Preparation of polystyrene/zirconia core-shell microspheres and zirconia hollow shells

Zirconia/polystyrene core-shell microspheres were prepared through room-temperature aging process and a solvothermal process with ethanol as solvent. Through the hydrolysis of zirconium propoxide, ZrO₂ was coated on PS cores to form the core-shell microspheres. And hollow ZrO₂ shells were formed by calcining the core-shell particles in a muffle oven under static air at 600 °C.     

Cobalt ferrite nanoparticles hosted in activated carbon from renewable sources as catalyst for methanol decomposition

High quality micro-mesoporous activated carbon was prepared from waste bio-mass (peach shells) and used as a host matrix of cobalt ferrite nanoparticles. The obtained materials were characterized by N₂ physisorption, XRD, FTIR and Moessbauer spectroscopy and tested as catalysts for hydrogen production from methanol. Depending on the Co/Fe ratio formation of pure CoFe₂O₄ or a mixture of CoO and ferrite phases were observed for carbon supported bi-component materials, while under the same condition the silica support provides the formation of non-stoichiometric ferrite phase. The catalytic active phase which is formed by the influence of the reaction medium represents a complex mixture of non-changed ferrite, magnetite, Co–Fe alloy and/or Fe₃C in different proportions.     

Suspension polymerization based on inverse Pickering emulsion droplets for thermo-sensitive hybrid microcapsules with tunable supracolloidal structures

Polymerization using Pickering emulsion droplets as reaction vessels is being developed to become a powerful tool for fabrication of hybrid polymer particles with supracolloidal structures. In this paper, two kinds of thermo-sensitive hybrid poly(N-isopropylacrylamide) (PNIPAm) microcapsules with supracolloidal structures were successfully prepared from suspension polymerization stabilized by SiO₂ nanoparticles based on inverse Pickering emulsion droplets. SiO₂ nanoparticles could self-assemble at liquid-liquid interfaces to form stable water-in-oil inverse Pickering emulsion. NIPAm monomers dissolving in suspended aqueous droplets were subsequently polymerized at different temperatures. The hollow microcapsules with SiO₂/PNIPAm nanocomposite shells were obtained when the reaction temperature was above the lower critical solution temperature (LCST) of PNIPAm. While the core-shell microcapsules with SiO₂ nanoparticles' shells and PNIPAm gel cores were produced when the polymerization was conducted at the temperature lower than LCST using UV light radiation. The supracolloidal structures with different cores could be tuned by simply changing reaction temperature, which was confirmed by confocal laser scanning microscopy and scanning electron microscopy. The interesting properties of both microcapsules were their ability of reversibly swelling during drying/wetting cycles and responsive to temperature stimulus. Such functional microcapsules may find applications in double control release system due to the presence of the supracolloidal structures and thermo-sensitivity.     

Synthesis and characteristics of carbon-coated iron and nickel nanocapsules produced by arc discharge in ethanol vapor

Fe(C) and Ni(C) nanocapsules with low carbon content have been produced via an arc discharge process in ethanol vapor. It is clarified by X-ray diffraction that the core of the Fe(C) nanocapsules consists of γ-Fe, α-Fe and Fe₃C phase, while that of the Ni(C) nanocapsules contains only nickel. High-resolution transmission electron microscopy imaging confirms that these particles have a broad size distribution and the core/shell structure. Besides mutually independent nanocapsules with segregate graphitic shells, those with sharing shells are also observed in the Fe(C) nanocapsules. The remanence and the coercivity at room temperature of both the nanocapsules are higher than those of the corresponding microcrystallines, while the saturation magnetization is lower.     

Enhanced Microwave Absorption Properties of Intrinsically Core/shell Structured La0.6Sr0.4MnO3 Nanoparticles

The intrinsically core/shell structured La_0.6Sr_0.4MnO₃nanoparticles with amorphous shells and ferromagnetic cores have been prepared. The magnetic, dielectric and microwave absorption properties are investigated in the frequency range from 1 to 12 GHz. An optimal reflection loss of −41.1 dB is reached at 8.2 GHz with a matching thickness of 2.2 mm, the bandwidth with a reflection loss less than −10 dB is obtained in the 5.5–11.3 GHz range for absorber thicknesses of 1.5–2.5 mm. The excellent microwave absorption properties are a consequence of the better electromagnetic matching due to the existence of the protective amorphous shells, the ferromagnetic cores, as well as the particular core/shell microstructure. As a result, the La_0.6Sr_0.4MnO₃nanoparticles with amorphous shells and ferromagnetic cores may become attractive candidates for the new types of electromagnetic wave absorption materials.     

