AA h BN crystal, basic structure of boron nitride nanotubes.

AA h boron nitride (BN) crystal, assigned to an orthorhombic space group (No. 31, Pm21), is reported here. This new AA h BN crystal exhibits a 'linear' morphology for high-resolution transmission electron microscopy (HRTEM) and a (non-hexagonal) 'diagonal' electron-diffraction pattern, which have been experimentally demonstrated in this article. It is also demonstrated that this new crystal is the basic structure of multi-walled BN nanotubes (BNNTs) existing in the form of a helix. The helical AA h BNNTs exist in a metastable phase owing to 〈200〉 texture growth of the orthorhombic crystal, where the energy is ∼15 meV higher than that of stable AB or AA' BN. It is shown that the typical scanning electron microscope 'fluffy cotton-like' morphology of BNNTs is due to secondary growth of diverse BN sheets (including mono-layers) on incoherently scrolled wall strands of BNNTs, providing further evidence for the helical structure with HRTEM evidence for a left-handed helix.

Raman Radial Mode Revealed from Curved Graphene.

One of the unsolved fundamental issues of graphene is establishing an appropriate way to discern layers of graphene structures. We report a simple methodology to analyze graphene structures using Raman signals in the range of ∼100 to ∼500 cm-1 comprising clear 118 or 175 cm-1 peaks. We demonstrate that the low-energy signals on Raman spectra of plasma-seeded grown graphene sheets originated from nanocurvature (c) of mono- (175 and 325-500 cm-1 signals) (c ≈ 1 nm) and bilayer (118 cm-1 peak) (c ≈ 2 nm) graphene with Raman simulations, based on Raman radial mode (RM) Eigen vectors. Our RM model provides a standard way of identifying and evaluating graphene structures.

Nickel Supported on Mesoporous Alumina for Dry Reforming of Methane: Combustion Method.

Ni catalysts supported on ordered mesoporous alumina (OMA) were prepared by EISA method and calcined under air and Ar atmospheres. Both catalysts showed stable performance for the dry reforming of methane for 24 h, however the catalytic activity of Ar calcined catalyst was relatively lower than that in the air calcined one. It was found that the carbon (C ß ) layer around nickel particles was observed for the Ar calcined catalyst after dry reforming of methane. The encapsulating carbon species in the Ar calcined catalyst lowering the mass transfer rate of feeds led to lower performance, but no whisker carbon was observed. In the case of the air calcined catalyst, whisker carbon (C(v)) which is inactive during dry reforming was accumulated on the catalyst, and it resulted in catalyst breakdown and pressure drop during the reaction.

Effect of Tungsten Addition on Nickel-Based Catalyst for Combined Steam and CO2 Reforming of Methane.

In this study, we investigated the effect of tungsten addition on Ni-based catalyst in methane steam-CO2 reforming. All the catalysts were prepared by the co-impregnation method with varied tungsten loading. The as-prepared catalysts were characterized by inductively coupled plasma atomic emission spectrometer, X-ray diffraction, temperature-programmed reduction and thermogravimetric analysis. The tungsten-loaded catalyst showed improved coke resistance and CO2 reactivity by the conducting activity test under fixed conditions.

Dispersion of Cobalt Nanoparticles on Nanowires Grown on Silicon Carbide-Alumina Nanocomposites.

Silicon carbide-alumina nanocomposite supports including a nanowire architecture for a high dispersion of cobalt nanocatalysts were fabricated using a modified sol­gel process and paste extrusion process to form cylindrical shape beads, followed by thermal treatment. Well-developed aluminosilicate nanowires were formed on a nanoporous support, which are grown from a catalytic metal seed at the nanowire growth tips during heat treatment at 1,100 °C for 1 h under nitrogen gas flow. Cobalt oxide precursors were highly dispersed on the nanowires grown on the surface of the nanoporous bodies through a supercritical carbon dioxide fluid-assisted wet-impregnation process. The highly-dispersed Co nanoparticles with size of less than 10 nm were finally obtained on the nanowires via phase transitions from Co3O4 to CoO and from CoO to Co during the thermal reduction.

