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1.
《Catalysis communications》2007,8(11):1763-1766
Selective hydrogenation of p-chloronitrobenzene to p-chloraniline over ruthenium catalyst was found to be promoted remarkably (Selectivity: from 80.4% to 98.6%; TON: from 0.89 × 10−2 s−1 to 3.20 × 10−2 s−1) by simply adding some water into the solvent of ethanol. The optimized volume percent of water in ethanol was 30%. The promoting effect of water was also found over various supported metal catalysts, such as Fe/SiO2, Co/SiO2, Ni/SiO2, Cu/SiO2, and Ag/SiO2.  相似文献   

2.
Hydrogen-terminated diamond surface exhibits p-type conductivity during its exposure to air. To investigate this phenomenon, we examined the influence of different gases on the surface conductivity. Exposure to NO2 gas resulted in the biggest increase in conductivity, while H2O vapor decreased the surface conductivity. Moreover, even very low concentrations of NO2 molecules in air increased the hole sheet concentration, and with increasing NO2 concentration, the hole sheet concentration increased up to 2.3 × 1014 cm? 2 (at 300 ppm NO2). This increase of hole sheet concentration was observed during exposure to NO2 gas and simultaneous adsorption of NO2 molecules on the diamond surface, while it decreased when the exposure stopped and NO2 molecules desorbed from the surface. X-ray photoelectron spectroscopy investigation showed upward band bending and partial oxidation of the hydrogen-terminated surface after exposure to air and NO2. FETs exposed to NO2 gas exhibited lower source and drain resistances, which led to a 1.8-fold increase of maximum drain current, transconductance increased 1.5-fold and maximum frequency of oscillation increased 1.6-fold.  相似文献   

3.
High-quality polycrystalline diamond film has been extremely attractive to many researchers, since the maximum transition frequency (fT) and the maximum frequency of oscillation (fmax) of polycrystalline diamond electronic devices are comparable to those of single crystalline diamond devices. Besides large deposition area, DC arc jet CVD diamond films with high deposition rate and high quality are one choice for electronic device industrialization. Four inch free-standing diamond films were obtained by DC arc jet CVD using gas recycling mode with deposition rate of 14 μm/h. After treatment in hydrogen plasma under the same conditions for both the nucleation and growth sides, the conductivity difference between them was analyzed and clarified by characterizing the grain size, surface profile, crystalline quality and impurity content. The roughness of growth surface with the grain size about 400 nm increased from 0.869 nm to 8.406 nm after hydrogen plasma etching. As for the nucleation surface, the grain size was about 100 nm and the roughness increased from 0.31 nm to 3.739 nm. The XPS results showed that H-termination had been formed and energy band bent upwards. The nucleation and growth surfaces displayed the same magnitude of square resistance (Rs). The mobility and the sheet carrier concentration of the nucleation surface were 0.898 cm/V s and 1013/cm2 order of magnitude, respectively; while for growth surface, they were 20.2 cm/V s and 9.97 × 1011/cm2, respectively. The small grain size and much non-diamond carbon at grain boundary resulted in lower carrier mobility on the nucleation surface. The high concentration of impurity nitrogen may explain the low sheet carrier concentration on the growth surface. The maximum drain current density and the maximum transconductance (gm) for MESFET with gate length LG of 2 μm on H-terminated diamond growth surface was 22.5 mA/mm and 4 mS/mm, respectively. The device performance can be further improved by using diamond films with larger grains and optimizing device fabrication techniques.  相似文献   

