Monolayer aspects of high-resolution αs-plots

The problem of the estimation of high resolution comparative plots (α_s method) is revised. Adsorption isotherms of Ar (T = 87 K) are simulated (GCMC) on the bundles of closed and opened multiwalled carbon nanotubes. Those materials are chosen in order to observe the influence of porosity on Ar adsorption, and consequently, on the comparative plots. The introduction of the structural heterogeneity (defects in the external and internal walls of osculating and separated nanotubes) is also studied. The monolayer and multilayer parts of adsorption are extracted from the total amount adsorbed for all studied adsorbents and the reference one (the bundle of the ideal 3-layered carbon tubes with very wide diameters). The significant influence of the distance between carbon nanotubes and defects (in the external and internal walls) is observed on the monolayer α_s-plots. In the case of comparative plots calculated for the multilayer adsorption the differences are also visible; however, the expected linear dependence of the amount adsorbed on a porous solid plotted against the amount adsorbed on a reference nonporous solid (the layer-by-layer adsorption occurs on both solid surfaces) in a wide range of relative pressures is not observed. The obtained results demonstrate the complexity of α_s method when both microporosity and surface heterogeneity are present. A comparison of isotherms shows that for the studied adsorbents Ar is sensitive to the appearance of the geometrical and structural defects, even at low coverage.     

Characterization of nanoporous carbons by combining CO2 and H2 sorption data with the Monte Carlo simulations

The Monte Carlo method in its grand ensemble variant (GCMC) is used in combination with experimental data in order to characterize microporous carbons and obtain the optimal pore size distribution (PSD). In particular, the method is applied in the case of AX-21 carbon. Adsorption isotherms of CO₂ (253 and 298 K) and H₂ (77 K) up to 20 bar have been measured, while the computed isotherms resulted from the GCMC simulations for several pore widths up to 3.0 nm. For the case of H₂ at 77 K quantum corrections were introduced with the application of the Feynman-Hibbs (FH) effective potential. The adsorption isotherms were used either individually or in a combined manner in order to deduce PSDs and their reliability was examined by the ability to predict the experimental adsorption isotherms. The combined approach was found to be capable of reproducing more accurately all the available experimental isotherms.     

Surface and adsorptive properties of carbons prepared from biomass

A number of activated carbons were prepared from a locally available by-product, corncobs, under currently established activation schemes. Obtained carbons were characterized by N₂ adsorption at 77 K and the isotherms were analyzed by BET and α_s methods. Steam-activation at 900 °C produced a microporous carbon having the highest S^α of 788 m² g⁻¹, whereas activation with air at 350 °C produced a carbon of S^α = 321 m²/g and possess wider pores. KOH impregnation with char in ratio 1:1 (w/w) and impregnated in the same ratio with the raw material prior to pyrolysis at 700 °C for 1 h, gave CK700, K700 respectively. An additional sample was obtained by oxidizing part of K700 with conc. HNO₃. All three KOH carbons show pore structures much close to char itself which may be due to potassium salt left in pores and is not easily leached with repeated water washings. In addition, KOH is more effective on the precursor itself than on its char of already developed porosity. FT-IR spectra show an increase in oxygen functionalties on the carbon surface as a result of activation process and the bands become stronger in the spectra of the acid-treated sample. The oxidized carbon sample showed relatively higher uptake of Pb²⁺ and MB and its surface chemistry plays the key role in their adsorption, while sharp decrease was observed in the uptake of phenol and mono-nitrophenols from aqueous solutions. An SEM study showed that air activation produce obvious voids reflecting its erosive effect on the external carbon surface.     

Adsorption in cylindrical pores: Mixed lattice-site/off-site Monte Carlo simulations in pores with heterogeneous wall structure

We present results of grand canonical Monte Carlo simulations of adsorption in cylindrical pores with rough surface modeled by lattice-site approach. Each site is characterized by two parameters: structural and energetic, which locally modify the structure and energy properties of the surface. There are three types of sites, randomly distributed over the wall: attractive, neutral and repulsive with respect to the smooth pore model. The results presented here show how this model affects the mechanism of adsorption and how it changes the forms of adsorption isotherm. We compare our numerical results with the experimental data of adsorption of a simple fluid (CH₄, T = 77 K) in cylindrical silica pore of diameter d = 4 nm (MCM-41 material).     

