Formation of Carbon Filaments from 1,3-Butadiene on Fe/Al2O3 Catalysts

The formation of carbon filaments with different crystallographic and morphological characteristics in the course of 1,3-butadiene decomposition on Fe/Al₂O₃ catalysts at low (500–600°C) and high (700–800°C) temperatures was considered in terms of a carbide cycle mechanism. The conditions of formation and decomposition of an iron carbide phase in the course of formation of graphite nanotubes in the low-temperature region were studied.     

Study on the hydrothermal reaction of FeCl<Subscript>3</Subscript> solution in the presence of poly(vinyl alcohol)

A 0.5 dm³ aqueous solution of 0.1 M FeCl₃ dissolving 1 wt% poly(vinyl alcohol) (PVA) was treated hydrothermally in a stainless steel autoclave at various temperatures (T _h=110–200 °C). Highly ordered red corpuscle-like hematite particles around 2 m in diameter were produced after aging the solution at T _h=110 °C for 7 days, though large numbers of spherical PVA microgels around 2–4 m in diameter were produced together with the red corpuscle-like particles at T _h120 °C. The number of red corpuscle-like hematite particles decreased but that of spherical PVA microgels increased with increasing T _h, leading to the proposal that the method carried out in the present study will become a new synthetic method of polymer microgels. The ferric ions acted as a cross-linking agent to make PVA insoluble in water. The red corpuscle-like hematite particles produced at T _h=110 °C had high specific surface areas and showed high mesoporosity. The mesoporosity appeared to be more pronounced after evacuating the particles above 300 °C. The diameter of the mesopores after evacuation above 300 °C ranged from 2 to 20 nm, with a maximum at around 5–6 nm. The H₂O and N₂ adsorption experiments revealed that there are no ultramicropores in the particles. The H₂O and CCl₄ adsorption experiments further disclosed that the surface hydrophobicity of the particles is low even though PVA molecules remain after evacuation of the particles at 100–400 °C. Furthermore, the micropores produced after evacuation of the particles at 400 °C exhibited a high size restriction effect, i.e., the micropores produced were accessible to H₂O (diameter 0.253 nm) and N₂ (diameter 0.318 nm) molecules but not to CCl₄ (diameter 0.514 nm).     

Preparation of TiO2 coating films containing Pd fine particles by sol-gel method

TiO₂ coating films of 0.3–0.4 m in thickness that contain fine Pd particles have been prepared by sol-gel method using Ti(OC₃H ₇ ⁱ )₄ and PdCl₂ as starting materials in an attempt to obtain optical materials that show surface plasma resonance in the visible range. A temperature higher than 900°C was required for formation of Pd metal particles when the heat-treatment was conducted in air. Heat-treatment of pre-heated amorphous films in air at 800°C resulted in precipitation of PdO particles, the size of which could be varied by changing the time of heat-treatment, and subsequent heat-treatment in H₂/Ar gas converted the PdO particles into Pd metal particles. Heat-treatment of pre-heated amorphous films in H₂/Ar gas also resulted in precipitation of Pd metal particles. The size of the Pd metal particles precipitated in the films was 6 to 90 nm, depending on the conditions of heat-treatment. The resultant TiO₂ films containing Pd metal particles were brownish grey in color and showed optical absorption in the visible range over 400 nm, which is attributed to surface plasma resonance of Pd metal particles.     

Formation of filamentous carbon from 1,3-butadiene over a Ni-Pd/Al2O3 catalyst

The formation of carbon filaments from 1,3-butadiene over a Ni-Pd/Al₂O₃ catalyst at 400–450?C was studied by high-resolution electron microscopy and X-ray diffraction analysis. The carbon filaments differ in morphology and in the arrangement of active metal inclusions: (1) abundant ～ 1000 å thick filaments contain biconical alloy particles in the middle of the filament, (2) thin filaments of a thickness less than 500 å rolled in helical fashion contain oval-shaped alloy particles in the middle, and (3) in a few filaments that are less than 200 å thick, alloy particles are positioned at the ends. When the first two types of filaments grow, decomposition of the hydrocarbon occurs at the active sites of the surface with the formation of a carbide microphase with a hexagonal structure. This phase is called the active microphase. When the reaction stops, the active phase decomposes to form carbon and hexagonal nickel. Extensive defects like grain boundaries and stacking fault dislocations are present in the bulk of Ni-Pd alloy particles. The origin of these defects is related to the epitaxial effect of the active microphase particles on the alloy.     