The Nature of Metastable AA' Graphite: Low Dimensional Nano- and Single-Crystalline Forms.

Over the history of carbon, it is generally acknowledged that Bernal AB stacking of the sp2 carbon layers is the unique crystalline form of graphite. The universal graphite structure is synthesized at 2,600~3,000 °C and exhibits a micro-polycrystalline feature. In this paper, we provide evidence for a metastable form of graphite with an AA' structure. The non-Bernal AA' allotrope of graphite is synthesized by the thermal- and plasma-treatment of graphene nanopowders at ~1,500 °C. The formation of AA' bilayer graphene nuclei facilitates the preferred texture growth and results in single-crystal AA' graphite in the form of nanoribbons (1D) or microplates (2D) of a few nm in thickness. Kinetically controlled AA' graphite exhibits unique nano- and single-crystalline feature and shows quasi-linear behavior near the K-point of the electronic band structure resulting in anomalous optical and acoustic phonon behavior.

Kinetic Study on the Effect of Chromium Addition to Ni-Based Catalysts for the Steam-CO2 Reforming of Methane.

In the present work, the kinetic effects of Ni-based catalysts containing various amounts of Cr on the steam-CO2 reforming (SCR) of methane were studied. Kinetic expressions for the SCR of methane over the Ni-based catalysts have been proposed using the power-law rate expression, based on the kinetic data obtained. In addition, the Arrhenius equation was used for calculating the activation energy. Analysis of the data revealed four simple results. Firstly, the partial pressure of CH4 exerts a major influence on the CH4 conversion rates. Secondly, the CH4 conversion rate is inversely proportional to the partial pressure of CO2. Thirdly, the partial pressure of steam has a very slight effect on the reaction rates. Finally, all the catalysts studied have similar apparent activation energies.

Carbon Deposition Onto Ni-Based Catalysts for Combined Steam/CO2 Reforming of Methane.

The present study was performed to suppress carbon deposition by Ce and Fe onto Ni-based catalysts in combined steam/CO2 reforming of methane (CSCRM), which is a process for producing synthesis gas (H2:CO = 2:1) for gas-to-liquids (GTL). The catalytic reaction was evaluated at 900 degrees C and 20 bar with a reactant feed ratio CH4:CO2:H20:Ar = 1:0.8:1.3:1 and gas hourly space velocity GHSV = 25,000 h(-1). The Ce and Fe modified Ni/gamma-A120, catalyst was characterized by BET surface area analysis, X-ray diffraction (XRD), H2 temperature-programmed reduction (TPR), H2 chemisorption, CO2 temperature-programmed desorption (TPD) and SEM. Ce- and Fe-modified Ni/Al2O3 catalysts exhibited remarkable activity and stability during the CSCRM over the course of 50 hours. It suggested that the Ni(12)-Ce(5)-Fe(5)/Al2O3 catalyst shows highly dispersed Ni particles with strong metal-to-support interaction (SMSI) as well as excellent catalytic activity.

Glycerol Steam Reforming Over Ni-Fe-Ce/Al2O3 Catalyst: Effect of Cerium.

In this work, hydrogen production from glycerol by steam reforming was studied using Ni-metal oxide catalysts. Ni-based catalyst becomes deactivated during steam reforming reactions because of coke deposits and sintering. Therefore, the aim of this study was to reduce carbon deposits and sintering on the catalyst surface by adding a promoter. Ni-metal oxide catalysts supported on Al2O3 were prepared via impregnation method, and the calcined catalyst was reduced under H2 flow for 2 h prior to the reaction. The characteristics of the catalysts were examined by XRD, TPR, TGA, and SEM. The Ni-Fe-Ce/Al2O3 catalyst, which contained less than 2 wt% Ce, showed the highest hydrogen selectivity and glycerol conversion. Further analysis of the catalysts revealed that the Ni-Fe-Ce/Al2O3 catalyst required a lower reduction temperature and produced minimum carbon deposit.