4.
A diamond-based field-effect transistor (FET) with SiNx and ZrO2 double dielectric layer has been demonstrated. The SiNx and ZrO2 gate dielectric are deposited by plasma-enhanced chemical vapor deposition (PECVD) and radio frequency (RF) sputter methods, respectively. SiNx layer is found to have the ability to preserve the conduction channel at the surface of hydrogen-terminated diamond film. The leakage current density (J) of SiNx/ZrO2 diamond metal-insulator-semiconductor FET (MISFET) keeps lower than 3.88 × 10 5 A·cm 2 when the gate bias was changed from 2 V to − 8 V. The double dielectric layer FET operates in a p-type depletion mode, whose maximum drain-source current, threshold voltage, maximum transconductance, effective mobility and sheet hole density are determined to be − 28.5 mA·mm 1, 2.2 V, 4.53 mS·mm 1, 38.9 cm2·V 1·s 1, and 2.14 × 1013 cm 2, respectively.  相似文献   

5.
Boron was doped into diamond films which were synthesized homoepitaxially on polished (100) diamond substrates by means of microwave plasma-assisted chemical vapor deposition (MPCVD) using trimethylboron as the dopant at a constant substrate temperature of 1073 K. The morphologies and electrical properties of the synthesized diamond films were dependent on the total reaction pressure. A maximum Hall mobility, 760 cm2 V−1 s−1, was obtained for the film synthesized at 10.7 kPa. The values of Hall mobility were comparable with those obtained for B2H6-doped films at corresponding hole concentrations.  相似文献   

6.
This paper deals with the systematic study of Fe/HBEA zeolites for the selective catalytic reduction (SCR) of NOx by NH3 in diesel exhaust. The catalysts are prepared by incipient wetness impregnation of H-BEA zeolite (Si/Al = 12.5). The SCR examinations performed under stationary conditions show that the pattern with a Fe load of 0.25 wt.% (0.25Fe/HBEA) reveals pronounced performance. The turnover frequency at 200 °C indicates superior SCR activity of 0.25Fe/HBEA (8.5 × 10−3 s−1) as compared to commercial Fe-exchanged BEA (0.99 × 10−3 s−1) and V2O5/WO3/TiO2 (1.0 × 10−3 s−1). Based upon powder X-ray diffraction (PXRD), temperature programmed reduction by H2 (HTPR), diffuse reflectance UV–vis spectroscopy (DRUV–VIS) and catalytic data it is concluded that the pronounced performance of 0.25Fe/HBEA is substantiated by its high proportion of isolated Fe oxo sites. Furthermore, isotopic studies show that no association mechanism of NH3 takes place on 0.25Fe/HBEA, i.e. N2 is mainly formed from NO and NH3.The evaluation of 0.25Fe/HBEA under more practical conditions shows that H2O decreases the SCR performance, while CO and CO2 do not affect the activity. Contrary, SCR is markedly accelerated in presence of NO2 referring to fast SCR. Moreover, hydrothermal treatment at 550 °C does not change SCR drastically, whereas a clear decline is observed after 800 °C aging.  相似文献   

7.
Contacts to boron-doped, (100)-oriented diamond implanted with Si or with Si and B were formed and the effects of dose, implantation energy and anneal treatment on the specific contact resistance were examined. Ti/Au contacts on heavily implanted diamond (1016 Si ions cm−2, Ei=30 keV or 1017 Si and B ions cm−2, Ei=15 keV (Si) and Ei=10 keV (B)) had a specific contact resistance lower than the best contacts produced on unimplanted diamond. A specific contact resistance of (1.4±6.4)×10−7 Ω cm−2 was achieved following a 450°C anneal. The results were consistent with a reduction in barrier height brought about by silicide formation. Light silicon implantation (1013 ions cm−2) or relatively light dual implantation (B, Si<1016 ions cm−2) did not reduce the specific contact resistance. Increasing the diamond conductivity by 4×104 decreased the specific contact resistance by over three orders of magnitude, in agreement with the trend observed by Prins (J.F. Prins, J. Phys. D 22 (1989) 1562).  相似文献   

