Ultrasound and Microwave-Assisted Co-precipitation Synthesis of La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript> Perovskite Nanoparticles from a New Lanthanum(III) Coordination Polymer Precursor

In the present study nano-sized strontium-doped lanthanum manganite, La_0.75Sr_0.25MnO₃ (LSM), were synthesized by three simple different methods (a) co-precipitation, (b) ultrasonic and (c) microwave-assisted co-precipitation. A lanthanum(III) coordination polymer, [pyda.H]₂[La₂(pydc)₄(H₂O)₄]·2H₂O, where [pyda.H]⁺?=?2,6-diaminopyridinium, and (pydc)^2??=?2,6-pyridinedicarboxylate, was used as a new precursor. The products were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), field emission scanning electron microscope (FESEM), thermal gravimetric (TG) and differential thermal analyses (DTA), as well as by Energy-dispersive X-ray spectroscopy (EDX). The XRD results showed that the crystal lattice of the product obtained was orthorhombic perovskite structure. The porosity, particle size and homogeneity of calcinated LSM were strongly dependent on the preparation method. In addition, the results proved that the product formation time was decreased considerably when ultrasonic or microwave irradiation methods were used.     

Li<Subscript>2</Subscript>Cu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> + SiO<Subscript>2</Subscript>/Ti compositions for the catalytic afterburning of diesel soot

Two methods were used to obtain a catalytically active oxide coating on the surface of titanium for the catalytic afterburning of diesel soot: plasma electrochemical formation of an oxide film on the surface of titanium and extraction pyrolytic deposition of the Li₂Cu₂(MoO₄)₃ compound. The Li₂Cu₂(MoO₄)₃/TiO₂ + SiO₂/Ti compositions synthesized by the single-step extraction pyrolytic treatment of the oxidized surface of titanium ensured a high burning rate of soot of ∼300°C. The subsequent deposition of Li₂Cu₂(MoO₄)₃ lowers the activity of the catalyst, due probably to the growth of molybdate phase crystallites and the filling of open oxide film pores. Double lithium-copper molybdate is able to reduce appreciably the concentration of CO in the oxidation products of soot. The advantages of these methods are the possibility of forming high-cohesion durable coatings on surfaces of any complexity, the simplicity of their implementation, and high productivity and low cost. The obtained results can be recommended for use in developing methods for creating composite coatings on catalytic soot filters.     

Synthesis and characterization of Ni–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite coatings containing different forms of alumina

Electrodeposited Ni–Al₂O₃ composite coatings were prepared using alumina powders synthesized from solution combustion method, precipitation method and a commercial source. Solution combustion synthesized alumina powder yielded α-phase; precipitation method yielded purely γ-phase; commercial alumina powder was a mixture of α-, δ- and γ-phases. A nickel sulfamate bath was used for electro-codeposition. The current densities (0.23 A dm⁻² for 20 h, 0.77 A dm⁻² for 6 h, 1.55 A dm⁻² for 3 h and 3.1 A dm⁻² for 1.5 h) and bath agitation speeds (100, 200, 600 and 1000 rpm) were varied. The pH variations of the bath were higher during the electrodeposition of combustion synthesized alumina. The effect of different forms of alumina particles on the microhardness and microstructure of the nickel composite coating was studied. Composite coating containing combustion synthesized alumina particles was found to have higher microhardness (550 HK). It was found that at lower agitation speed (100 rpm), bigger particles were incorporated and at higher agitation speed (1000 rpm), smaller particles were incorporated. The area fraction of alumina particles incorporated in nickel matrix was highest for commercial alumina (24%). This study shows that it is not suffice to take just the current density and stirring speeds into account to explain the properties of the coatings but also to take into account the source of particles and their properties.     