Formation of bamboo-shape carbon nanotubes by controlled rapid decomposition of picric acid

In the presence of catalysts, carbon nanotubes (CNTs) can efficiently grow in the environment generated by the rapid decomposition of normal explosives. Controlling the reaction parameters of a mixture of picric acid (PA) with cobalt acetate and paraffin can lead to a well-defined morphology of CNTs. The formation of bamboo-shape tubes is favorable at relatively high Co(AC)₂/PA and paraffin/PA ratios. It is found that the bamboo-shape tubes are different in morphology and structure and can be categorized roughly into two types, according to the participation of the catalyst nanoparticles. The formation of the two types is discussed.     

A practical route to the production of carbon nanocages

Carbon-coated iron nanoparticles with diameters ranging from 5 to 50 nm and a few layers of graphitic shells have been synthesized in a mass scale by laser-induction complex heating evaporation. Through the studies on the dissolution behavior of the inner iron cores under the treatments of HCl and HNO₃ acids at different conditions, a practical route with the combined treatments of HNO₃ and HCl acids has been optimized to produce carbon nanocages. The nanocages thus obtained have some channels and are full of defects in the shells, as characterized by high-resolution transmission electron microscopy and Raman spectroscopy. Similar treatments should also be applicable to some other carbon-coated metal nanoparticles, e.g., Ni-C and Co-C, for the same purpose.     

Preparation and formation mechanism of Al-Si/Al2O3 core-shell structured particles fabricated via steam corrosion

In this study, Al-Si/Al₂O₃ core-shell structured particles were fabricated via pressurized steam corrosion for 1 h followed by heating for 3 h at 1100 °C. After steam corrosion, a layer composed of disordered crystals covered the surfaces of the Al-Si alloy particles. After heating, Al-Si/Al₂O₃ core-shell structured particles with complete shells were prepared. The thickness of the shell was approximately 2 μm, and it enclosed the Al-Si alloy core. The shell exhibited excellent thermal stability because, even at 1100 °C, the mass gain ratio of the encapsulated particle was less than 0.5%. Scalloped patterns of alumina were formed by the oxidation of Al, which was inlaid through and upon the alumina shell. The shell formation mechanism suggested that the α-Al₂O₃ shell resulted from the combination of the decomposition of surface Al(OH)₃ crystals and the oxidation of Al from the core.     

Fluorinated carbon blacks: influence of the morphology of the starting material on the fluorination mechanism

The effect of fluorination, using CF₄ r.f. plasmas, has been studied on three different types of carbon blacks: a thermal black, a furnace black and a high electrical conducting black. The influences of the morphology and structure of the three blacks on the fluorination mechanism have been investigated. In particular, the ratio Type I/Type II structures (i.e., surface (CF) and border groups of graphitic domains with sp²C/polyalicyclic perfluorinated structures with sp³C), has been correlated to the microstructural organisation. The transformation into Type II structures is more easily achieved in highly accessible XE2 blacks, whereas in materials with lower crystallinity (MT), the presence of numerous defects leads preferentially to surface (CF_x) perfluorinated groups.     

Cs-modified iron nanoparticles encapsulated in microporous and mesoporous SiO2 for COx-free H2 production via ammonia decomposition

The stable core–shell Fe@SiO₂ catalysts reported in this paper are highly efficient for the generation of CO_x-free H₂ through ammonia decomposition. By tuning the porosity of SiO₂ shells (using C₁₈TMS agent) and with the introduction of an appropriate amount of Cs dopant (via pre-deposition as well as post-impregnation), the diffusion efficiency of the catalysts and the surface property of Fe cores can be modified for better performance. The Fe@SiO₂ structures function as microcapsular-like reactors during ammonia decomposition. Naked nanoparticles of metallic iron tend to aggregate into bulk particles spontaneously. The role of the stable SiO₂ shells is to prevent the enwrapped core particles from aggregation at high reaction temperatures.     