Synthesis and characterization of tin(IV) antimonate and study of its ion-exchange equilibria

Tin(IV) antimonate with different Sb/Sn molar ratios has been prepared. The characterization of the product materials was carried out using X-ray diffraction pattern, themal analysis and infrared spectra. The saturation capacities of sodium and cesium were found to increase with Sb/Sn molar ratios. TheK _d values on thermal treatment of tin(IV) antimonate, as a cation exchanger, have been measured for some heavy metal ions in the temperature range of 50–400 °C. The maximum adsorption of 10^–4M of the metal ions studied was obtained at 400 °C. The selectivity sequence was Eu³⁺>Co²⁺>Sr²⁺>Cs⁺ for the sample heated up to 400 °C. No adsorption was observed on the sample heated at 700 °C because of the formation of SnO₂ and Sb₆O₁₃.     

Effect of the Structure of Carbon Nanofibers on the State of an Active Component and on the Catalytic Properties of Pd/C Catalysts in the Selective Hydrogenation of 1,3-Butadiene

The state of highly dispersed palladium particles supported on filamentous carbon was studied using high-resolution electron microscopy, XPS, and X-ray diffraction analysis. Three types of filamentous carbon were used, in which the basal planes of graphite were arranged along, across, and at an angle to the nanofiber axis. The amount of supported palladium was 0.25–5.8 wt %. The structure of the carbon support was found to affect the properties of the active component. Highly dispersed palladium particles exhibited the strongest interaction with a carbon surface formed by the butt ends of graphite (002) layers. This interaction resulted in electron transfer from the metal to the support and in the stabilization of palladium in the most dispersed state. A change in the properties of palladium particles caused a change in the catalytic properties of Pd/C catalysts in the reaction of selective 1,3-butadiene hydrogenation to butenes. The strong interaction of Pd²⁺ with the butt ends of graphite resulted in the stabilization of palladium in an ionic state. An increase in the fraction of Pd²⁺ in the catalysts was responsible for a decrease in both the overall activity and selectivity of Pd/C catalysts in the reaction of 1,3-butadiene hydrogenation to butenes.     

Submonolayer-Deposition of Mass-Selected Au+ and Au n + (n = 3 and 7) on HOPG and Amorphous Carbon

Ions of gold monomer and clusters emitted from a liquid metal ion source were mass-selected, and deposited on cleaved HOPG (highly oriented pyrolytic graphite) surfaces and on amorphous carbon thin films at room temperature with the impinging energy E _i from 0 to 500 eV. The coverage of deposited ions were 1/100 and 1/1000 monolayers on HOPG surfaces and 1/3 monolayers on carbon films. Scanning tunneling microscopy of the HOPG surfaces deposited with low impinging energy (E _i<50 eV) revealed that large clusters with diameters ranging from 2 to 5 nm and height of 1–2 layers were present instead of isolated monomers and original clusters. When E _i was higher than 100 eV, HOPG surfaces were damaged and only bumpy surfaces were observed by STM. Transmission electron microscopy of Au⁺-deposited carbon films showed the formation of clusters with diameter 0.5–20 nm, depending on the E _i and the time elapsed after deposition.     

Formation of the Pore Structure of Oxide Vanadium–Titanium–Phosphorus Catalysts in the Course of Thermal Treatment

The effect of the conditions of the thermal treatment of vanadium–titanium–phosphorus catalysts on the formation of the pore structure and phase composition was studied. It was found that the optimum doping of catalysts with phosphorus (5 wt % P₂O₅) was favorable for retention of the high dispersity of primary particles up to 450°C. The main change in the texture of the catalysts occurred within the range of micropores and mesopores with D < 10 nm. The formation of the coarsely dispersed well-crystallized phase of a vanadium–titanium–phosphorus compound was detected.     

Silicon Carbide Modified Carbon Materials. Formation of Nanocrystalline SiC from Thermochemical Processes in the System Coal Tar Pitch/Poly(carbosilane)

Poly(carbosilane) or PCS, {–CH₂–SiH(CH₃)–} _n , is used as a Si-bearing precursor in combination with a coal tar pitch to study thermally induced transformations toward SiC-modified carbon composites. Following mixing of the components in the molten pitch at 160°C, the mixture is heated under argon atmosphere at 500°C yielding a solid carbonizate that is further subjected to separate pyrolysis experiments at 1300°C or 1650°C. At temperatures up to 500°C, the PCS reacts with suitable pitch components as well as undergoing decomposition reactions. At higher temperatures, clusters of prevailingly nanocrystalline -SiC are confirmed after the 1650°C pyrolysis step with indications that the formation of the compound starts at 1300°C. ²⁹Si MAS NMR, XRD, FT-IR, XPS, and elemental analysis are used to characterize each pyrolysis step, especially, from the viewpoint of transformation of silicon species to silicon carbide in the carbon matrix evolved from the pitch.     