Synthesis and properties of the composite ceramics from nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-30% Y<Subscript>0.1</Subscript>Zr<Subscript>0.9</Subscript>O<Subscript>2</Subscript> prepared from a water-alcohol solution

The hydrogel of the mixed oxide Al₂O₃-30% Y_0.1Zr_0.9O₂ was prepared by precipitation of ammonia from a water-alcohol mixture (1 : 5). The Al₂O₃-30% Y_0.1Zr_0.9O₂ compound thus synthesized was characterized using differential scanning calorimetry, transmission electron microscopy, and the BET adsorption method. The obtained sample consisted of spherical particles with an average size of 16–20 nm and a specific surface area of 167 m²/g. The Al₂O₃-30% Y_0.1Zr_0.9O₂ powder was pressed at 300 MPa and then calcinated at 1600°C for 2 h in air. The topographic and structural features of the prepared ceramics were determined using atomic force microscopy and X-ray electron probe microanalysis. The porosity, the Vickers microhardness, and the tensile strength were determined by mercury porometry.     

Effect of surface modification of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles on the preparation of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/polystyrene composite particles via miniemulsion polymerization

Fe₃O₄ nanoparticles were modified by n-octadecyltrimethoxysilane (C18TMS) and 3-trimethoxysilylpropylmethacrylate (MPS). The modified Fe₃O₄ nanoparticles were used to prepare Fe₃O₄/polystyrene composite particles by miniemulsion polymerization. The effect of surface modification of Fe₃O₄ on the preparation of Fe₃O₄/polystyrene composite particles was investigated by transmission electron microscopy, Fourier transform infrared spectrophotometer (FT-IR), contact angle, and vibrating sample magnetometer (VSM). It was found that C18TMS modified Fe₃O₄ nanoparticles with high hydrophobic property lead to the negative effect on the preparation of the Fe₃O₄/polystyrene composite particles. The obtained composite particles exhibited asymmetric phase-separated structure and wide size distribution. Furthermore, un-encapsulated Fe₃O₄ were found in composite particles solution. MPS modified Fe₃O₄ nanoparticles showed poor hydrophobic properties and resulted in the obtained Fe₃O₄/polystyrene composite particles with regular morphology and narrow size distribution because the ended C=C of MPS on the surface of Fe₃O₄ nanoparticles could copolymerize with styrene which weakened the phase separation distinctly.     

Soft Template Synthesis of Super Paramagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles a Novel Technique

The present study reports a facile technique for the synthesis of crystalline super paramagnetic nano ferrite (Fe₃O₄) particles using diethyl amine as a soft template. The spectral properties of Fe₃O₄ nanoparticles were characterized by UV–visible and Fourier Transform Infrared (FTIR) spectroscopies while the crystalline structure and particle size was estimated using X-Ray diffraction (XRD) as well as transmission electron microscopy (TEM) techniques. The super paramagnetic behavior of Fe₃O₄ nanoparticles was determined using vibrating sample magnetometer (VSM) at 300 K. The results of the studies revealed that this technique could be adopted to synthesize agglomerate free super paramagnetic Fe₃O₄ nanoparticles which may find potential application in the filed of biosensor and corrosion protective coatings.     

Effect of specimen orientation and heat treatment on electroless Ni-PTFE-MoS<Subscript>2</Subscript> composite coatings

In this study, the effects of simultaneous co-deposition of polytetrafluoroethylene (PTFE) and MoS₂ particles on tribological properties of electroless nickel (EN) coating were studied. The influences of specimen orientation and heat treatment on EN-PTFE-MoS₂ composite coatings were also investigated. Scanning electron microscopy was used to study the morphology of coatings and the distributions of the lubricant particles in the deposits. Chemical analyses of coatings were done by electron dispersive spectrometry. The phases of the coatings were identified by X-ray diffraction utilizing CuKα radiation. Wear and friction properties of the coatings were also determined by pin-on-disk wear tester. The wear investigations showed that the EN-PTFE-MoS₂ composite coating performs better than EN-PTFE and EN-MoS₂ coatings in terms of friction coefficient and wear resistance. PTFE and MoS₂ contents of the EN-PTFE-MoS₂ coating were increased by changing the specimen orientation from vertical to horizontal configuration, which leads to enhancement in tribological properties of the coating. After heat treatment, the wear rate of EN matrix composite coating decreased with corresponding change in phase structure.     

