Kinetic behaviour of HC-SCR over Ag/alumina catalyst using a model paraffinic second generation biodiesel compound

The effect of longer paraffins on the mechanism of the HC-SCR reaction over a 1.91 wt.% Ag/alumina catalyst was investigated by kinetic studies. Hexadecane (C₁₆H₃₄) was chosen as a model compound as it is also a representative molecule for a second generation biodiesel consisting of only long-chain paraffins. The kinetic behaviour of the catalytic reduction of NO_x was examined at steady-state conditions in the temperature range 250–550 °C (50 °C ramping) and by using the following gas concentrations: P_NO = 100, 250, 500, 750 or 1000 ppm, P_hexadecane = 31, 94, 188, 281 or 375 ppm and P_O2=1.5, 3, 4.5, 6 or 9 vol.%. Results showed that in the temperature range 250–425 °C high hexadecane concentration had an inhibiting effect on the NO reduction. At temperatures above 350 °C the apparent reaction orders for hexadecane with respect to hexadecane increased to close or above 1. Reaction orders towards NO were close to 0.55 indicating that NO adsorption on the catalyst surface is stronger than hexadecane adsorption. Based on the experimental data it is proposed that small clusters alone cannot be the active sites for HC-SCR over Ag/Al₂O₃ but the important requirement for high activity over the catalyst is the local concentrations of hydrocarbon and NO on the interface of silver and the support.     

Chlorobenzene total oxidation over palladium supported on ZrO2, TiO2 nanostructured supports

Two series of supported Pd catalysts were synthesized on new mesoporous–macroporous supports (ZrO₂, TiO₂) labelled M (Zr and Ti). The deposition of palladium was carried out by wet impregnation on the calcined TiO₂ and ZrO₂ supports at 400 °C (Pd/Zr₄, Pd/Ti₄) and 600 °C (Pd/Zr₆, Pd/Ti₆) and followed by a calcination at 400 °C for 4 h. The pre-reduced Pd/MX catalysts were investigated for the chlorobenzene total oxidation and their catalytic properties where compared to those of a reference catalyst Pd/Ti-Ref (TiO₂ from Huntsman Tioxide recalcined at 500 °C) and of a palladium supported on the fresh mesoporous–macroporous TiO₂ (Pd/Ti). Based on the activity determined by T₅₀, the Pd/Ti and Pd/Ti₄ catalysts have been found to be more active than the reference one. Moreover activity decreased owing to the sequence: Pd/TiX  Pd/ZrX and in each series when the temperature of calcination of the support was raised. The overall results clearly showed that the activity was dependant on the nature of the support. The better activity of Pd/TiX compared to Pd/ZrX was likely due to a better reducibility of the TiO₂ support (Ti⁴⁺ into Ti³⁺) leading to an enhancement of the oxygen mobility. Production of polychlorinated benzenes PhCl_x (x = 2–6) and of Cl₂ was also observed. Nevertheless at 500 °C the selectivity in HCl was higher than 90% for the best catalysts.     

The influence of sintering aids for Nd(Mg0.5Ti0.5)O3 microwave dielectric ceramics properties

The influence of various sintering aids on the microwave dielectric properties and the structure of Nd(Mg_0.5Ti_0.5)O₃ ceramics were investigated systematically. B₂O₃, Bi₂O₃, and V₂O₅ were selected as liquid-phase sintering aids to lower the sintering temperature. The sintered Nd(Mg_0.5Ti_0.5)O₃ ceramics are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and microwave dielectric properties. The sintering temperature of Nd(Mg_0.5Ti_0.5)O₃ microwave dielectric ceramics is generally high, about 1500 °C. However, the sintering temperature was significantly lowered about 175 °C from 1500 °C to 1325 °C by incorporating in 10 mol% B₂O₃ and revealed the optimum microwave dielectric properties of dielectric constant (_r) value of 26.2, a quality factor (Q × f) value of 61,307 (at 9.63 GHz), and τ_f value of −45.5 ppm/°C. NdVO₄ secondary phase was observed at 10 mol% V₂O₅ addition in the sintering temperature range of 1300–1325 °C, which led the degradation in microwave dielectric properties. The microwave dielectric properties as well as grain sizes, grain morphology, and bulk density were greatly dependent on sintering temperature and various sintering aids. In this study, it is found that Nd(Mg_0.5Ti_0.5)O₃ incorporated with 10 mol% B₂O₃ with lower sintering temperature and excellent dielectric microwave properties may be suggested for application in microwave communication devices. The use of liquid-phase sintering, the liquid formed during firing normally remains as a grain boundary phase on cooling. This grain boundary phase can cause a deterioration of the microwave properties. Therefore, the selection of a suitable sintering aid is extremely important.     