Studies on the Role of Nitrogen in the Feed for Fischer-Tropsch Synthesis Under Fixed-Bed Reactor System.

In this study, Co/Al203 catalyst for Fischer-Tropsch synthesis was prepared via slurry impregnation method and the catalyst was characterized by various techniques such as TPR, XRD, TGA and N2 physisorption. To dissolve the wax, after-reaction catalyst was dewaxed using n-Hexane at 60 *C. The experiments were performed in a bench-scale fixed-bed reactor, under the reaction condition of 230 degrees C, 20 bar and feed volume ratio of H2:CO:N2 = 2:1:0.5-1.5. The methane selectivity and the ratio of olefin to paraffin among C2-C4 hydrocarbons were increased with higher contents of nitrogen in feed gas which result in higher partial pressure ratio of H2 to CO, and also affect methane selectivity which has a significant role in increased CO conversion.

The Effect of Fe in Perovskite Catalysts for Steam CO2 Reforming of Methane.

In this work, La0.95Sr0.05Ni(1-x)Fe(x)O3 catalysts were prepared by modified EDTA-cellulose method and the catalysts were characterized by various techniques such as N2 physisorption, TPR, XRD, SEM, TEM-EDS and TG analysis. La00.95Sr0.05Ni0.5Fe0.5O3 catalyst showed better catalytic performance under the reaction conditions of 900 degrees C, 21 bar and feed molar ratio of CH4:CO2:H20 = 1:0.7:1.5. It is considered that the dilution effect on nickel prevented the formation of large monometallic ensembles that favour the carbon deposition in reforming reactions, and the mean metallic particle size of Ni decreased with increasing substitution rate in B site. Therefore, partial substitution of Fe in B site enhances the dilution effect and induces a reaction between CO2 and La2O3, thereby resisting the carbon deposition and increasing CO2 conversion.

Formation and Characterization of Ni Nanofiber Catalysts on Nickel Metallic Foam by Electrospinning Process.

We report the fabrication of nickel nanofiber catalysts supported on nickel metallic foam using a modified electrospinning with a grounded rotor and sequential reduction process. The robust deposition of aligned Ni nanofibers with a uniform morphology on the highly porous surfaces of the metallic foam could be achieved by controlling electrospinning parameters such as applied voltage, tip-collector-distance (TCD), concentration of polymer, and humidity. The diameters of the obtained nanofibers decreased with increasing voltage and TCDs. The uniform and thinnest Ni nanofibers on the Ni foam were obtained at a humidity of less than 30%, 15 kV applied voltage, and 17 cm TCD when using a precursor composed of nickel nitrate salt and poly(vinyl) pyrrolidone. The Ni foam catalyst support exhibited the superior thermal conducting property than other supports of MgO-MgAl2O4, Al2O3, and SiC, enabling to a higher heat transfer during catalytic reaction. As a result, the Ni nanofiber catalyst with a high surface area and superior heat transfer performance, which is supported on the metallic foam, were successfully fabricated via a modified electrospinning for potential application of XTL process converting anything to liquids, such as for Gas-to-Liquid (GTL), Coal-to-Liquid (CTL), and Biomass-to-Liquid (BTL).

Kinetics for Steam and CO2 Reforming of Methane Over Ni/La/Al2O3 Catalyst.

Kinetic studies of mixed (steam and dry) reforming of methane on Ni/La/Al2O3 and Ni/La-Co (1, 3 wt%)/Al2O3 catalysts were performed in an atmospheric fixed-bed reactor. Kinetic parameters for the mixed reforming over these catalysts were obtained under reaction conditions free from heat and mass transfer limitations. Variables for the mixed reforming were the reaction temperature and partial pressure of reactants. The fitting of the experimental data for the rate of methane conversion, rCH4, using the power law rate equation rCH4 = k(PrCH4)α(PCO2)ß(PH2O)γ showed that the reaction orders α, ß, and γ are steady and obtained values equal to α = 1, ß = 0, and γ = 0. In other words, among CH4, CO2, H2O, and H2, only CH4 reaction orders were not zero and they were affected by the promoters. The apparent activation energy on catalysts Ni/La/Al2O3, Ni/La-Co (1)/Al2O3 and Ni/La-Co (3)/Al2O3 is 85.2, 93.8, and 99.4 kJ/mol, respectively. The addition of Co to Ni/La/Al2O3 was increased the apparent activation energy of the mixed reforming reaction. And the Ni/La-Co (3 wt%)/Al2O3 catalyst showed the highest reforming activity and apparent activation energy. The Co promoters can increase the apparent activation energy of mixed reforming of methane.