Size-dependent luminescent properties of hollow and dense BaMgAl<Subscript>10</Subscript>O<Subscript>17</Subscript>: Eu blue phosphor particles prepared by spray pyrolysis

Hollow and dense BaMgAl10O17: Eu₂₊ (BAM) phosphor particles were synthesized by a spray pyrolysis process and their luminescent properties were investigated under vacuum ultraviolet (VUV) excitation as varying the average particle size. The dependence of the luminescent intensity on the particle size was greatly influenced by the morphology of BAM particles. For the BAM particles with a hollow structure, the luminescent intensity linearly increased with increasing the particle size. However, no significant change in the luminescent intensity was observed for dense particles as the particle size changed. Also, all dense BAM particles had higher photoluminescence intensity than that of the hollow ones regardless of the particle size. The luminescent intensity of BAM phosphor particles prepared by spray pyrolysis was found to have a linear relationship with the crystallite size. Therefore, it was concluded that suppressing the formation of a hollow structure and increasing the crystallite size are needed to obtain high luminous BAM phosphor particles with a spherical shape and fine size of less than 1 Μm. On the basis of penetration depth of VUV, a simple relation equation between the particle size and the luminescent intensity was derived and correlated with experimental results in order to interpret the luminescent behavior of BAM phosphor as the particle size changes.     

Effect of Annealing Temperature and Alumina Particles on Mechanical and Tribological Properties of Ni-P-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Composite Coatings

In this study, the effect of annealing temperature and alumina particles on micro-hardness, corrosion, wear, and friction of Ni-P-Al₂O₃ composites coating is studied. The electroless nickel composite coating with various alumina particle content is deposited on a mild steel substrate. The corrosion behaviour and tribological behaviour (wear and friction) of the composite coated samples are investigated and compared with Ni-P coated samples. The micro-hardness, wear resistance, and corrosion resistance of the composite coating improved significantly after heat treatment (400 °C) and in the presence of alumina particles. The composite coating deposited with alumina particle concentration of 10 g/L in an electroless bath and heat treated at 400 °C shows excellent results compared to Ni-P, as-deposited Ni-P-Al₂O₃ coating and coatings heat treated at different annealing temperature (200 °C, 300 °C, and 500 °C). Microstructure changes and composition of the composite coatings due to incorporation of alumina particles and heat treatment are studied with the help of SEM (scanning electron microscopy), EDX (energy dispersive X-ray analysis and XRD (X-ray diffraction analysis).     

Nonionic polymeric surfactant template for mesoporous NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> formation

Mesostructured NiCo₂O₄ is synthesized in presence of nonionic glucose based polymeric surfactant, β-C₁₀Alkyl Poly Glucoside (β-C₁₀APG). Formed NiCo₂O₄ mesostructures have pore size in the range of 25–65 Å and surface area of 202.9 m²/g. Formed particles are rod shape with 2d hexagonal pattern and Fd3m space group point symmetry. The formation of mesostructure phase is explained by coordination bond formation between metal ions with surfactant head. β-C₁₀APG has the potential to be explored as green template for mesopore formation.     

Controlling exchange bias in Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/FeO composite particles prepared by pulsed laser irradiation

Spherical iron oxide nanocomposite particles composed of magnetite and wustite have been successfully synthesized using a novel method of pulsed laser irradiation in ethyl acetate. Both the size and the composition of nanocomposite particles are controlled by laser irradiation condition. Through tuning the laser fluence, the Fe₃O₄/FeO phase ratio can be precisely controlled, and the magnetic properties of final products can also be regulated. This work presents a successful example of the fabrication of ferro (ferri) (FM)/antiferromagnetic (AFM) systems with high chemical stability. The results show this novel simple method as widely extendable to various FM/AFM nanocomposite systems.     