Effect of sintering temperature on varistor properties and aging characteristics of ZnO–V2O5–MnO2 ceramics

The microstructure, electrical properties, dielectric characteristics, and DC accelerated aging behavior of the ZVM-based varistors were investigated for different sintering temperatures of 800–950 °C. The microstructure of the ZVM-based ceramics consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂, which acts as liquid-phase sintering aid. The Zn₃(VO₄)₂ has a significant effect on the sintered density, in the light of an experimental fact, which the decreases of the Zn₃(VO₄)₂ distribution with increasing sintering temperature resulted in the low sintered density. The breakdown field exhibited the highest value (17,640 V/cm) at 800 °C in the sintering temperature and the lowest value (992 V/cm) at 900 °C in the sintering temperature. The nonlinear coefficient exhibited the highest value, reaching 38 at 800 °C and the lowest value, reaching 17 at 850 °C. The varistor sintered at 900 °C exhibited not only high nonlinearity with 27.2 in nonlinear coefficient, but also the highest stability, in which %ΔE_1 mA = −0.6%, %Δα = −26.1%, and %Δ tan δ = +21.8% for DC accelerated aging stress of 0.85 E_1 mA/85 °C/24 h.     

Effect of the crystallinity of kaolinite precursors on the properties of mesoporous silicas

Mesoporous silicas (MesoPSs) were hydrothermally synthesized from calcined and selectively acid-leached kaolinites with a range of crystallinity, using cetyltrimethyl ammonium bromide (CTABr), to investigate the effect of the kaolinite crystallinity on the porous properties of the resulting MesoPSs. Four kaolinites were used, with Hinckley indices ranging from 0.51 to 1.20 and (001) crystallite sizes ranging from 20 to 37 nm. After calcination at 600 °C for 24 h they were selectively leached with 2.5 M H₂SO₄ at 90 °C for 2 h to prepare microporous silica (MicroPSs). The Si/Al ratios of these MicroPSs varied from 21 to 82 and their specific surface areas (S_BET) ranged from 169 to 370 m²/g, these parameters tending to increase with decreasing Hinckley index of the kaolinite. MesoPSs were synthesized by reacting the resulting MicroPSs with CTABr in NaOH solution under hydrothermal conditions. The MicroPS was mixed with CTABr, NaOH and water in the molar ratio (MicroPS):CTABr:NaOH:H₂O = 1:0.1:0.3:150. The synthesis was carried out by stirring the suspension at room temperature for 24 h, aging for 24 h, hydrothermal treatment at 110 °C for 24 h and calcination at 560 °C for 6 h to remove the surfactants. The S_BET values of the resulting MesoPSs ranged from 932 to 1240 m²/g, correlating with the S_BET values of the precursor MicroPS and the crystallinity of the kaolinite starting materials.     

