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1.
The samples of dibarium magnesium orthoborate Ba2Mg(BO3)2 were synthesized by solid-state reaction. The X-ray diffraction (XRD) patterns and Raman spectra of the samples were collected. Electronic structure and vibrational spectroscopy of Ba2Mg(BO3)2 were systematically investigated by first principle calculation. A direct band gap of 4.4 eV was obtained from the calculated electronic structure results. The top valence band is constructed from O 2p states and the low conduction band mainly consists of Ba 5d states. Raman spectra for Ba2Mg(BO3)2 polycrystalline were obtained at ambient temperature. The factor group analysis results show the total lattice modes are 5Eu + 4A2u + 5Eg + 4A1g + 1A2g + 1A1u, of which 5Eg + 4A1g are Raman-active. Furthermore, we obtained the Raman active vibrational modes as well as their eigenfrequencies using first-principle calculation. With the assistance of the first-principle calculation and factor group analysis results, Raman bands of Ba2Mg(BO3)2 were assigned as Eg (42 cm−1), A1g (85 cm−1), Eg (156 cm−1), Eg (237 cm−1), A1g (286 cm−1), Eg (564 cm−1), A1g (761 cm−1), A1g (909 cm−1), Eg (1165 cm−1). The strongest band at 928 cm−1 in the experimental spectrum is assigned to totally symmetric stretching mode of the BO3 units.  相似文献   

2.
Vanadium dioxide (VO2) nano-sheets were directly synthesized via a continuous hydrothermal process and were investigated as electrodes in a wide potential range of 0.05–3 V vs. Li/Li+. The nano-sheets showed excellent capacity retention, with a specific capacity of 350 mAh g 1 at an applied current of 0.1 A g 1 and 95 mAh g 1 at 10 A g 1. Further electrochemical testing suggested that a significant proportion of the charge storage in the cells was due to pseudocapacitive processes.  相似文献   

3.
A micro-bomb combustion calorimeter recently designed for samples of mass   80 mg has been improved and tested with m -methoxybenzoic acid in order to verify the chemistry of the combustion process and the accuracy of the energy corrections involved in the analysis of results. From measurements in this calorimeter, the standard massic energy of combustion of 1,2,4-triazole was determined to beΔcuo =   (19200.3  ±  3.4)J · g  1. Some new measurements with our macro combustion calorimeter confirm an earlier result from this laboratory of   (19203.1  ±  1.2)J · g  1. Determination of the purity by d.s.c. of 1,2,4-triazole purified some 10 years ago reveals that samples of this compound remained unchanged and suggest that 1,2,4-triazole be used as a possible reference material for organic compounds with a high content of nitrogen. From the experimental results with the micro-bomb combustion calorimeter, the actual and earlier results from macro-bomb combustion calorimetry, and those obtained in other laboratories, the standard massic energy of combustion of 1,2,4-triazole was deduced to beΔcuo =   (19202.5  ±  1.7)J · g  1.  相似文献   

4.
《Vibrational Spectroscopy》2007,45(2):375-381
Fourier transform infrared (FTIR) spectroscopy was used to examine the conformation of proteins in spray-dried milk protein concentrate (MPC) powders and to determine if the spectral changes could be related to nitrogen solubility of these powders. MPC samples (83–92% protein, dry basis) were prepared using a range of processing conditions and stored for 4 weeks at 21 °C. FTIR spectra were collected in the mid infrared (MIR) region between 4000 and 600 cm−1. FTIR data was pre-processed to remove physical effects causing discrimination between samples using firstly second derivatives and normalization and secondly the extended multiplicative scatter correction (EMSC) technique. The FTIR spectral changes were subsequently assessed using second derivative spectroscopy and principal components analysis (PCA) in the amide I and II regions (1700–1400 cm−1) and the fingerprint region (1800–700 cm−1). PCA analysis showed that the different powder preparations could be separated on scores plots but the separation was not related to nitrogen solubility per se. However, changes in nitrogen solubility of individual MPC powders during storage could be correlated to changes in FTIR spectra. PCA analysis of FTIR spectra could generally discriminate between MPC powders that had lost significant nitrogen solubility (9–20%) and those in which nitrogen solubility was preserved on storage. There were changes in intensity and/or position of bands at 1630 cm−1 when the solubility of a stored sample decreased substantially. The results of this work also show that EMSC data pre-processing for these samples gives comparable results when compared with more complicated data pre-processing for the removal of physical effects.  相似文献   