Studies on hydrolyzable carbides. XXII: The carbothermal reduction of scandium oxide Sc2O3

The composition of the products of carbothermal reduction of Sc₂O₃ is examined by X-ray diffraction and chemical analysis and by the hydrolysis method. At pressures of 10^–2-1 Pa, the reaction starts in the temperature region of 1 000–1 200°C. The first product is Sc₂OC of NaCl type; at 1 Pa and 1 400–1 500°C this substance is formed quantitatively (according to stoichiometry) within 50–100 h, repeated homogenization, however, is necessary, or else Sc₂OC reacts locally with Sc₂O₃ giving Sc₂O_1+x C_1–x . The lattice parameter of Sc₂OC in the presence of Sc₁₅C₁₉ is 457.6₃pm. At temperatures above 1 500°C, Sc₁₅C₁₉ is incompletely formed by subsequent reaction with carbon. The product melts at cca. 1 800°C; carbon dissolves and the final composition approaches ScC₂. Carbon separates during solidification. The phase fractions in the products are affected by evaporation, the vapour pressures above both Sc₂OC and Sc₁₅C₁₉ being comparable with the pressure requisite for the carboreduction process. The results are discussed with respect to the often ambiguous published data.

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Untersuchung hydrolysierbarer Carbide, XXII. Die karbothermische Reduktion von Scandiumoxid

Zusammenfassung Zur Untersuchung von Produkten der karbothermischen Reduktion von Scandiumoxid wurden sowohl röntgenographische und chemische Analyse als auch die hydrolytische Methode verwendet. Bei 10^–2 bis 1 Pa beginnt die Reaktion im Temperaturintervall von 1 000–1 200°C. Das erste Reaktionsprodukt ist das Scandiumoxidcarbid Sc₂OC von NaCl-Typ, das quantitativ (der Stöchiometrie entsprechend) bei 1 400–1 500°C und 1 Pa in 50–100 Stunden entsteht. Eine wiederholte Homogenisierung ist allerdings notwendig, damit es zu keiner lokalen Reaktion zwischen Sc₂OC und Sc₂O₃ kommt, bei der dann die Phase Sc₂O_1+x C_1–x entsteht. In Gegenwart von Sc₁₅C₁₉ ist der Gitterparameter von Sc₂OCa=457.6₃pm. Über 1 500°C führt eine weitere Reaktion mit Kohlenstoff zu einer nicht ganz vollendeten Bildung von Sc₁₅C₁₉. Bei cca. 1 800°C schmilzt das Reaktionsprodukt bei gleichzeitiger Auflösung von weiterem Kohlenstoff und die Zusammensetzung nähert sich der Formel ScC₂, beim Erstarren fällt der Kohlenstoff wieder aus. Die Verteilung der Phasen im Produkt wird von der Verdampfung beeinflußt, da die Dampfdrucke von Sc₂OC und Sc₁₅C₁₉ mit dem zum Karboreduktionverlauf notwendigen Druck vergleichbar sind. Die erhaltenen Ergebnisse werden in Relation mit den nicht eindeutigen Angaben in der Literatur diskutiert.

     

Synthesis and Electrical Properties of Lithium Metazirconate

Lithium metazirconate Li₂ZrO₃ with a monoclinic lattice is synthesized; the lattice parameters are: a = 0.5432 nm, b = 0.5427 nm, c = 0.903 nm, = 112.72°, and Z = 4. The conductivity of both the stoichiometric compound and samples rich or deficient in Li₂O near this composition is determined. The conductivity of the synthesized compound reaches 0.029 S cm^–1 at 600°C. The activation energy for the high-temperature segment is 13.8 kJ mol^–1. An abnormal behavior (abrupt jump) of the temperature dependence of the conductivity at 430°C is discovered and attributed to a phase transition. The change in the structure in this temperature domain (400 to 500°C) is corroborated by the high-temperature X-ray analysis.     