8.
《Ceramics International》2016,42(3):4361-4369
We study the thermal, mechanical and electrical properties of B4C, BCN, ZrBC and ZrBCN ceramics prepared in the form of thin films by magnetron sputtering. We focus on the effect of Zrx(B4C)1−x sputter target composition, the N2+Ar discharge gas mixture composition, the deposition temperature and the annealing temperature after the deposition. The thermal properties of interest include thermal conductivity (observed in the range 1.3–7.3 W m−1 K−1), heat capacity (0.37–1.6×103 J kg−1 K−1 or 1.9–4.1×106 Jm−3 K−1), thermal effusivity (1.6–4.5×103 J m−2 s−1/2 K−1) and thermal diffusivity (0.38–2.6×10−6 m2 s−1). We discuss the relationships between materials composition, preparation conditions, structure, thermal properties, temperature dependence of the thermal properties and other (mechanical and electrical) properties. We find that the materials structure (amorphous×crystalline hexagonal ZrB2-like×nanocrystalline cubic ZrN-like), more than the composition, is the crucial factor determining the thermal conductivity and other properties. The results are particularly important for the design of future ceramic materials combining tailored thermal properties, mechanical properties, electrical conductivity and oxidation resistance.  相似文献   

9.
Boron doped diamond layers have been grown on (110) single crystal diamond substrates with B/C ratios up to 20 ppm in the gas phase. The surface of the diamond layers observed by scanning electron microscopy consists of (100) and (113) micro-facets. Fourier Transform Photocurrent Spectroscopy indicates substitutional boron incorporation. Electrical properties were measured using Hall effect from 150 to 1000 K. Secondary ion mass spectrometry analyses are consistent with the high incorporation of boron determined by electrical measurements. A maximum mobility of 528 cm2 V 1 s 1 was measured at room temperature for a charge carrier concentration of 1.1 1013 cm 3. Finally, properties of boron doped (110) diamond layers are compared with layers on (100) and (111) orientated substrates.  相似文献   

10.
The aim of this work was to assess and model supercritical carbon dioxide (ScCO2) extraction kinetics of pre-pelletized Jalapeño peppers (Capsicum annuum L.). Pepper flakes were conditioned to low moisture, ground finely and pelletized at high pressure, and pellets were subsequently ground and size classified. The effects of average sample particle size (Dp=0.28–3.19 mm) and superficial solvent velocity (Us=0.14–2.62 mm s−1) were evaluated at 40 °C and 120 or 320 bar. Extraction rate increased as a result of a decrease in Dp. It also increased as a result of an increase in Us at 120 bar, but the effect was almost negligible at 320 bar. Integral extraction yields of capsicum oleoresin and capsaicinoids were ≈0.102 g g−1 and ≈240 mg kg−1, respectively, independent of extraction conditions. External mass transfer coefficients (kf) increased with Us, but this effect was less pronounced than commonly reported in the literature. Values of kf increased as Dp or process pressure decreased, due respectively to increments in specific area and improvements in transport properties. Internal mass transfer coefficients, on the other hand, were 5.3×10−8 m s−1 at 40 °C and 120 bar, and 34.7×10−8 m s−1 at 40 °C and 320 bar. Solutes were effectively liberated from the original matrix with our multistage pretreatment, so that the fraction of free solute did not depend on Dp (α=0.46). Pseudosolubilities for capsicum oleoresin in ScCO2 (≈2100 mg l−1 at 40 °C and 120 bar; ≈13,700 mg l−1 solute/CO2 at 40 °C and 320 bar) were of the same order of magnitude as corresponding true solubilities of capsaicin (5600 and 11,800 mg l−1, respectively). Estimated true solubilities of chlorophyll-a in ScCO2 (2 mg l−1 at 40 °C and 120 bar; 18 mg l−1 at 40 °C and 320 bar), on the other hand, were orders of magnitude smaller, which justifies a much slower extraction rate for green pigments than pungent compounds. Thus, oleoresin obtained after 4 h at 40 °C and 120 bar had a very attractive light yellow tinge.  相似文献   