Effect of PbTe on Thermoelectric Properties of Co<Subscript>0.88</Subscript>Ni<Subscript>0.12</Subscript>Sb<Subscript>2.91</Subscript>Sn<Subscript>0.09</Subscript>

The Co_0.88Ni_0.12Sb_2.91Sn_0.09 compound was synthesized by a metallurgical route, and PbTe powder was prepared by the low-temperature aqueous chemical method. Composite materials (xPbTe/Co_0.88Ni_0.12Sb_2.91Sn_0.09) were prepared by the ball-milling and the hot-pressed process. Electrical conductivities of xPbTe/Co_0.88Ni_0.12Sb_2.91Sn_0.09 hot-pressed samples decrease with increase of PbTe content, but their thermal conductivities were effectively improved due to induction of disperse phase. Due to agglomeration of the disperse phase, little thermal conductivity improvement occurs for composite material with low PbTe content. The ZT values of xPbTe/Co_0.88Ni_0.12Sb_2.91Sn_0.09 samples were hardly enhanced due to the negative contribution of electrical conductivity.     

Preparation of hydrophobic SiO<Subscript>2</Subscript>@(TiO<Subscript>2</Subscript>/MoS<Subscript>2</Subscript>) composite film and its self-cleaning properties

TiO₂/MoS₂ composite was encapsulated by hydrophobic SiO₂ nanoparticles using a sol–gel hydrothermal method with methyltriethoxysilane (MTES), titanium tetrachloride (TiCl₄), and molybdenum disulfide (MoS₂) as raw materials. Then, a novel dual functional composite film with hydrophobicity and photocatalytic activity was fabricated on a glass substrates via the combination of polydimethylsiloxane adhesives and hydrophobic SiO₂@(TiO₂/MoS₂) composite particles. The influence of the mole ratios of MTES to TiO₂/MoS₂ (M:T) on the wettability and photocatalytic activity of the composite film was discussed. The surface morphology, chemical compositions, and hydrophobicity of the composite film on the glass substrate were investigated by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and water contact angle (water CA) measurements. The results indicated that the composite film exhibited stable superhydrophobicity and excellent photocatalytic activity for degradation of methyl orange (MO) even after five continuous cycles of photocatalytic reaction when M/T was 7:1. The water CA and degradation efficiency for MO remained at 154° and 94%, respectively. Further, the composite film showed a good non-sticking characteristic with the water sliding angle (SA) at about 4°. The SiO₂@(TiO₂/MoS₂) composite consisting of hydrophobic SiO₂ nanoparticles and TiO₂/MoS₂ heterostructure could provide synergistic effects for maintaining long-term self-cleaning performance.     

Formation of La<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> crystals from amorphous La<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> powders synthesized by the polymerized complex method

Amorphous La₂O-TiO₂ powders were synthesized by the polymerized complex (PC) method. The activation energies for crystallization and grain growth of La₂Ti₂O₇ from these precursors were determined from results of XRD and DTA and compared with those for La₂Ti₂O₇ precursors by the conventional solid-state reaction (SSR). Activation energy of grain growth of La₂Ti₂O₇ in PC-sample was determined to be 7.1 kJ/mol while that of SSR sample was 14.8 kJ/mol. The energy required for the phase transformation from amorphous PC sample to layered perovskite was 432 kJ/mol, while the SSR sample did not show this transition below 900‡C. It was clearly demonstrated that the La₂Ti₂O₇ crystals were formed at a lower temperature and they grew in size faster in the sample prepared by the PC method relative to the sample prepared by the SSR method. Mixing of elements in molecular level in PC preparation appeared responsible for these differences.     