The phenol steam reforming reaction towards H2 production on natural calcite

The steam reforming of phenol towards H₂ production was studied in the 650–800 °C range over a natural pre-calcined (air, 850 °C) calcite material. The effects of reaction temperature, water, hydrogen, and carbon dioxide feed concentrations, and gas hourly space velocity (GHSV, h⁻¹) were investigated. The increase of reaction temperature in the 650–800 °C range and water feed concentration in the 40–50 vol% range were found to be beneficial for catalyst activity and H₂-yield. A similar result was also obtained in the case of decreasing the GHSV from 85,000 to 30,000 h⁻¹. The effect of concentration of carbon dioxide and hydrogen in the phenol/water feed stream was found to significantly decrease the rate of phenol steam reforming reaction. The latter was probed to be related to the reduction in the rate of water dissociation as evidenced by the significant decrease in the concentration of adsorbed bicarbonate and OH species on the surface of CaO according to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)-CO₂ adsorption experiments in the presence of water and hydrogen in the feed stream. Details of the CO₂ adsorption on the CaO surface at different reaction temperatures and gas atmospheres using in situ DRIFTS and transient isothermal adsorption experiments with mass spectrometry were obtained. Bridged, bicarbonate and unidentate carbonate species were formed under CO₂/H₂O/He gas mixtures at 600 °C with the latter being the most populated. A substantial decrease in the surface concentration of bicarbonate and OH species was observed when the CaO surface was exposed to CO₂/H₂O/H₂/He gas mixtures at 600 °C, result that probes for the inhibiting effect of H₂ on the phenol steam reforming activity. Phenol steam reforming reaction followed by isothermal oxygen titration allowed the measurement of accumulated “carbonaceous” species formed during phenol steam reforming as a function of reaction temperature and short time on stream. An increase in the amount of “carbonaceous” species with reaction time (650–800 °C range) was evidenced, in particular at 800 °C (4.7 vs. 6.7 mg C/g solid after 5 and 20 min on stream, respectively).     

Densification rate and phase structure changes during sintering of zinc titanate ceramics

Densification rate and phase structure changes during sintering of nanosized ZnTiO₃ were studied. Sintering was performed in a dilatometer in two regimes: the first to 900 °C (heating rates 5, 10 and 15 °C/min) and the second to 1200 °C (heating rates 3, 5 and 10 °C/min). XRD analysis of samples sintered at both temperatures combined with Rietveld structure refinement enabled determination of all phases present and their structure parameters. Samples sintered to 900 °C contained ZnTiO₃ and Zn₂TiO₄ with traces of r-TiO₂ (rutile) and Zn₂Ti₃O₈, while samples sintered to1200 °C contained only r-TiO₂ and Zn₂TiO₄. A master sintering curve was defined for sintering to 900 °C enabling determination of the sintering process activation energy as 313 kJ/mol.     

Pyrolysis by thermogravimetric analysis of blends of peat with coals of different characteristics and biomass

In this study, an investigation was carried out into the thermal behaviours of peat, reed, lignite, bituminous coal and blends of these with peat. The blends were prepared in 20:80, 40:60, 60:40, 80:20. The samples were pyrolysed in a TG analyzer in a nitrogen atmosphere (50 mL/min) at temperatures ranging from 25 to 900 °C. Using TG/DTG graphs, variations were investigated, which occurred in reaction intervals, percent of weight loss, peak temperatures and maximum devolatilization rate. The activation energy (E) and pre-exponential constant (A) were calculated using the Arrhenius type kinetic model.     

Thermal and mechanical properties of LaNbO4-based ceramics

Thermal and mechanical properties of polycrystalline La_1−xA_xNbO₄ (x = 0, 0.005, 0.02 and A = Ca, Sr and Ba) are reported. The materials possess a ferroelastic to paraelastic phase transition close to 500 °C, and the linear thermal expansion is significantly lower (8.6 ± 0.5 × 10⁻⁶ °C⁻¹) for the paraelastic phase compared to the ferroelastic phase (15 ± 3 × 10⁻⁶ °C⁻¹). The hardness was significantly higher for acceptor doped materials (6 GPa) compared to pure LaNbO₄ (3 GPa) due to a significantly smaller average grain size. The fracture toughness of La_0.98Sr_0.02NbO₄, measured by single edge V-notched beam method, was 1.7 ± 0.2 MPa m^1/2 independent of temperature up to 600 °C. The ferroelastic properties of the materials were confirmed by non-linear relationships between stress and strain during compression/decompression, a remnant strain after decompression and the presence of ferroelastic domains. The mechanical properties of LaNbO₄-based materials are discussed with focus on ferroelasticity, microcracking due to crystallographic anisotropy and pinning of ferroelastic domain boundaries.     