Effect of Bimetallic Ni-Cr Catalysts for Steam-CO2 Reforming of Methane at High Pressure.

The present work was to carry out the development of high performance Ni-based catalyst for Steam-CO2 reforming of methane (SCR) which is suitable for Fischer-Tropsch synthesis of GTL- FPSO (floating, production, storage and offloading) process. The bimetallic Ni-Cr catalysts were prepared by co-impregnation method. The Ni and Cr loading amount were fixed at 12 wt% and 3~7 wt%, respectively. The catalytic reaction was conducted at 900 °C and 20 bar with reactant feed ratio of CH4:CO2:H2O:Ar = 1:0.8:1.3:1 and GHSV = 25,000 h(-1). The Cr-modified Ni/γ-Al2O3 catalyst was characterized by BET surface area analysis, X-ray diffraction (XRD), H2-temperature programmed reduction (TPR), H2-chmisorption, CO2-temperature programmed desorption (TPD) and Transmission electron microscopy(TEM). To confirm the amount and type of the carbon deposition, the used catalysts were examined by Thermogravitic analysis (TGA) and Field emission-scanning microscopy/Energy dispersive X-ray analysis (FE-SEM/EDX). It was found that the bimetallic Ni-Cr catalyst exhibits highly dispersed Ni particles with strong metal-to-support interaction (SMSI) as well as excellent catalytic activity, resulting in the suppression of Ni sintering and carbon deposition.

Modified Nano-Perovskite Catalysts for the Steam and CO2 Reforming of Methane.

This paper describes the synthesis and characterization of La0.8Sr0.2NiO3 nano-perovskite type catalyst for steam-CO2 reforming (SCR) and CO2 reforming (DR) of methane. Effect of gelation agents such as PVA, EDTA and PAA on nano-perovskite structures was investigated. XRD, H2-TPR and FT-IR analysis were used to characterize the prepared catalysts. The catalytic reaction was performed in a fixed bed reactor system at 1 atm and 800 °C. The feed ratio of CH4:H2O:CO2 as reactants was adjusted according to the SCR and DR reactions. As a result, CH4 and CO2 conversions of PVA agent catalyst were higher than that of PAA and EDTA agent catalyst for DR reaction because the PVA agent catalyst had a well-established perovskite, a high absorption, a high reducibility. However, the PAA agent catalyst had a higher reactivity due to its high interaction of catalysts for SCR of methane due to its strong interaction of catalysts.

Ni/MgO-MgAl2O4 Catalysts with Bimodal Pore Structure for Steam-CO2-Reforming of Methane.

The bead type MgO-MgAl2O4 catalyst supports with bimodal pore structures were fabricated via an extrusion molding of gels derived from the precursor mixture of mesoporous MgO particles and aluminum magnesium hydroxide, followed by heat treatment. To investigate the effect of macro pore structures on the catalytic activity of the Ni/MgO-MgAl2O4 catalysts in the steam and carbon dioxide reforming of methane (SCR), two kinds of the catalysts with largely different macro pore volumes and sizes but nearly the same meso pore volume and size were compared. The bimodal catalyst with a large macro pore size and volume exhibited a highly enhanced CO2 conversion from 22.3 to 37.1% but a slightly reduced CH4 conversion from 95.3 to 92.1% at the same feed ratio. The SCR results show that the large macro pores can lead to a highly enhanced mass transfer rate of CO2 absorption into the pore channels of the magnesium alumina spinel.