Polyaniline/g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> composites as novel media for anticorrosion coatings

In this paper, graphitic carbon nitride (g-C₃N₄) was first proposed for the pioneer application of anticorrosion coatings. Original g-C₃N₄ was facilely treated using HNO₃ and the exfoliated g-C₃N₄ sheets (E-g-C₃N₄) were fabricated, and then, polyaniline/E-g-C₃N₄ composites (PANI/E-g-C₃N₄) as novel anticorrosive media were synthesized by chemical oxidative polymerization and devoted to the corrosion protection of coatings. The E-g-C₃N₄ sheets and PANI/E-g-C₃N₄ composites were characterized by X-ray diffraction, Fourier transform infrared, thermogravimetric analysis, and transmission electron microscopy. The anticorrosion properties of the samples prepared were investigated by electrochemical measurements including Tafel plots, electrochemical impedance spectra, and open-circuit potential. Accelerated corrosion tests of iron panels coated by PANI/E-g-C₃N₄ were performed in 3.5 wt% NaCl solution. Anticorrosive mechanism of PANI/E-g-C₃N₄ was discussed in detail. PANI/E-g-C₃N₄-3 fillers possessed superior corrosion inhibition than individual components on iron coatings, which was due to the synergetic effect of anticorrosion between E-g-C₃N₄ and PANI.     

Chemical Vapor Deposition of Pd(C<Subscript>3</Subscript>H<Subscript>5</Subscript>)(C<Subscript>5</Subscript>H<Subscript>5</Subscript>) to Synthesize Pd@MOF-5 Catalysts for Suzuki Coupling Reaction

Abstract  

The highly porous metal organic framework MOF-5 was loaded with the metal–organic compound [Pd(C₃H₅)(C₅H₅)] by metal–organic chemical vapor deposition (MOCVD) method. The inclusion compound [Pd(C₃H₅)(C₅H₅)]@MOF-5 was characterized by powder X-ray diffraction (PXRD), Fourier-transform infrared (FT-IR) spectroscopy, and solid-state nuclear magnetic resonance spectroscopy. It was found that the host lattice of MOF-5 remained intact upon precursor insertion. The –C₃H₅ ligand in the precursor is easier to lose due to the interaction between palladium and the benzenedicarboxylate linker in MOF-5, providing a possible explanation for the irreversibility of the precursor adsorption. Pd nanoparticles of about 2–5 nm in size was formed inside the cavities of MOF-5 by hydrogenolysis of the inclusion compound [Pd(C₃H₅)(C₅H₅)]@MOF-5 at room temperature. N₂ sorption of the obtained material confirmed that high surface area was retained. In the Suzuki coupling reaction the Pd@MOF-5 materials showed a good activity in the first catalytic run. However, the crystal structure of MOF-5 was completely destroyed during the following reaction runs, as confirmed by PXRD, which caused a big loss of the activity.     

Optimization of High Conducting Na<Subscript>3</Subscript>Zr<Subscript>2</Subscript>Si<Subscript>2</Subscript>PO<Subscript>12</Subscript> Phase by new Phosphate Salt for Solid Electrolyte

A composition of NASICON (Na₃Zr₂Si₂PO₁₂) was synthesized by the solid-state reaction method using a new compound Na₂HPO₄2H₂O. The X-ray diffraction patterns of all samples exhibit monoclinic Na₃Zr₂Si₂PO₁₂ as a major phase with a very small amount of monoclinic-ZrO₂. The maximum relative density (97 %) and maximum conductivity is obtained in the samples sintered at 1200 °C (N3) which is slightly higher than β-Al₂O₃. The activation energy is ～ 0.20 eV for the N3 sample which is lower than for β-Al₂O₃. The dilatometeric study and Arrhenius plots confirmed a phase transition of NASICON from monoclinic to rhombohedral. The micro-structural study of the samples done by scanning electron microscopy (SEM) indicated a significant influence of the processing conditions on the microstructures. Raman spectroscopy demonstrated that the sample N3 exhibits minor structural changes compared to other samples.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript>@TiO<Subscript>2</Subscript>-OSO<Subscript>3</Subscript>H: an efficient hierarchical nanocatalyst for the organic quinazolines syntheses