Characterization of sepiolite as a support of silver catalyst in soot combustion

Turkish sepiolite–zirconium oxide mixtures were applied as a support for the silver catalyst in a soot combustion. Sepiolite–Zr–K–Ag–O catalyst was characterized by XRD, N₂ adsorption, SEM, TPR-H₂ and EGA-MS. The combustion of soot was studied with a thermobalance (TG-DTA). The modification resulted in a partial degradation of the sepiolite structure, however, the morphology was preserved. The adsorption of N₂ of the modified sepiolite is a characteristic for mesoporous materials with a wide distribution of pores. The specific surface area S_BET equals 83 m²/g and the pores volume is 0.23 cm³/g. The basic character of the surface centers of sepiolite is indicated by CO₂ desorption (TPD-MS) at 170 °C and at about 620 °C due to a surface carbonates decomposition. The thermodesorption of oxygen at 650–850 °C indicates the decomposition of AgO_x phases at the surface. The presence of AgO_x phases is also confirmed by TPR-H₂ spectrum (low temperature reduction peak at 130 and 180 °C). The high-temperature reduction at about 570 °C is probably related to Ag–O–M phases on the support.The soot combustion takes place at T₅₀ = 575 °C. Without silver (sepiolite–Zr–K–O) T₅₀ = 560 °C but sepiolite modified with silver (sepiolite–Zr–K–Ag–O) undergoes the same process at T₅₀ = 490 °C.     

Enhancement of oxygen storage capacity by reductive treatment of Al2O3 and CeO2–ZrO2 solid solution nanocomposite

Oxygen storage capacity (OSC) of CeO₂–ZrO₂ solid solution, Ce_xZr_(1−x)O₄, is one of the most contributing factors to control the performance of an automotive catalyst. To improve the OSC, heat treatments were employed on a nanoscaled composite of Al₂O₃ and CeZrO₄ (ACZ). Reductive treatments from 700 to 1000 °C significantly improved the complete oxygen storage capacity (OSC-c) of ACZ. In particular, the OSC-c measured at 300 °C reached the theoretical maximum with a sufficient specific surface area (SSA) (35 m²/g) after reductive treatment at 1000 °C. The introduced Al₂O₃ facilitated the regular rearrangement of Ce and Zr ions in CeZrO₄ as well as helped in maintaining the sufficient SSA. Reductive treatments also enhanced the oxygen release rate (OSC-r); however, the OSC-r variation against the evaluation temperature and the reduction temperature differed from that of OSC-c. OSC-r measured below 200 °C reached its maximum against the reduction temperature at 800 °C, while those evaluated at 300 °C increased with the reduction temperature in the same manner as OSC-c.     

Hydrogenation of aromatic compounds during gas oil hydrodewaxing: I. Effect of ruthenium content and method of nickel catalyst preparation

Ni-based (8 wt.% NiO) dewaxing catalysts for the hydroconversion of the hydroraffinate of oil fraction (d_20 °C = 0.845 g/cm³; cloud point (CP) = −2 °C; aromatics = 25.8 wt.%; S = 25 ppm) were modified with Ru. The effect of Ru content (0.6, 0.75 and 0.9 wt.% of RuO₂) and the methods of Ni catalyst preparation were examined. The catalysts were characterised by N₂ sorption, TPR, ICP, XRD, SEM, XPS, H₂ chemisorption. Activity was tested in a continuous-flow system at 6 MPa (LHSV, 2.5 h⁻¹; H₂:CH, 350 N m³/m³). NiO and RuO₂ were found to exert a synergic effect on catalytic activity. The rise in RuO₂ content from 0.6 to 0.9 wt.% increased the HDA of HON from 23 to 65% at 240 °C and was parallelled by a drop in CP (by about 15 °C). The effect of Ru was found to depend on the method of Ni catalyst preparation.     