11.
《Ceramics International》2017,43(4):3726-3733
Ta-doped lead-free 0.94NBT-0.06BT-xTa (x=0.0–1.0%) ceramics were synthesized by a conventional solid-state route. XRD shows that the compositions are at a morphotropic phase boundary where rhombohedral and tetragonal phases coexist. The depolarization temperature (Td) shifted to lower temperature with the increase of Ta content. The pyroelectric coefficient (p) of doped ceramics greatly enhanced compared with undoped material and reached a maximum of 7.14×10−4 C m−2 °C−1 at room temperature (RT) and 146.1×10−4 C m−2 °C−1 at Td at x=0.2%. The figure of merits, Fi and Fv, also showed a great improvement from 1.12×10−10 m v−1 and 0.021 m2 C−1 at x=0.0 to 2.55×10−10 m v−1 and 0.033 m2 C−1 at x=0.2% at RT. Furthermore, Fi and Fv show the huge improvement to 52.2×10−10 m v−1 and 0.48×10−10 m v−1 respectively at Td at x=0.2%. FC shows a value between 2.26 and 2.42 ×10−9 C cm−2 °C−1 at RT at x=0.2%. The improved pyroelectric properties make NBT-0.06BT-0.002Ta ceramics a promising infrared detector material.  相似文献   

12.
The oxygen permeability of mixed-conducting Sr1−xCaxFe1−yAlyO3−δ (x=0–1.0; y=0.3–0.5) ceramics at 850–1000 °C, with an apparent activation energy of 120–206 kJ/mol, is mainly limited by the bulk ionic conduction. When the membrane thickness is 1.0 mm, the oxygen permeation fluxes under pO2 gradient of 0.21/0.021 atm vary from 3.7×10−10 mol s−1 cm−2 to 1.5×10−7 mol s−1 cm−2 at 950 °C. The maximum solubility of Al3+ cations in the perovskite lattice of SrFe1−yAlyO3−δ is approximately 40%, whilst the brownmillerite-type solid solution formation range in Sr1−xCaxFe0.5Al0.5O3−δ system corresponds to x>0.75. The oxygen ionic conductivity of SrFeO3-based perovskites decreases moderately on Al doping, but is 100–300 times higher than that of brownmillerites derived from CaFe0.5Al0.5O2.5+δ. Temperature-activated character and relatively low values of hole mobility in SrFe0.7Al0.3O3−δ, estimated from the total conductivity and Seebeck coefficient data, suggest a small-polaron mechanism of p-type electronic conduction under oxidising conditions. Reducing oxygen partial pressure results in increasing ionic conductivity and in the transition from dominant p- to n-type electronic transport, followed by decomposition. The low-pO2 stability limits of Sr1−xCaxFe1−yAlyO3−δ seem essentially independent of composition, varying between that of LaFeO3−δ and the Fe/Fe1−γO boundary. Thermal expansion coefficients of Sr1−xCaxFe1−yAlyO3−δ ceramics in air are 9×10−6 K−1 to 16×10−6 K−1 at 100–650 °C and 12×10−6 K−1 to 24×10−6 K−1 at 650–950 °C. Doping of SrFe1−yAlyO3−δ with aluminum decreases thermal expansion due to decreasing oxygen nonstoichiometry variations.  相似文献   

13.
Polarized negative muons were used to study the dynamics of non-equilibrium charge carriers in diamond. From the behavior of the muon polarization it is concluded that the acceptor center μB in diamond is formed in the diamagnetic state (with the probability close to unity) and then, by capturing a hole, turns to the paramagnetic state. The hole capture rate by an ionized acceptor center μB in synthetic diamond was found to depend on temperature as 1/Tα, where α = (1.5–2.5) at T > 80 K.  相似文献   