Neutron scattering study on CeAgAs2

CeAgAs₂, an HfCuSi₂ like layered pnictide, orders antiferromagnetically at T_N=6.2(1) K. The ordering process was monitored in neutron diffraction experiments in the temperature range 10 K≥T≥3.5 K. At T=4 K the lattice parameters are a=5.7438(1) Å, b=5.7696(1) Å and c=21.0067(2) Å. The diffraction pattern of the antiferromagnetic phase with a propagation vector k=[0,0,0] point towards ferromagnetically ordered moments in Ce layers stacked along [001], the individual layers are coupled antiferromagnetically with a +− −+type sequence. The alignment of moments within the Ce layers cannot be determined reliably from the experimental data so that two different structure models are discussed. The proposed metamagnetic transition was confirmed by diffraction experiments applying an external magnetic field at T<T_N. In the interval 4 K≤T≤6 K, a relatively small field of μ₀H≈0.3 T suffices to fully suppress the antiferromagnetic ordering. The effect is completely reversible yet subject to hysteresis: After switching off the external field at any T<T_N the magnetic reflections gain their original intensity within several 10 min indicating the restoring of the antiferromagnetic phase.     

Cationic starch as a precursor to prepare porous activated carbon for application in supercapacitor electrodes

Three activated carbons (ACs) for the electrodes of supercapacitor were prepared from cationic starch using KOH, ZnCl₂ and ZnCl₂/CO₂ activation. The BET surface area, pore volume and pore size distribution of the ACs were evaluated using density functional theory method, based on N₂ adsorption isotherms at 77 K. The surface morphology was characterized with SEM. Their electrochemical performance in prototype capacitors was determined by galvanostatic charge/discharge characteristics and cyclic voltammetry, and compared with that of a commercial AC, which was especially prepared for use in supercapacitors. The KOH-activated starch AC presented higher BET surface area (3332 m² g⁻¹) and larger pore volume (1.585 cm³ g⁻¹) than those of the others, and had a different surface morphology. When used for the electrodes of supercapacitors, it exhibited excellent capacitance characteristics in 30 wt% KOH aqueous electrolytes and showed a high specific capacitance of 238 F g⁻¹ at 370 mA g⁻¹, which was nearly twice that of the commercial AC.     

Effect of combined activation on the preparation of high porous active carbons from granulated post-consumer polyethyleneterephthalate

Activated carbons were prepared from granulated post-consumer PET by combined activation including heat treatment with sulphuric acid (chemical activation) followed by steam activation. The effect of activation time, temperature, impregnation coefficient in the activation process was studied in order to optimize those reception parameters. One of the most important parameter in combined activation of crushed PET was found to be impregnation coefficient. It was defined that the optimal impregnation coefficient is equal 28%. Activation temperature is another variability which has a significant effect on the pore volume evolution. The increasing of activation temperature enhances the surface area and pore volumes of active carbons. The yield of final product which composes of nearly 15% is the factor limited the activation temperature above 800 °C. Textural characteristics of the samples were carried out by performing N₂ adsorption isotherm at −196 °C. The obtained active carbons were mainly micro- and mesoporous and with BET apparent surface areas of up to 1030 m²/g. The adsorption capacity on methylene blue reaches 1.0 mmol/g, the sorption activity on iodine comes to 77%.     

Nonlinear conductivity of quasi-one-dimensional layered compound TiS3

The crystal structure and transport properties of TiS₃ whiskers in the plane of layers (ab) have been studied. Maxima of the logarithmic derivative of resistance, dln R/d(1/T), are observed at 17, 60 and 120 K both along and across the chains. Strong nonlinearity of the current–voltage characteristics has been revealed in both directions. Nonlinear conductivity along the chains is observed up to T=60 K, while in the transverse direction it is observed up to T=130 K. The results indicate possible phase transitions of electrons to collective states, probably, charge density waves.     