Activated carbon supported bimetallic CoMo carbides synthesized by carbothermal hydrogen reduction

A carbothermal hydrogen reduction method was employed for the preparation of activated carbon supported bimetallic carbide. The resultant samples were characterized by BET surface area measurement, X-ray diffraction, and temperature-programmed reduction-mass spectroscopy. The results showed that nanostructured β-Mo₂C can be formed on the activated carbon by carbothermal hydrogen reduction above 700 °C. The particle sizes of β-Mo₂C increase with increasing reaction temperatures and Mo loading. The bimetallic CoMo carbide can be synthesized by the carbothermal hydrogen reduction even around 600 °C. The bimetallic CoMo carbide is from carbothermal hydrogen reduction of CoMoO₄ precursor and is easily formed when the Co/Mo molar ratio is 1.0. Separation of the bimetallic CoMo carbide phase into Mo carbide and Co metal occurs when the temperature of the reduction is above 700 °C. The addition of a second metal such as Co and Ni, decreases the formation temperature of carbide because the second metal promotes formation of CHx species from reactive carbon atoms or groups on carbon material and hydrogen, which further carburizes oxide precursors.     

Nanographite structures formed during annealing of disordered carbon containing finely-dispersed carbon nanocapsules with iron carbide cores

Disordered carbon containing finely-dispersed carbon nanocapsules with iron carbide cores were synthesized by a modified method in which low-current plasma discharge was generated in liquid ethanol with ultrasonic irradiation. The structure of nanographite forms prepared by the annealing at 900 °C for 2 h of disordered carbon containing finely-dispersed carbon nanocapsules was studied. Transmission electron microscopy (TEM) studies of the powder sample after annealing revealed most part of disordered carbon was transformed into nanographite ribbons, hollow polyhedral graphitic cages and thick carbon shells with the turbostratic structure of carbon layers. TEM observations of the carbon layers revealed stacking defects. Selected-area diffraction and fast Fourier transforms of digitized images revealed that carbon inter-layer spacings vary from 3.4 to 3.5 Å. XRD analysis showed that annealing of the powder sample at 900 °C for 2 h resulted in the decompositions of iron carbide cores and a well-defined broad carbon peak (0 0 2) centered at 2θ ≈ 25.9° (d₀₀₂ = 3.44 Å) was detected. The growth of the I_D/I_G ratio and shift of the D peak to a lower wavenumber may indicate increase in size the graphite clusters and ordering carbon structure, i.e. appearance of nanographite structures.     

Fluorination of carbon blacks: an X-ray photoelectron spectroscopy study: IV. Reactivity of different carbon blacks in CF4 radiofrequency plasma

The effect of CF₄-plasma enhanced fluorination on the surface modification of carbon blacks has been examined using XPS. Three different types of carbon blacks have been studied: a thermal black, a furnace black and a high electrical conducting black. The analysis of the XPS spectra of fluorinated carbon black samples indicates that all fluorine atoms, fixed at the surface and in a subsuperficial zone of the particles, are covalently linked to carbon atoms. The influence of the physicochemical properties and morphology of these three types of carbon blacks on the fluorination reaction has also been investigated. The proportion of different types of fluorinated carbon atoms, i.e. on one hand CF_x surface and border groups of graphitic bulk domains for which the planar configuration of the graphene layers is preserved together with the sp² character of C, i.e. structures of type I, on the other hand polyalicyclic perfluorinated structures in which sp³C form puckered layers similar to those of covalent fluorographites, i.e. structures of type II, and also the F/C ratio of the fluorinated groups are related to the surface morphology and depend on the microstructural organization of particles. When the microstructure ordering and graphitic character of the carbon increase, the size of the ordered graphitic domain also increases. At the same time the density, the size of defects and proportion of protonated sp³C entities bridging the graphene layers decrease. As a consequence, the proportion of carbon atoms, potentially able to form perfluorinated CF₂ and CF₃ groups, decreases. The relative contribution of those groups is appreciably higher in fluorinated compounds which are derived from carbon blacks with a lower structural order.     

Decomposition of metal carbides as an elementary step of carbon nanotube synthesis

The role of catalyst components in catalysts containing molybdenum, Mo/M/MgO (MNi, Co, and Fe), as well as Mo-free catalysts, M/MgO (MNi, Co, and Fe), for carbon nanotube (CNT) synthesis have been investigated by TEM, XRD, and Raman spectroscopy. CNT synthesis by the catalytic decomposition of CH₄ over M/MgO catalysts can proceed at reaction temperatures higher than the decomposition temperature of the metal carbides (Ni₃C, Co₂C, and Fe₃C), which indicates that carbon in the CNT originates from the graphitic carbon formed on the catalyst surface by the decomposition of metal carbides. For all catalysts containing Mo, thin CNT formation starts at an identical temperature of 923 K, corresponding to the decomposition temperature of MoC_1−x into Mo₂C. The significant effect of the addition of Mo is concerned with the formation of Mo₂C in a catalyst particle during CNT synthesis at high reaction temperatures. The presence of a stable Mo₂C phase leads to the formation of thin CNT with better crystallinity at high reaction temperatures. The role of Ni, Co, and Fe in the Mo/M/MgO catalysts is ascribed to the dissociation of CH₄.     