14.
In this paper we give the first report of a high-density phase of condensed electron–hole drops in diamond. Synthetic crystals grown by the high pressure–high temperature technique were optically highly excited by laser pulses with photon energies above the band-gap of diamond. At temperatures below ≈170 K we observe novel broad luminescence bands, in addition to the well-known free exciton spectra, with characteristic features identifying them as originating from electron–hole drops. Fits to the photoluminescence spectra yield an electron–hole density within the drops of n0=9.6×1019 cm−3, a reduced band-gap of Eg′=5.224 eV (instead of Eg=5.49 eV) due to the attractive interaction of the particles in the condensed phase, and a work function of φ=52 meV with respect to the free exciton threshold Egx.  相似文献   

15.
Electron paramagnetic resonance (EPR) and optical absorption data on the negative and neutral vacancy in diamond are presented. We determine directly the constant of proportionality between the concentration of V and the integrated intensity of its zero-phonon line (ND1). Using the standard notation, the calculated value is fND1=4.8(2)×10−16 meV cm2. This differs significantly from previous accepted results which used indirect methods of calculation. Using this new number we calculate a creation rate of 0.50(5) cm−1 for 1.9 MeV electrons at room temperature — a factor of nearly seven greater than was previously thought.  相似文献   

16.
The spark plasma sintering (SPS) behaviour of nano-sized Bi4Ti3O12 (BIT) and micron-sized CaBi2Nb2O9 (CBNO) powders is described. The densification process of both powders is very rapid, i.e. the densification occurs within a very narrow time interval (2–3 min using a heating rate of 100 °C min−1 and a pressure of 50 MPa). The BIT powder exhibits a lower densification onset temperature (∼650 °C) and higher maximum shrinkage rate (8.9 × 10−3 s−1 at 780 °C) than that of the CBNO powder (∼825 °C and 4.5 × 10−3 s−1 at 950 °C). Isothermal compaction studies revealed that fully dense nano-sized BIT compacts could be obtained within the temperature region 750 °C < Tiso < 850 °C while for Tiso > 850 °C compacts containing elongated platelet grains are formed. A new preparation route to produce highly textured compacts is described in detail. Appropriate pre-forms are prepared by spark plasma sintering (SPS) and these fully dense compacts are subject to superplastic deformation in the SPS unit to achieve a total compressive strain of ∼60%. This strain was achieved within a period of 1.5 min and with a maximum strain rates of 1.1 × 10−2 s−1 achieved at ∼840 °C and 1.3 × 10−2 s−1 at 1020 °C for the BIT and CBNO compacts, respectively. The X-ray studies showed that the Lotgering orientation factors of grains in the deformed BIT and CBNO compacts are 99% and 70%. The formation of highly textured compacts is suggested to be governed by a superplastic deformation-induced directional dynamic ripening mechanism.  相似文献   

17.
It is generally accepted that SiC layers are often involved in the adhesion efficiency of chemical vapour deposition (CVD) diamond films on Si-containing substrates. Si3N4–SiC composite substrates with different amounts of SiC particles (0–50 wt%) were then used for diamond deposition. Samples were produced by pressureless sintering (1750°C, N2 atmosphere, 2–4 h). The diamond films were grown on a commercial MPCVD reactor using H2/CH4 mixtures. Despite there being no special substrate pre-treatment, the films were densely nucleated when SiC was added (Nd≈1×1010 cm−2) with primary nanosized (∼100 nm) particles, followed by a less dense (Nd≈1×106 cm−2) secondary nucleation. Indentation experiments with a Brale tip of up to 588 N applied load corroborated the benefit of SiC inclusion for a strong adhesion. The low thermal expansion coefficient mismatch between Si3N4 and diamond resulted in very low compressive stresses in the film, as proved by micro-Raman spectroscopy.  相似文献   