5.
《Tetrahedron: Asymmetry》2014,25(23):1501-1504
A new NADH-dependent carbonyl reductase RhCR capable of efficiently reducing the ε-ketoester ethyl 8-chloro-6-oxooctanoate (ECOO) to give ethyl (S)-8-chloro-6-hydroxyoctanoate [(S)-ECHO], an important chiral precursor for the synthesis of (R)-α-lipoic acid, was identified from Rhodococcus sp. ECU1014. Using recombinant Escherichia coli cells expressing RhCR and glucose dehydrogenase used for the regeneration of cofactor, 440 g L−1 (2 M) of ECOO were stoichiometrically converted to (S)-ECHO in a space–time yield of 1580 g L−1 d−1 without the external addition of any expensive cofactor.  相似文献   

6.
《Chemical physics letters》1999,291(1-2):75-81
The fluorescence spectrum of all-trans-β-carotene was recorded at 170 K. The 1Bu+  1Ag fluorescence exhibited clear vibrational structures constituting a mirror image with those of the 1Bu+  1Ag absorption, and the deconvolution of the entire spectrum identified the 2Ag(0)  1Ag(0) transition at 14 500 cm−1. The displacements of the 1Bu+ and 2Ag potential minima along ν1 and ν2 (the CC stretching and C–C stretching normal coordinates, respectively) were determined to be 1.2 and 0.9, and 1.6 and 1.5, respectively. Thus, much larger potential displacements in the 2Ag state than in the 1Bu+ state have been shown.  相似文献   

7.
《Microchemical Journal》2008,88(2):128-131
The present work proposes a direct method based on slurry sampling for the determination of zinc and copper in human hair samples by multi-element sequential flame atomic absorption spectrometry. The slurries were prepared by cryogenic grinding and sonication of the samples. The optimization step was performed using univariate methodology and the factors studied were: nature and concentration of the acid solution, amount sample/slurry volume, sonication time, and particle size. The established experimental conditions are the use of a sample mass of 50 mg, 2 mol L 1 nitric acid solution, sonication time of 20 min and slurry volume of 10 mL. Adopting the optimized conditions, this method allows the determination of zinc and copper with detection limits of 88.3 and 53.3 ng g 1, respectively, and precision expressed as relative standard deviation (RSD) of 1.7% and 1.6% (both, n = 10) for contents of zinc and copper of 100.0 and 33.3 μg g 1, respectively. The accuracy was checked and confirmed by analysis of two certified reference materials of human hair. The procedure was applied for the determination of zinc and copper in two human hair samples. The zinc and copper contents varied from 100.0 to 175.6 and from 3.2 to 32.8 μg g 1, respectively. These samples were also analyzed after complete digestion in a closed system and determination by FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results.  相似文献   

8.
An electrothermal vaporization (ETV) system useful for the analysis of solutions and slurries has been coupled with a sector-field inductively coupled plasma mass spectrometer (ICP–MS) equipped with an array detector. The ability of this instrument to record the transient signals produced for a number of analytes in ETV–ICP–MS is demonstrated. Detection limits for Mn, Fe, Co, Ni, Cu, Zn and Ga are in the range of 4–60 pg μL 1 for aqueous solutions and in the low μg g 1 range for the analysis of 10 mg mL 1 slurries of Al2O3 powders. The dynamic ranges measured for Fe, Cu and Ga spanned 3–5 orders of magnitude when the detector was operated in the low-gain mode and appear to be limited by the ETV system. Trace amounts of Fe, Cu and Ga could be directly determined in Al2O3 powders at the 2–270 μg g 1 level without the use of thermochemical reagents. The results well agree with literature values for Fe and Cu, whereas deviations of 50% at the 90 μg g 1 level for Ga were found.  相似文献   

9.
Excess molar volumes VmE of binary mixtures of 2,2,2-trifluoroethanol with water, or acetone, or methanol, or ethanol, or 1-alcholos, or 1,4-difluorobenzene, or 4-fluorotoluene or α,α,α-trifluorotoluene were measured in a vibrating tube densimeter at temperature 298.15 K and pressure of 101 kPa. The VmE extrema are: 1.540 cm3 · mol−1 for (2,2,2-trifluoroethanol + 1-heptanol); 1.452 cm3 · mol−1 for (2,2,2-trifluoroethanol + 1-hexanol); 1.238 cm3 · mol−1 for (2,2,2-trifluoroethanol + 1-butanol); 0.821 cm3 · mol−1 for (2,2,2-trifluoroethanol + 4-fluorotoluene); 0.817 cm3 · mol−1 for (2,2,2-trifluoroethanol + ethanol); 0.647 cm3 · mol−1 for (2,2,2-trifluoroethanol + methanol); 0.618 cm3 · mol−1 for (2,2,2-trifluoroethanol + acetone); 0.605 cm3 · mol−1 for (2,2,2-trifluoroethanol + α,α,α-trifluorotoluene); 0.485 cm3 · mol−1 for (2,2,2-trifluoroethanol + 1,4-difluorobenzene); and −0.656 cm3 · mol−1 for (2,2,2-trifluoroethanol + water). The limiting excess partial molar volumes are estimated.  相似文献   