Effect of sintering on the catalytic activity of a Pt based catalyst for CO oxidation: Experiments and modeling

The goal of this paper was to make the link between sintering of a 1.6% Pt/Al₂O₃ catalyst and its activity for CO oxidation reaction. Thermal aging of this catalyst for different durations ranging from 15 min to 16 h, at 600 and 700 °C, under 7% O₂, led to a shift of the platinum particle size distributions towards larger diameters, due to sintering. These distributions were studied by transmission electron microscopy. The number and the surface average diameters of platinum particles increase from 1.3 to 8.9 nm and 2.1 to 12.8 nm, respectively, after 16 h aging at 600 °C. The catalytic activity for CO oxidation under different CO and O₂ inlet concentrations decreases after aging the catalyst. The light-off temperature increased by 48 °C when the catalyst was aged for 16 h at 600 °C. The CO oxidation reaction is structure sensitive with a catalytic activity increasing with the platinum particle size. To account for this size effect, two intrinsic kinetic constants, related either to platinum atoms on planar faces or atoms on edges and corners were defined. A platinum site located on a planar face was found to be 2.5 more active than a platinum site on edges or corners, whatever the temperature. The global kinetic law {r (mol m⁻² s⁻¹) = 103 × exp(−64,500/RT)[O₂]^0.74[CO]^−0.5)} related to a reaction occurring on a platinum atom located on planar faces allows a simulation of the CO conversion curves during a temperature ramp. Modeling of the catalytic CO conversion during a temperature ramp, using the different aged catalysts, allows prediction of the CO conversion curves over a wide range of experimental conditions.     

The enantioselective hydrolysis of racemic naproxen methyl ester in supercritical CO2 using Candida rugosa lipase

The enantioselective hydrolysis of racemic naproxen methyl ester by Candida rugosa lipase (CRL) was studied in aqueous buffer solution/isooctane reaction system in the presence of supercritical CO₂. The effects pressure (75–160 bar), temperature (32–42 °C) and reaction time (0.5–12 h) on the enantiomeric excesses of the product (ee_p) and the substrate (ee_s), enantiomeric ratio (E), conversion (x) and enzyme activity were investigated in a batch reactor system. The highest enantiomeric ratio achieved at 120 bar of pressure, 37 °C of temperature and 2 h of reaction time was E = 193 with x = 41.3%, ee_p = 97.9% and ee_s = 68.8%. CRL remained active at least for 12 h at 37 °C and 120 bar in supercritical CO₂ medium. Furthermore, enantiomeric ratio increased with increasing reaction time and reached the value of E = 236 with ee_p = 98.2%, ee_s = 70.0% and x = 41.6% after 12 h of hydrolysis.     

Development of kinetic model for the reaction between SO2/NO and coal fly ash/CaO/CaSO4 sorbent

Sorbents for semidry-type flue gas desulfurization (FGD) process can be synthesized by mixing coal fly ash, calcium oxide, and calcium sulfate in a hydration process. As sorbent reactivity is directly correlated with the specific surface area of the sorbent, reacting temperature, concentration of the reacting gas species and relative humidity, two major aim in the development of a kinetic model for the FGD process are to obtain an accurate model and at the same time, incorporating all the parameters above. Thus, the objective of this work is to achieve these two aims. The kinetic model proposed is based on the material balance for the gaseous and solid phase using partial differential equations incorporating a modified surface coverage model which assumes that the reaction is controlled by chemical reaction on sorbent grain surface. The kinetic parameters of the mathematical model were obtained from a series of experimental desulfurization reactions carried out under isothermal conditions at various operating parameters; inlet concentration of SO₂ (500 ppm  C_0,SO2  2000 ppm), inlet concentration of NO (250 ppm  C_O,NO  750 ppm), reaction temperature (60 °C  T  80 °C) and relative humidity (50%  RH  70%). For a variety of initial operating conditions, the mathematical model is shown to give comparable predictive capability when used for interpolation and extrapolation with error less than 7%. The model was found useful to predict the daily operation of flue gas desulfurization processes by using CaO/CaSO₄/coal fly ash sorbent to remove SO₂ from flue gas.     

