability and efficiency of electrocatalysts are crucial for hydrogen evolution reaction (HER) toward water splitting in an alkaline media. Herein, a novel nano-Pt/Nb-doped Co(OH)₂ (Pt/Nb Co(OH)₂) nanosheet is designed and synthesized using water-bath treatment and solvothermal reduction approaches. With nano-Pt uniformly anchored onto Nb Co(OH)₂ nanosheet, the synthesized Pt/Nb Co(OH)₂ shows outstanding electrocatalytic performances for alkaline HER, achieving a high stability for at least 33 h, a high mass activity of 0.65 mA µg⁻¹ Pt, and a good catalytic activity with a low overpotential of 112 mV at 10 mA cm⁻². Both experimental and theoretical results prove that Nb-doping significantly optimizes the hydrogen adsorption free energy to accelerate the Heyrovsky step for HER, and boosts the adsorption of H₂O, which further enhances the water activation. This study provides a new design methodology for the Nb-doped electrocatalysts in an alkaline HER field by facile and green way.     

Pd-Doped Co3O4 Nanoarray for Efficient Eight-Electron Nitrate Electrocatalytic Reduction to Ammonia Synthesis

Ammonia (NH₃) is an indispensable feedstock for fertilizer production and one of the most ideal green hydrogen rich fuel. Electrochemical nitrate (NO₃⁻) reduction reaction (NO₃⁻RR) is being explored as a promising strategy for green to synthesize industrial-scale NH₃, which has nonetheless involved complex multi-reaction process. This work presents a Pd-doped Co₃O₄ nanoarray on titanium mesh (Pd-Co₃O₄/TM) electrode for highly efficient and selective electrocatalytic NO₃⁻RR to NH₃ at low onset potential. The well-designed Pd-Co₃O₄/TM delivers a large NH₃ yield of 745.6 µmol h⁻¹ cm⁻² and an extremely high Faradaic efficiency (FE) of 98.7% at −0.3 V with strong stability. These calculations further indicate that the doping Co₃O₄ with Pd improves the adsorption characteristic of Pd-Co₃O₄ and optimizes the free energies for intermediates, thereby facilitating the kinetics of the reaction. Furthermore, assembling this catalyst in a Zn-NO₃⁻ battery realizes a power density of 3.9 mW cm⁻² and an excellent FE of 98.8% for NH₃.     

Z-Scheme Modulated Charge Transfer on InVO4@ZnIn2S4 for Durable Overall Water Splitting

The charge transfer within heterojunction is crucial for the efficiency and stability of photocatalyst for overall water splitting (OWS). Herein, InVO₄ nanosheets have been employed as a support for the lateral epitaxial growth of ZnIn₂S₄ nanosheets to produce hierarchical InVO₄@ZnIn₂S₄ (InVZ) heterojunctions. The distinct branching heterostructure facilitates active site exposure and mass transfer, further boosting the participation of ZnIn₂S₄ and InVO₄ for proton reduction and water oxidation, respectively. The unique Z-scheme modulated charge transfer, visualized by simulation and in situ analysis, has been proved to promote the spatial separation of photoexcited charges and strengthen the anti-photocorrosion capability of InVZ. The optimized InVZ heterojunction presents improved OWS (153.3 µmol h⁻¹ g⁻¹ for H₂ and 76.9 µmol h⁻¹ g⁻¹ for O₂) and competitive H₂ production (21090 µmol h⁻¹ g⁻¹). Even after 20 times (100 h) of cycle experiment, it still holds more than 88% OWS activity and a complete structure.     

Constructing Co@TiO2 Nanoarray Heterostructure with Schottky Contact for Selective Electrocatalytic Nitrate Reduction to Ammonia

Electrochemical nitrate (NO₃⁻) reduction reaction (NO₃⁻RR) is a potential sustainable route for large-scale ambient ammonia (NH₃) synthesis and regulating the nitrogen cycle. However, as this reaction involves multi-electron transfer steps, it urgently needs efficient electrocatalysts on promoting NH₃ selectivity. Herein, a rational design of Co nanoparticles anchored on TiO₂ nanobelt array on titanium plate (Co@TiO₂/TP) is presented as a high-efficiency electrocatalyst for NO₃⁻RR. Density theory calculations demonstrate that the constructed Schottky heterostructures coupling metallic Co with semiconductor TiO₂ develop a built-in electric field, which can accelerate the rate determining step and facilitate NO₃⁻ adsorption, ensuring the selective conversion to NH₃. Expectantly, the Co@TiO₂/TP electrocatalyst attains an excellent Faradaic efficiency of 96.7% and a high NH₃ yield of 800.0 µmol h⁻¹ cm⁻² under neutral solution. More importantly, Co@TiO₂/TP heterostructure catalyst also presents a remarkable stability in 50-h electrolysis test.     

One-step and cost-effective synthesis of micrometer-sized saw-like silver nanosheets by oil/water interfacial method

One-step synthesis of silver saw-like nanosheets was introduced by using aqueous AgNO₃ and benzene-soluble p-phenylenediamine (pPD). Based on the X-ray diffraction pattern and selected-area electron diffraction pattern, the silver was single crystal. As indicated by Scanning Electron Microscopy, Transmission Electron Microscopy and the auxiliary characterization by Fourier transform infrared and Raman Spectroscopy, the nanosheets are ~ 20 μm in edge length and are coated by poly(p-phenylenediamine) (PpPD) thin films. The role of oil/water interface and PpPD on the formation of sheet-like morphology was analyzed. This method is facile and cost-effective.     

Fibrinogen adsorption onto macroporous polymeric surfaces: correlation with biocompatibility aspects

The present work focus on the adsorption of fibrinogen (Fgn) on to the semi-interpenetrating polymer networks (IPNs) of polyethylene glycol (PEG) and poly(2-hydroxyethyl methacrylate-co-acrylonitrile) and attempts to correlate the adsorption behaviour of proteins to the blood compatible aspects of the polymeric surfaces. The semi-IPNs were prepared by copolymerizing 2-hydroxyethyl methacrylate and acrylonitrile in the presence of PEG and a crosslinker ethyleneglycol dimethacrylate (EGDMA). The prepared spongy gels were characterized by FTIR and Environmental Scanning Electron Microscopy (ESEM) for structural and morphological analysis. The prepared semi IPNs were studied for their water sorption capacity and the data were utilized to evaluate network parameters such as average molecular weight between crosslinks (M_c) and crosslink density (q). The adsorption of Fgn was carried out on to the prepared polymeric matrices and static and dynamic aspects of the adsorption process were investigated. The adsorption process was also studied as a function of pH and ionic strength of the protein solution and chemical architecture of the semi IPN. The antithrombogenic properties of the IPN’s were also judged and correlated with water sorption and protein adsorption findings.