Magnetic and optical properties of self-organized InMnAs quantum dots

Ten layers of self-assembled InMnAs quantum dots with InGaAs barrier were grown on high resistivity (1 0 0) p-type GaAs substrates by molecular beam epitaxy (MBE). The presence of ferromagnetic structure was confirmed in the InMnAs diluted magnetic quantum dots. The ten layers of self-assembled InMnAs quantum dots were found to be semiconducting, and have ferromagnetic ordering with a Curie temperature, T_C=80 K. It is likely that the ferromagnetic exchange coupling of sample with T_C=80 K is hole mediated resulting in Mn substituting In and is due to the bound magnetic polarons co-existing in the system. PL emission spectra of InMnAs samples grown at temperature of 275, 260 and 240 °C show that the interband transition peak centered at 1.31 eV coming from the InMnAs quantum dot blueshifts because of the strong confinement effects with increasing growth temperature.     

Numerical study of growth and relaxation of small C60 nanoclusters

We investigate by means of kinetic Monte Carlo simulations the growth and thermal relaxation of small fullerene nanoclusters modelled by the Pacheco-Prates Ramalho pair potential. The activation barriers for diffusion processes are calculated on the fly by the dimer method. The elementary transitions which are likely to occur around room temperature are figured out. We study island growth on a perfect fullerene cluster and obtain a morphological transition of the island with increasing temperature. At T = 150 K, the islands are small and irregular. Around room temperature, elongated chain islands are obtained while at higher temperature, they are compact with an anti-Mackay stacking. These island morphologies have been shown to influence the character of the growth. Thus, growing fullerene clusters are disordered with rough surface below T = 300 K whereas at T = 450 K the growth occurs facet-by-facet within the growing shell.     

Air-activated carbons from almond tree pruning: Preparation and characterization

In this work the results obtained in the preparation and characterization of carbons made from almond tree pruning by non-catalytic and catalytic gasification (using K and Co) with air are analyzed and discussed. The main aim was to obtain high quality activated carbons at the lowest possible cost. The variables studied have been the temperature (190-260 °C) and the time (1-10 h) in non-catalytic gasification and the influence of the catalyst type (K and Co, 1 wt.% referred to cation, at 190 °C and 1 h) and the time (1-4 h) in catalytic gasification with Co at 190 °C. The air flow rate used in all the series was 167 cm³ min⁻¹. In non-catalytic gasification the reaction normalized rate versus the conversion degree was maintained until a conversion value of 10% for the experiment made at 260 °C since, at lower temperatures, this rate drops quickly for low conversion values. The N₂ adsorption isotherms for the carbons of this series resemble type I, although there is an increase of N₂ adsorbed volume at relatively high pressures. A temperature rise produced an increase of the carbon porosity and BET specific surface (116-469 m² g⁻¹). The activation time has a positive effect on the N₂ volume adsorbed by the carbons. The isotherms shapes were similar to those previously commented. A concentration equal to 1 wt.% was used to study the influence of the catalyst type. Under the studied experimental conditions, Co drives to a bigger porosity development than K, although with both catalysts a very similar pore size distribution is obtained. The activation time, in the gasifications catalyzed with Co, gives rise to a very important porosity development in the carbons. This produces a strong increase of the carbon specific surface area with very high values in the 4 h experiment, in which a BET specific surface of 959 m² g⁻¹ was obtained.     

Preparation of activated carbons from used tyres by gasification with steam and carbon dioxide

Activated carbons were prepared from waste tyres by gasification with steam and carbon dioxide and their characteristics were investigated. A two-stage activation procedure (pyrolysis at 800 °C in N₂ atmosphere, followed by steam or carbon dioxide activation) was used for the production of activated samples. The effect of the activation temperature (750-900 °C) and the activation time (1-3 h) on the surface characteristics of the prepared carbon was investigated. Carbons produced to different degrees of burn-off were characterized by means of their nitrogen adsorption isotherms at 77 K. In both sets of experiments, the mesopore, micropore volume, and BET surface area increased almost linearly with the degree of activation. For burn-off values lower than 53%, the steam activation produced carbons with a narrower and more extensive microporosity and higher BET and external surface area than the carbon dioxide activation. As the activation proceeds (burn-off > 53%), a strong development of the mesoporosity in the carbons was observed and the micropores size distribution revealed broader micropores, that is, a more heterogeneous distribution.     