18.
Boron-doped diamond electrodes have received much attention for electrochemical determination due to their attractive electrochemical properties over other electrodes. The electrooxidation of fluvastatin sodium at boron-doped diamond electrode was investigated using cyclic, differential pulse and square wave voltammetry. The possible mechanism of oxidation was discussed with model compounds that have indole oxidation. The dependence of the peak current and potentials on pH, concentration, scan rate, and the nature of the buffer were investigated. The oxidation of fluvastatin was irreversible and exhibited a diffusion-controlled fashion. The slope of the log ip–log v linear plot was 0.44 indicating the diffusion control for pH 10.00 Britton–Robinson buffer solution. The linear response was obtained in the ranges of 1 × 10 6 M–6 × 10 4 M in pH 10.00 BR buffer solution. The detection limit of the standard solution is estimated to be 1.37 × 10 7 M for DPV, 1.44 × 10 7 M for SWV. The repeatability of the methods was found as 0.66 and 0.15 RSD % for peak currents for differential pulse and square wave voltammetry, respectively. The practical analytical value of the method is demonstrated by quantitative determination of fluvastatin in pharmaceutical formulation and human serum, without the need for separation or complex sample preparation, since there was no interference from the excipients and endogenous substances. Selectivity, reproducibility and accuracy of the developed methods were demonstrated by recovery studies.  相似文献   

19.
Lead-free 0.94NBT-0.06BT-xLa ceramics at x = 0.0–1.0 (%) were synthesized by a conventional solid-state route. XRD shows that the compositions are at a morphotropic phase boundary where rhombohedral and tetragonal phases coexist. With increasing La3+ content pyroelectric coefficient (p) and figures of merits greatly increase; however, the depolarization temperature (Td) decreases. p is 7.24 × 10−4C m−2 °C−1 at RT at x = 0.5% and 105.4 × 10−4C.m−2 °C−1 at Td at x = 0.2%. Fi and Fv show improvements at RT from 1.12 (x = 0%) to 2.65 (x10 −10 m v−1) (x = 0.5%) and from 0.021 to 0.048 (m2.C−1) respectively. Fi and Fv show a huge increase to 37.6 × 10−10 m v−1 and 0.56 m2 C−1 respectively at Td at x = 0.2%. FC shows values of 2.10, 2.89, and 2.98 (x10−9C cm−2 °C−1) at RT at 33, 100 and 1000 (Hz) respectively. Giant pyroelectric properties make NBT-0.06BT-xLa at x = 0.2% and 0.5% promising materials for many pyroelectric applications.  相似文献   

20.
《Ceramics International》2016,42(8):9605-9612
Inorganic pigments are substances that develop colour in organic solids such as ceramics and glazes, and are usually a complex mixture of oxides, and relatively low-cost. Their chromatic properties have been extensively studied, yet surprisingly the magnetic and electrical properties of these economic and common materials have been neglected, despite the fact many are based on ferrite spinels. Therefore, we investigated these properties in commercial black and brown pigments, to assess their potential as magnetic materials. The brown and black pigments were found to be spinel ferrites, with estimated formulas of Fe1.34Cr0.62Mn0.66Zn0.22Ni0.10Co0.06O4 and Fe1.02Cr0.97Co0.57Mn0.23Ni0.21O4, respectively. The brown pigment also contained a higher amount of SiO2 compared to the black pigment (~7 mol% vs. ~2 mol%), which appeared as a second phase of crystalline quartz, and adversely affected its porosity, magnetisation and electrical ac conductivity, compared to the black pigment. However, both were very magnetic and very soft ferrites. The brown pigment had Ms=11.7 A m2 kg−1 and Hc of 1.5 kA m−1, with a high electrical conductivity (σ) of 4×10−4−7×10−3 Ω−1 m−1 between 100 Hz and 1 MHz. The black pigment was equally magnetically soft, but had a much greater magnetisation and lower electrical conductivity, with Ms=18.7 A m2 kg−1, Hc=2.4 kA m−1, and σ=5×10−6−8×10−5 Ω−1 m−1 between 100 Hz and 1 MHz.This work has revealed the potential hidden value of low-cost commercial inorganic pigments based on spinel ferrites as magnetic materials. This demonstrates their potential at low-cost alternative materials for applications such as in power supply transformers, switching materials and sensors, where soft magnetisation is especially important.  相似文献   

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