The role of particle size on the electrochemical properties at 25 and at 55 °C of the LiCr0.2Ni0.4Mn1.4O4 spinel as 5 V-cathode materials for lithium-ion batteries

The role of the particle size on the electrochemical properties at 25 and at 55 °C of the LiCr_0.2Ni_0.4Mn_1.4O₄ spinel synthesized by combustion method has been determined. Samples with different particle size were obtained by heating the raw spinel from 700 to 1100 °C, for 1 h in air. X-ray diffraction patterns revealed that all the prepared materials are single-phase spinels. The main effect of the thermal treatment is the remarkable increase of the particles size from 60 to 3000 nm as determined by transmission electron microscopy. The electrochemical properties were determined at high discharge currents (1C rate) in two-electrode Li-cells. At 25 and at 55 °C, in spite of the great differences in particle size, the discharge capacity drained by all samples is similar (Q_dch ≈ 135 mAh g⁻¹). Instead, the cycling performances strongly change with the particle size. The spinels with Φ > 500 nm show better cycling stability at 25 and at 55 °C than those with Φ < 500 nm. The samples heated at 1000 and 1100 °C, with high potential (E ≈ 4.7 V), elevate capacity (Q ≈ 135 mAh g⁻¹), and remarkable cycling performances (capacity retention after 250 cycles >96%) are very attractive materials as 5V-cathodes for high-energy Li-ion batteries.     

Thermal cracking and combustion kinetics of asphaltenes derived from Fosterton oil

Thermal behavior of crude oil (Fosterton) asphaltenes mixed with reservoir sand was investigated using thermogravimetric analysis (TGA), in nitrogen and air atmospheres for different heating rates up to 800 °C. In this study, four sets of TGA runs were performed to examine the thermal behavior of Fosterton asphaltenes and the coke derived from the asphaltenes. The parameters studied were heating rate (10, 15 and 20 °C min^− 1) and the type of purge gas (N₂ and air) employed for the process of thermal degradation of asphaltenes. Distributed activation energy model (DAEM) has been applied to study the asphaltene pyrolysis kinetics. It was observed that the activation energy was distributed from 46.16 to 72.17 kJ/mol, for the conversion range of 0.1 to 0.4. The general model for nth order reaction was used to obtain the kinetic parameters of coke oxidation reaction from the TGA data. From the model, the calculated activation energy, E, was 93.46 kJ/mol and the pre-exponential factor was 9.59 × 10⁵ min^− 1 for the coke combustion. The apparent order of combustion reaction gradually increased from 0.7 to 0.8 for different temperatures.     

Evaluation of kinetic parameters for the crystallization and degradation process of synthesized strontium mercaptosuccinate functionalized poly(ε-caprolactone) by non-isothermal approach