Structural and Electrochemical Characteristics of Lithiated Manganese Oxides

An LiMn₂O₄ spinel of a poorly ordered structure is produced by subjecting MnO₂ + LiOH and MnO₂ + LiOH + 5 wt % Cr₂O₃ mixtures to plastic deformation at 1–2 GPa and then annealing them at 400°C. The size of individual particles is 10–100 nm. Cathodes based on chromium-modified spinels have a higher stability and a longer shelf life.     

The effect of high pressure on the ion pair equilibrium constant of alkali metal fluorides: A spectrophotometric study

Bromophenol blue indicator was used in UV-visible spectrophotometric measurements to study ion association constants of alkali metal fluorides. The equilibrium constants for the ion pair formation of the alkali metal fluorides were determined as a function of ionic strength at one atmosphere pressure and 25°C. The effect of pressure on these association constants was measured at a constant total ionic strength of 1.0 mol-kg^–1 over a pressure range of 1 to 2000 atmospheres at 25°C. The pressure dependences of the stoichiometric association constants of the alkali metal fluorides are given by: lnK _LiF ^* =0.77–2.47×10^–4P–2.12×10^–8P²; lnK _NaF ^* =0.53–1.08×10^–4P–1.66×10^–8P²; lnK _KF ^* =0.24–4.41×10^–5P–7.15×10^–8P²; lnK _RbF ^* =–0.17–8.65×10^–5P–4.51×10^–8P²; and lnK _CsF ^* = –0.37–1.14×10^–4P–6.82×10^–8P², where P is the pressure in atmospheres. The stoichiometric molar volume and compressibility changes for ion pair formation of the alkali metal fluorides were evaluated from the pressure dependence of K _MF ^* data. The thermodynamic association constants were also calculated making use of activity coefficient data from the Pitzer equations. The partial molal volume and compressibility changes for ion pair formation of each alkali metal fluoride are reported.     

Thermogravimetric studies of the synthesis of cas from gypsum, CaSo4·2H2O and phosphogypsum

Using a heating rate of 2°C min^–1, CaS reacts with oxygen in air from 700°C to form CaSO₄, with a complete conversion at 1100°C. Synthesis of CaS from the reaction between CaSO₄ containing compounds and carbon compounds in air would not be possible, as the carbon reacts from 600°C with oxygen in the air to give CO₂. Heating stoichiometric amounts of carbon and pure CaSO₄, synthetic gypsum or phosphogypsum in a nitrogen atmosphere, results in the formation of CaS from 850°C. Using a heating rate of 10°C min^–1, the formation of CaS is completed at 1080°C. Addition of 5% Fe₂O₃ as a catalyst lowers the starting temperature of the reaction to 750°C. Activation energy values at different fraction reaction values () differ between 340 and 400 kJ mol^–1. The relationship between the activation energy values and conversion () indicates that the reaction proceeds via multiple steps.     

Formation of small rhodium metal particles on the surface of a carbon support

A rhodium catalyst supported on a Sibunit graphitized carbon carrier was studied by in situ XAFS spectroscopy. A comparative study of the reduction of rhodium was performed for the following two samples: Rh/C(120) dried at 120°C and Rh/C(350) calcined at 350°C. EXAFS data showed an absence of carbon atoms within the nearest environment of rhodium atoms in the Rh/C(120) uncalcined sample, which implies the absence of direct interaction between rhodium and the carbon support. In the course of the reduction of this sample (200°C), coarse particles with small metal cores were initially formed. These metal particles rapidly agglomerated upon the complete reduction of rhodium (350°C). These reduction of the Rh/C(350) calcined sample at 100–500°C resulted in the formation of small metal particles early in the reduction (100°C). The high dispersity of these particles was retained as the temperature of treatment in hydrogen was increased to 500°C due to metal-support interaction. The conversion of benzene into cyclohexane on the Rh/C(350) catalyst containing small rhodium particles was much higher at the same temperature of hydrogenation.Translated from Kinetika i Kataliz, Vol. 46, No. 1, 2005, pp. 122–130. Original Russian Text Copyright © 2005 by Stakheev, Tkachenko, Klementev, Grünert, Bragina, Mashkovskii, Kustov.     