Low-temperature STM/STS studies on boron-doped (1 1 1) diamond films

We have performed scanning tunneling microscopy/spectroscopy (STM/STS) experiments on (1 1 1)-oriented epitaxial films of heavily boron-doped diamond (T_c∼5.4 K). We present that tunneling conductance spectra show temperature-dependent spatial variations. In the low-temperature region (T=0.47 K), the tunneling spectra do not show strong spatial dependence and a superconducting energy gap is observed independent of the surface morphology. In the high-temperature region (T=4.2 K), on the other hand, the tunneling conductance spectra show significant spatial dependence, indicating the inhomogeneous distribution of the superconducting property due to the distribution of boron atoms.     

Laser desorption of NO from a thick C60 film

The desorption of NO molecules from a thick C₆₀ film is reported. A thermal desorption spectrum indicates two adsorption sites with binding energies of E_b = 0.30 eV and 0.55 eV. For laser desorption the fullerene surface is exposed to NO and excited by 7 ns UV laser pulses. Desorbing NO molecules are recorded state selectively as well as time resolved. The time-of-flight measurement indicates three different desorption pathways. A fast channel shows rovibronic temperatures of T_rot(v″ = 0) = 370 K, T_rot(v″ = 1) = 390 K and T_vib = 610 K as well as strong rotational-translational coupling. The desorption yield for the fast channel increases linearly with pulse energy with a desorption cross section of σ = (5.1 ± 0.9) × 10⁻¹⁷ cm². Dominating the signal for small J″ values is a slow channel with low rotational and translational temperatures of about 110 K. We assign this peak to a laser-induced thermal desorption. For large pump-probe delays the data deviate from the Maxwellian flux distribution and a third channel appears with extremely late arrival times.     

A Grand Canonical Monte Carlo Study of Adsorption and Capillary Phenomena in Nanopores of Various Morphologies and Topologies: Testing the BET and BJH Characterization Methods

We report a Grand Canonical Monte Carlo simulation study of Ar adsorption at 77 K in silica nanopores having various morphologies/topologies. Both the morphological and topological disorders are shown to significantly affect the capillary condensation phenomenon. In the case of an ellipsoidal pore, we observe that the filling mechanism is similar to that of a cylindrical pore having the same section area but with a lower condensation pressure. We show that the adsorption/desorption hysteresis loop is asymmetrical for the pore with constrictions while it is symmetrical for the regular cylindrical pore. Moreover, the Ar adsorption isotherm for the constricted pore reproduces the main features of that for the fully disordered Vycor‐like porous matrix. The results for the different pore geometries (having no direct interface with the gas reservoir) indicate that the desorption occurs through cavitation at a pressure driven by the smallest void size. We also consider the validity of the BET and BJH methods for the different porous matrices. Except for the Vycor‐like matrix, the BET surface assessed from Ar adsorption isotherm at 77 K always significantly overestimates the intrinsic surface of the pore (even for a planar surface). The disagreement between the BET surface and the geometrical surface is found to increase as the confinement increases (cylindrical pore) and/or the shape of the pore becomes asymmetrical (ellipsoidal pore). Interestingly, the best agreement between the BET and the geometrical surface is found in the case of the pore with a constriction, i.e. a system that exhibits a surface with both negative and positive curvature regions. This idea is supported by the results for the Vycor‐like matrix, which has a distorted surface (many negative curvature regions combined with positive curvature regions): for this disordered porous matrix, the BET surface is found to underestimate the intrinsic surface. Finally, we show that the pore size determined using the BJH method always underestimates the pore size, in agreement with previous experimental and simulation studies.     

Determination of the rate of H + O2 + M → HO2 + M (M = N2, Ar, H2O) from ignition of syngas at practical conditions