Polymer-derived Co2Si@SiC/C/SiOC/SiO2/Co3O4 nanoparticles: Microstructural evolution and enhanced EM absorbing properties

In this work, porous core-shell structured Co₂Si@SiC/C/SiOC/SiO₂/Co₃O₄ nanoparticles were fabricated by a polymer-derived ceramic approach. The in situ formation of mesopores on the shell, microstructural, and phase evolution of resulting nanoparticles were investigated in detail. The obtained nanoparticles-paraffin composites possess a very low minimum reflection coefficient (RC_min) −60.9 dB, broad effective absorption bandwidth 3.50 GHz in the X-band and 15.5 GHz in the whole frequency range (from 2.5 to 18 GHz). The results indicate outstanding electromagnetic wave (EMW) absorbing performance among all the reported cobalt-based nanomaterials, due to the reasons as follows: (a) The unique core-shell structure as well as complex phase composition of SiC/C/SiOC/SiO₂/Co₃O₄ in the shell, result in a large number of heterogeneous interfaces in the nanoparticles; (b) Nanoparticles have both dielectric and magnetic loss; (c) Mesopores in the shell prolong the propagation path of EMW, thereby increasing the absorption/reflection ratio of EMWs. Thanks to the material structure design, the resulting core-shell structured cobalt-containing ceramic nanoparticles have great potential for thin and high-performance EMW absorbing materials applied in harsh environment.     

Influence of anionic and non-ionic surfactants on the synthesis of core-shell Fe3O4@TiO2 nanocomposite synthesized by hydrothermal method

Magnetite spinel nanoparticles (Fe₃O₄) coated titanium dioxide has been prepared by the solvo-hydrothermal method for application in dye degradation and wastewater remediation. The core-shell Fe3O4@TiO2 nanoparticles have been synthesized using titanium butoxide (TBT) and ferric chloride as precursors. In this method, firstly, magnetite nanoparticles have been prepared through a solvothermal process using ethylene glycol as a solvent. Then, titanium butoxide was used as a precursor to synthesize Fe₃O₄@TiO₂ core-shell nanoparticles using the hydrothermal method. The surfactants that were added, in separate synthetic processes, were anionic oleic acid and Sodium Dodecyl sulfonate, and non-ionic Polyvinylpyrrolidone and Polyethylene glycol. The effects of the various surfactants on the fabrication of core-shell magnetic nanoparticles were studied. Various characterization methods have been established to examine the morphology and magnetization features of the nanostructured particles, such as XRD, FTIR, TEM, FESEM, UV-spectroscopy, and VSM, etc., which validated the formation of Titania coated magnetite nanoparticles. The TiO₂ shell formation drastically reduces the saturation magnetization of the magnetic nanoparticles. The Oleic acid as a surfactant produces the smallest nanoparticles. The PVP coating is best amongst these surfactants for the retention of saturation magnetization upon coating.     

Facile fabrication of nanocomposite microspheres with polymer cores and magnetic shells by Pickering suspension polymerization

Pickering suspension polymerization was used to prepare magnetic polymer microspheres that have polymer cores enveloped by shells of magnetic nanoparticles. Styrene was emulsified in an aqueous dispersion of Fe₃O₄ nanoparticles using a high shear. The resultant Pickering oil-in-water (o/w) emulsion stabilized solely by magnetic nanoparticles was easily polymerized at 70 °C without stirring. Fe₃O₄ nanoparticles act as effective stabilizers during polymerization and as building blocks for creating the organic–inorganic hybrid nanocomposite after polymerization. The fabricated magnetic nanocomposites were characterized by FTIR, XRD, TGA, DSC, GPC, XPS and SEM. The structures of the polymer core and the nanoparticle shell were analyzed. We investigated the effects on the products of the weight of Fe₃O₄ nanoparticles used to stabilize the original Pickering emulsions. Pickering suspension polymerization provides a new route for the synthesis of a variety of hybrid nanocomposite microspheres with supracolloidal structures.     