A sulfonic acid functionalized titanium dioxide quasi-superparamagnetic nanocatalyst Fe₃O₄@SiO₂@TiO₂-OSO₃H with average size of 61 nm and semispherical shape with surface area about 97 m² g^?1 with saturation magnetization 17.7 emu g^?1 and the coercivity 9.84 Oe was successfully synthesized. The structure and morphology of the nanocatalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), energy-dispersive X-ray spectroscopy, X-ray diffraction pattern, transmission electron microscopy, field-emission scanning electron microscopy, vibrating sample magnetometer and Brunauer–Emmett–Teller surface area analysis. The catalytic usage of the nanocatalyst was exemplified in synthesis of 2,3-dihydroquinazolin-4(1H)-one and spiroquinazolin-4(3H)-one derivatives in deep eutectic solvents (DESs) based on choline chloride and urea. We suggest that the synergistic effects in catalytic activities of titanium dioxide, organic acid and the CO₂ capture property of DES are the main reasons for the improvement of catalytic activity. The synthesized spiroquinazolinones and dihydroquinazolinones derivatives were characterized by FT-IR, ¹H and ¹³C nuclear magnetic resonance spectroscopy. The magnetic nanocatalyst exhibit high catalytic activity and can be simply separated from reaction media by an external magnet in a few seconds and could be reused for six cycles without significant loos in activity, which indicates the good immobilization of sulfonic acid on the magnetic titanium dioxide support. Furthermore, the solvent which has been used in this work can be readily isolated and reused for several times.     

Effect of synthesis condition and annealing on the sensitivity and stability of gas sensors made of Zn-doped <Emphasis Type="Italic">γ</Emphasis>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> particles

Gas sensors made of flame-synthesized Zn-doped γ-Fe₂O₃ nanoparticles were found to have high sensitivity and high aging resistance. Zinc-doped γ-Fe₂O₃ nanoparticles and microparticles were synthesized by flame spray pyrolysis (FSP). Gas sensors were fabricated with as-synthesized particles, and with particles that had been annealed. The sensors’ response to acetone vapor and H₂ was measured as fabricated, and measured again after the sensors were aged for three days. The sensors made from as-synthesized particles showed a gas sensing sensitivity 20 times higher than the literature value. However, sensors made of microparticles lost their sensing ability after three days of aging; sensors made of nanoparticles retained their gas sensing capability after aging. Sensors made of annealed particles did not have significant gas sensing capabilities. Analysis using the William and Hall method showed that the microstrains decreased significantly in both H₂/O₂ and H₂/Air flame synthesized particles after annealing. The results showed that sensors made of flame-synthesized particles have much higher sensitivity than sensors made of particles previously reported. Especially, sensors made of flame-synthesized nanoparticles are resistant towards aging. This aging resistance may be attributed to the particles’ ability to retain their microstrains.     

Properties of unsupported MoS<Subscript>2</Subscript> species produced in the preparation of MoS<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> using a sonochemical method

Unsupported MoS₂ particles, which were produced in the preparation of MoS₂/Al₂O₃ using a sonochemical method, were successfully separated from the prepared sample catalyst by adding oleylamine as an agent for dispersing the unsupported particles. The fraction of the unsupported MoS₂, which was estimated based on Mo balance, varied between 0.03 and 0.4, independent of the Mo loading levels investigated (6–54 wt% of Mo). The activity of the unsupported MoS₂ for the hydrodesulfurization of dibenzothiophene was nearly the same as that of the Al₂O₃-supported MoS₂, indicating that the activity of the prepared catalyst was not affected by the presence of the unsupported MoS₂ particles.