Carbon Deposition from the CO2-Steam Reforming of Methane Over Modified Ni/γ-Al2O3 Catalysts.

The aim of this work is to study the catalytic activity and suppression of carbon deposition in the CO2-Steam reforming of methane (SCR) to develop a high performance catalyst for GTL-FPSO application which is required to high pressure (20 bar) for F-T synthesis. Ni/La-X(6)/Al2O3 (X = Ce, Mg, Zr) catalysts were prepared by the impregnation method. The catalytic reaction was studied in a fixed bed reactor system at high pressure. X-ray diffraction (XRD), BET specific surface area and H2-temperature programmed reduction (TPR) were used to observe the characteristics of the prepared catalysts. The carbon deposition and the carbon amount in the used catalysts were examined by SEM and TGA, respectively. As a result, it was found that the Ni/La-Mg(6)/Al2O3 catalyst showed the highest activity and high carbon resistance. The highest activity in Ni/La-Mg(6)/Al2O3 was attributed to the proper Mg loading. It also had the lowest Ni particle and formed relatively stable MgAl2O4, which have an effect on the catalytic activity.

The Effect of Cobalt Loading on Fischer Tropsch Synthesis Over Silicon Carbide Supported Catalyst.

A series of Co (5-30 wt%) based SiC supported catalysts were prepared by impregnation method and investigated for FTS reaction. The FTS reaction was carried out in a fixed bed reactor system with the H2/CO molar ratio of 2, reaction temperature of 230 degrees C and reaction pressure of 20 bar for 120 h. All catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM techniques. It was found that 15 wt% Co/SiC catalyst showed better catalytic performance with high selectivity of C(5+) hydrocarbons than the other catalysts. The results, suggest that the catalytic performance of the catalysts depends on average pore size of support and surface density of cobalt, metal and support interactions.

Methanol Synthesis Over Cu-ZnO-Al2O3 Catalyst at Low Pressure.

A series of Cu-ZnO-Al2O3 catalysts were prepared by coprecipitation method. The pH of solution was adjusted from 6 to 8 by using Na2CO3 solution. The prepared catalysts were evaluated for methanol synthesis from syngas (H2, CO and CO2) at lower temperature and pressures. Catalysts have been characterized by N2 physisorption, porosity measurements, XRD, TG/DTA, TPD (CO2/NH3) and XPS. Among all the catalysts pH 7 catalyst was shown higher catalytic activity towards methanol formation. It was found that the catalyst is mainly possessed the higher number of surface active sites (Cu0/Cu+), acidic and basic nature and optimum synergism between three components (Cu-ZnO-Al2O3). The activity results were evaluated with and without CO2 in syngas and it was found that higher CO conversion and higher methanol selectivity in the presence CO2.

The Influence of Promoter on Ni(15)/La(5)/γ-Al2O3 Catalyst in CO2-Steam Reforming of Methane to Syngas at High Pressure.

Catalysts were investigated with respect to catalytic activity and coke formation in combined steam and carbon dioxide reforming of methane to develop a highly active and stable catalyst for gas to liquid processes. Ni/La-X/Al2O3 (X = Co, Ce, Mo) catalysts were prepared by an impregnation method. The combined steam and carbon dioxide reforming of methane reaction were studied as a function of high pressure (20 bar) in a fixed bed reactor system. X-ray diffraction, BET surface area, and H2-temperature programmed reduction were used to observe the characteristics of the prepared catalysts. Coke formation of used catalysts was examined by scanning electron microscopy, transmission electron microscopy and the coke amount of used catalysts was measured by thermo gravimetric analysis. Catalysts with smaller particle size had a higher temperature of reduction, which had a positive effect on catalytic activity. The improvement in active site rise and dispersion and the lowest metal crystal size had an effect on catalyst activity. As a result, the Ni/La-Co/Al2O3 catalyst showed the highest activity at a reaction temperature of 800 degrees C and a reaction pressure of 20 bar.