Electrochemical reduction of trinitrotoluene on core-shell tin-carbon electrodes

In this work, we studied the electrochemical process of 2,4,6-trinitrotoluene (TNT) reduction on a new type of electrodes based on a core-shell tin-carbon Sn(C) structure. The Sn(C) composite was prepared from the precursor tetramethyl-tin Sn(CH₃)₄, and the product contained a core of submicron-sized tin particles uniformly enveloped with carbon shells. Cyclic voltammograms of Sn(C) electrodes in aqueous sodium chloride solutions containing TNT show three well-pronounced reduction waves in the potential range of −0.50 to −0.80 V (vs. an Ag/AgCl/Cl⁻ reference electrode) that correspond to the multistep process of TNT reduction. Electrodes containing Sn(C) particles annealed at 800 °C under argon develop higher voltammetric currents of TNT reduction (comparing to the as-prepared tin-carbon material) due to stabilization of the carbon shell. It is suggested that the reduction of TNT on core-shell tin-carbon electrodes is an electrochemically irreversible process. A partial oxidation of the TNT reduction products occurred at around −0.20 V. The electrochemical response of TNT reduction shows that it is not controlled by the diffusion of the active species to/from the electrodes but rather by interfacial charge transfer and possible adsorption phenomena. The tin-carbon electrodes demonstrate significantly stable behavior for TNT reduction in NaCl solutions and provide sufficient reproducibility with no surface fouling through prolonged voltammetric cycling. It is presumed that tin nanoparticles, which constitute the core, are electrochemically inactive towards TNT reduction, but Sn or SnO₂ formed on the electrodes during TNT reduction may participate in this reaction as catalysts or carbon-modifying agents. The nitro-groups of TNT can be reduced irreversibly (via two possible paths) by three six-electron transfers, to 2,4,6-triaminotoluene, as follows from mass-spectrometric studies. The tin-carbon electrodes described herein may serve as amperometric sensors for the detection of trace TNT.     

Photocatalytic Preparation of Encapsulated Gold Nanoparticles by Jingle-bell-shaped Cadmium Sulfide–silica Nanoparticles

Gold (Au) nanoparticles were deposited inside silica: (SiO₂) shells containing cadmium sulfide (CdS) nanoparticles through photocatalytic reduction of potassium dicyanogold(I) by CdS. Photocatalytic Au deposition occurred only when core-shell nanoparticles having a void space between the core and shell, i.e., a jingle-bell-shaped structure, were used. These core-shell nanoparticles were prepared by size-selective photoetching of SiO₂ -covered CdS nanoparticles. The size of Au nanoparticles could be controlled by adjustment of the void space in SiO₂-covered CdS. Dissolution of CdS by acid treatment from the Au-deposited jingle-bell nanoparticles did not have any effect on the surface-plasmon absorption by Au. These facts indicate that Au nanoparticles of adjustable size can be prepared in an SiO₂ shell that prevents mutual coalescence of Au nanoparticles but allows permeation of molecules and ions.     

Fe/N/C non-precious catalysts for PEM fuel cells: Influence of the structural parameters of pristine commercial carbon blacks on their activity for oxygen reduction

Fifteen commercial SRCC furnace carbon blacks of various grades, ranging from N1 to N9, were used as carbon supports in the preparation of Fe/N/C type electrocatalysts for the oxygen reduction reaction (ORR) in PEM fuel cell conditions. All catalysts were prepared by loading the various carbon grades with 0.2 wt.% Fe as iron acetate and heat-treating the resulting material at 950 °C in pure NH₃. This reaction provides the nitrogen content and the microporosity necessary to synthesize and host the Fe/N/C catalytic sites that perform ORR. The maximum catalytic activity (V_pr max) for each carbon grade was determined by optimizing pyrolysis time. The aim of this study is to determine which structural characteristics of the pristine carbon black are important for maximizing catalytic activity. Three structural parameters that influenced the catalytic site density on the carbon support were identified. They are: (i) the average particle diameter of the pristine carbon black, d_particle, available from BET area measurements; (ii) the amount of disordered phase which is proportional to W_D, the width at half maximum of the D peak in the Raman spectrum of the pristine carbon; and (iii) the mean size of the graphene layers characterizing the graphitic crystallites in the carbon black, L_a. The latter is available by Rietveld analysis of the XRD spectra of the pristine carbons. The best catalytic activities are obtained for the smallest d_particle, the largest W_D, and the largest L_a. Optimizing these three parameters maximizes the fraction of the pristine carbon black that becomes microporous upon reaction with NH₃ and, therefore, enables the formation of Fe/N/C catalytic sites. A FeN₂₊₂/C structure bridging two adjacent graphitic crystallites is proposed as a potential model for most of the catalytic sites present in such Fe/N/C type catalysts.