In H₂ and H₂/CO oxidation, the H + O₂ + M termination step is one of the most important reactions at elevated pressures. With the recent, increased interest in synthetic fuels, an accurate assessment of its rate coefficient becomes increasingly important, especially for real fuel/air mixtures. Ignition delay times in shock-tube experiments at the conditions selected in this study are only sensitive to the rates of the title reaction and the branching reaction H + O₂ = OH + O, the rate of which is known to a high level of accuracy. The rate coefficient of the title reaction for M = N₂, Ar, and H₂O was determined by adjusting its value in a detailed chemical kinetics model to match ignition delay times for H₂/CO/O₂/N₂, H₂/CO/O₂/Ar, and H₂/CO/O₂/N₂/H₂O mixtures with fuel/air equivalence ratios of ? = 0.5, 0.9, and 1.0. The rate of H + O₂ + N₂ = HO₂ + N₂ was measured to be 2.7 (−0.7/+0.8) × 10¹⁵ cm⁶/mol² s for T = 916-1265 K and P = 1-17 atm. The present determination agrees well with the recent study of Bates et al. [R.W. Bates, D.M. Golden, R.K. Hanson, C.T. Bowman, Phys. Chem. Chem. Phys. 3 (2001) 2337-2342], whose rate expressions are suggested herein for modeling the falloff regime. The rate of H + O₂ + Ar = HO₂ + Ar was measured to be 1.9 × 10¹⁵ cm⁶/mol² s for T = 932-965 K and P = 1.4 atm. The rate of H + O₂ + H₂O = HO₂ + H₂O was measured to be 3.3 × 10¹⁶ cm⁶/mol² s for T = 1071-1161 K and P = 1.3 atm. These are the first experimental measurements of the rates of the title reactions in practical combustion fuel/air mixtures.     

Surface structures of K on Mo(1 1 0) surface investigated by RHEED

Phase transitions of K on Mo(1 1 0) have been studied by RHEED technique. As Ba and Cs structures on the bcc(1 1 0) surface, surface structures of K were hexagonal from RT to 250 °C for θ > 0.9 ML. The hexagonal structure successively expanded from α to γ structure with Nishiyama-Wassermamm (N-W) orientation relationship. The nearest neighbor spacing in the α structure at RT was 4.50 Å, which is very closed to the atomic distance of K in metal, and stretched to 5.14 Å in the γ structure at T = 200 °C. At temperatures greater than T = 250 °C, the γ structure oriented in N-W and Kurdjumov-Sachs (K-S) relationships at the same time and stayed up to the temperature of 450 °C. These two orientations of γ structure also appeared in all temperature range for 0.4 < θ < 0.9 ML.     

Surface mass diffusion and step stiffness on an anisotropic surface; Mo(0 1 1)

Results of step fluctuation experiments for Mo(0 1 1), using low-energy electron microscopy, are re-examined using recently developed procedures that offer accurate coefficients of surface mass diffusion. By these means, surface diffusion D_s is documented at T/T_m ∼ 0.5, while the crossover to relaxation driven by bulk vacancy diffusion is inferred for T/T_m ∼ 0.6. Here, T_m is the melting temperature T_m = 2896 K. We obtain D_s = 4 × 10⁻⁴ exp(−1.13 eV/k_BT) cm²/s for the temperature interval 1080-1680 K. Possible indications of diffusion along step edges appear for T/T_m ∼ 0.4. The same measurements of step fluctuation amplitudes determine also the step stiffness, which by symmetry is anisotropic on Mo(0 1 1). It is shown that three independent procedures yield mutually consistent step stiffness anisotropies. These are (1) step fluctuation amplitudes; (2) step relaxation rate anisotropies; and (3) the observed anisotropies of islands in equilibrium on the Mo(0 1 1) surface. The magnitude of the step stiffness obtained from step edge relaxation is consistent with earlier measurements that determine diffusion from grain boundary grooving.     

Effect of substrate temperature on structure and electrical resistivity of laser-ablated IrO2 thin films

IrO₂ thin films were prepared on Si(1 0 0) substrates by laser ablation. The effect of substrate temperature (T_sub) on the structure (crystal orientation and surface morphology) and property (electrical resistivity) of the laser-ablated IrO₂ thin films was investigated. Well crystallized and single-phase IrO₂ thin films were obtained at T_sub = 573-773 K in an oxygen partial pressure of 20 Pa. The preferred orientation of the laser-ablated IrO₂ thin films changed from (2 0 0) to (1 1 0) and (1 0 1) depending on T_sub. With the increasing of T_sub, both the surface roughness and crystallite size increased. The room-temperature electrical resistivity of IrO₂ thin films decreased with increasing T_sub, showing a low value of (42 ± 6) × 10⁻⁸ Ω m at T_sub = 773 K.