Strontium (Sr) mercaptosuccinate (MS) functionalized poly(ε-caprolactone) (PCL) was prepared by ring opening polymerization technique in the presence of Sr-MS nanohybrid initiator and stannous octoate (SO) catalyst for 2 h at 160 °C under nitrogen atmosphere. FTIR, NMR, DSC, TGA, GPC, POM, TEM and AFM techniques were employed to characterize the Sr-MS functionalized polymer. The FTIR spectrum showed a small peak at 526 cm⁻¹ due to the Sr–O stretching. The particle size of the Sr-MS nanohybrid functionalized PCL matrix was determined as less than 30 nm. The crystallization rate and crystallinity percentage were estimated from the non-isothermal exothermic curves. The crystallization temperature (T_c) was found to be decreased with increasing the cooling rate whereas the degradation temperature (T_d) was increased with increasing the heating rate. Various kinetic models were applied to comprehend the degradation behaviour of Sr-MS functionalized PCL as well as its related kinetic parameters under non-isothermal condition. The activation energy (E_a) was calculated for both crystallization (138.5 kJ/mol) and degradation (187 kJ/mol) behaviours of Sr-MS functionalized PCL under non-isothermal condition.

     

Phenol methylation over nanoparticulate CoFe2O4 inverse spinel catalysts: The effect of morphology on catalytic performance

A series of CoFe₂O₄ nanoparticles have been prepared via co-precipitation and controlled thermal sintering, with tunable diameters spanning 7–50 nm. XRD confirms that the inverse spinel structure is adopted by all samples, while XPS shows their surface compositions depend on calcination temperature and associated particle size. Small (<20 nm) particles expose Fe³⁺ enriched surfaces, whereas larger (50 nm) particles formed at higher temperatures possess Co:Fe surface compositions close to the expected 1:2 bulk ratio. A model is proposed in which smaller crystallites expose predominately (1 1 1) facets, preferentially terminated in tetrahedral Fe³⁺ surface sites, while sintering favours (1 1 0) and (1 0 0) facets and Co:Fe surface compositions closer to the bulk inverse spinel phase. All materials were active towards the gas-phase methylation of phenol to o-cresol at temperatures as low as 300 °C. Under these conditions, materials calcined at 450 and 750 °C exhibit o-cresol selectivities of 90% and 80%, respectively. Increasing either particle size or reaction temperature promotes methanol decomposition and the evolution of gaseous reductants (principally CO and H₂), which may play a role in CoFe₂O₄ reduction and the concomitant respective dehydroxylation of phenol to benzene. The degree of methanol decomposition, and consequent H₂ or CO evolution, appears to correlate with surface Co²⁺ content: larger CoFe₂O₄ nanoparticles have more Co rich surfaces and are more active towards methanol decomposition than their smaller counterparts. Reduction of the inverse spinel surface thus switches catalysis from the regio- and chemo-selective methylation of phenol to o-cresol, towards methanol decomposition and phenol dehydroxylation to benzene. At 300 °C sub-20 nm CoFe₂O₄ nanoparticles are less active for methanol decomposition and become less susceptible to reduction than their 50 nm counterparts, favouring a high selectivity towards methylation.     

Thermal properties of the nitrogen-rich Ca-α-Sialons

Nitrogen-rich Ca-α-Sialon (Ca_xSi_12−2xAl_2xN₁₆ with x = 0.2, 0.4, and 0.8, 1.2 and 1.6) ceramics were prepared from the mixtures of Si₃N₄, AlN and CaH₂ powders in a hot press at 1800 °C using a pressure of 35 MPa and a holding time of 4 h, and then were investigated with respect to reaction mechanism, phase stability and oxidation resistance. In addition the sample with x = 1.6 was prepared in the temperature range 600–1800 °C using a pressure of 35 MPa and a holding time of 2 h. The α-Sialon phase was first observed at 1400 °C but the α-Si₃N₄ and AlN phases were still present at 1700 °C. Phase pure Ca-α-Sialon ceramics could not be obtained until the sintering temperature reached 1800 °C. The phase pure nitrogen-rich Ca-α-Sialon exhibited no phase transformation in the temperature range 1400–1600 °C. In general, mixed α/β-Sialon showed better oxidation resistance than pure α-Sialon in the low temperature range (1250–1325 °C), while α-Sialons with compositions located at α/β-Sialon border-line showed significant weight gains over the entire temperature range tested (1250–1400 °C). The phases formed upon oxidation were characterized by X-ray, SEM and TEM studies.