Development of the specific surface areas of natural coal in the course of thermolysis in the presence of potassium hydroxide

The development of the surface of natural coal from Donets field in the course of thermolysis with KOH was studied. The dependences of the specific surface area of coal containing 90% carbon on the activation time, temperature (400–800°C), and KOH/coal ratio (0.75–4.5 g g^–1) were determined. The effect exerted on the development of the porous coal structure by low-temperature (20±2°C) oxidative modification causing formation of oxygen functional groups and reorganization of the coal three-dimensional structure was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1452–1455.Original Russian Text Copyright © 2004 by Tamarkina, Kucherenko, Shendrik.     

Ground state C2 density measurement in carbon plume using laser-induced fluorescence spectroscopy

The temporal evolution and spatial distribution of C₂ molecules produced by laser ablation of a graphite target is studied using optical emission spectroscopy, dynamic imaging and laser-induced fluorescence (LIF) investigations. We observe peculiar bifurcation of carbon plume into two parts; stationary component close to the target surface and a component moving away from the target surface which splits further in two parts as the plume expands. The two distinct plumes are attributed to recombination of carbon species and formation of nanoparticles. The molecular carbon C₂ moves with a faster velocity and dies out at ~ 800 ns whereas the clusters of nanoparticle move with a slower velocity due to their higher mass and can be observed even after 1600 ns. C₂ molecules in the d³Π_g state were probed for laser-induced fluorescence during ablation of graphite using the Swan (0,0) band at 516.5 nm. The fluorescence spectrum and images of fluorescence d³Π_g − a³Π_u(0,1)(λ = 563.5 nm) are recorded using a spectrograph attached to the ICCD camera. To get absolute ground state C₂ density from fluorescence images, the images are calibrated using complimentary absorption experiment. This study qualitatively helps to get optimum conditions for nanoparticle formation using the laser ablation of graphite target and hence deducing optimum conditions for thin film deposition.     

A facile preparation of nanocrystalline Mo2C from graphite or carbon nanotubes

Nanocrystalline Mo₂C powders were successfully synthesized at 500 °C by reacting molybdenum chloride (MoCl₅) with C (graphite or carbon nanotube) in metallic sodium medium. X-ray powder diffractometer (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscope (XPS) and surface area analyzer (BET method) were used to characterize the samples. Experiments reveal that the carbon source used for the carbide synthesis has a great effect on the particle size and the surface area of the samples. When micro-sized graphite was used as C source the obtained nanocrystalline Mo₂C powder consists of particles of 30∼100 nm, with a surface area of 2.311 m²/g. When carbon nanotubes were used as C source, the as-synthesized Mo₂C sample is composed of particles of 20∼50 nm, with a surface area of 23.458 m²/g, which is an order of magnitude larger than that of the carbide prepared from the graphite.     

Methyltriethoxysilane-derived sol-gel coatings doped with silver metal particles

Silica sol-gel films were prepared by dipping, starting from an acid catalyzed solution of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS). Silver metal nanoparticles were produced in the silica layer by introducing in the sol-gel precursor solution AgNO₃ or AgClO₄·H₂O. The silver ions were thermally reduced in air at 800°C, giving an intense yellow coating film. The silver metal particles were observed by transmission electron microscopy and X-ray diffraction. The diameter of the silver particles was found to be about 10 nm. Absorption measurements in the UV-Vis were used to evaluate the volume fraction of silver colloids embedded in the silica layer.     

Thermo-Raman spectroscopy in situ monitoring study of solid-state synthesis of NiO-Al2O3 nanoparticles and its characterization

Hyphenation of thermogravimetric analyzer (TGA) and thermo-Raman spectrophotometer for in situ monitoring of solid-state reaction in oxygen atmosphere forming NiO-Al₂O₃ catalyst nanoparticles is investigated. In situ thermo-Raman spectra in the range from 200 to 1400 cm⁻¹ were recorded at every degree interval from 25 to 800 °C. Thermo-Raman spectroscopic studies reveal that, although the onset of formation is around 600 °C, the bulk NiAl₂O₄ forms at temperatures above 800 °C. The X-ray diffraction (XRD) spectra and the scanning electron microscopy (SEM) images of the reaction mixtures were recorded at regular temperature intervals of 100 °C, in the temperature range from 400 to 1000 °C, which could provide information on structural and morphological evolution of NiO-Al₂O₃. Slow controlled heating of the sample enabled better control over morphology and particle size distribution (∼20-30 nm diameter). The observed results were supported by complementary characterizations using TGA, XRD, SEM, transmission electron microscopy, and energy dispersive X-ray analysis.