10.
A method for the direct determination of trace rare earth elements in ancient porcelain samples by slurry sampling fluorinating electrothermal vaporization inductively coupled plasma mass spectrometry was developed with the use of polytetrafluoroethylene as fluorinating reagent. It was found that Si, as a main matrix element in ancient porcelain sample, could be mostly removed at the ashing temperature of 1200 °C without considerable losses of the analytes. However, the chemical composition of ancient porcelain sample is very complicated, which makes the influences resulting from other matrix elements not be ignored. Therefore, the matrix effect of ancient porcelain sample was also investigated, and it was found that the matrix effect is obvious when the matrix concentration was larger than 0.8 g l 1. The study results of particle size effect indicated that when the sample particle size was less than 0.057 mm, the particle size effect is negligible. Under the optimized operation conditions, the detection limits for rare earth elements by fluorinating electrothermal vaporization inductively coupled plasma mass spectrometry were 0.7 ng g 1 (Eu)–33.3 ng g 1(Nd) with the precisions of 4.1% (Yb)–10% (La) (c = 1 μg l 1, n = 9). The proposed method was used to directly determine the trace rare earth elements in ancient porcelain samples produced in different dynasty (Sui, Ming and Qing), and the analytical results are satisfactory.  相似文献   

11.
Arsenic and germanium have been evaluated as internal standards to minimize matrix effects on the direct determination of selenium in milk by graphite furnace atomic absorption spectrometry (GFAAS) using tubes with integrated platform, pre-treated with W together with Pd as chemical modifier. The efficiency of As and Ge as internal standards for 25 μg L 1 Se plus 500 μg L 1 As or Ge in diluted (1 + 9 v/v) milk plus 1.0% (v/v) HNO3 was evaluated by means of correlation graphs plotted from the normalized absorbance signals (n = 20) of internal standard (axis y) versus analyte (axis x). The equations that describe the linear regression were: AAs =  0.004 ± 0.019 + 1.02 ± 0.019 ASe (r = 0.9967 ± 0.005); AGe =  0.017 ± 0.015 + 1.01 ± 0.015 ASe (r = 0.9978 ± 0.004). Samples and reference solutions were automatically spiked with 500 μg L 1 Ge or As and 1.0% (v/v) HNO3 by the autosampler. For 20 μL of aqueous standard solutions, analytical curves in the 5.00–40.0 μg L 1 Se range were established using the ratio of Se absorbance to internal standard absorbance (ASe / AIS) versus analyte concentration, and good linear correlations were obtained. The characteristic mass was 40 pg Se. Limits of detection were 0.55 and 0.40 μg L 1 with As and Ge as the internal standard, respectively. Relative standard deviations (RSD) for a sample containing 25 μg L 1 Se were 1.2% and 1.0% (n = 12) using As and Ge, respectively. The RSD without internal standardization was about 6%. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values were in the 99–105% range with IS and in the 70–80% range without IS. Using Ge as the internal standard, results of analysis of standard reference materials were in agreement with certified values at a 95% confidence level. The selenium concentration for 10 analyzed milk samples varied from 5.0 to 20 μg L 1.  相似文献   

12.
Submicro/micro-scaled spherical Sn–Ni–C alloy powders synthesized from oxides of Sn and Ni via carbothermal reduction at 900 °C were examined for use as anode materials in Li-ion battery. The synthesized spherical Sn–Ni–C particles show a loose micro-sized structure and a multi-phase composition. The reaction product carbon oxide gases yielded in the carbothermal reduction process should be responsible to the loose structure characteristics of Sn–Ni–C particles. The prepared Sn–Ni–C alloy composite electrode exhibits a stable reversible capacity of 310 mA h g−1 at constant current density of 100 mA g−1, and can be retained at 290 mA h g−1 after 25 cycles. The space existing in loose particle can accommodate the large volume changes during charge/discharge cycling. The ductile component Ni plays as a buffer to relieve the mechanical stress induced by the large volume changes upon cycling. The remained carbon can prevent the aggregation between small alloy particles. All these factors contribute greatly to the excellent cycling stability of Sn–Ni–C alloy electrode. This carbothermal reduction method is simple, cheap and mass-productive, thus suitable to large scale production of alloy anode powders used for lithium ion batteries.  相似文献   

13.
Cu was determined in a wide range of petroleum products from crude oil distillation using flame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICP-MS). Different procedures of sample preparation were evaluated: (i) mineralization with sulfuric acid in an open system, (ii) mineralization in a closed microwave system, (iii) combustion in hydrogen–oxygen flame in the Wickbold's apparatus, (iv) matrix evaporation followed by acid dissolution, and (v) acidic extraction. All the above procedures led to the transfer of the analyte into an aqueous solution for the analytical measurement step. It was found that application of FAAS was limited to the analysis of the heaviest petroleum products of high Cu content. In ICP-MS, the use of internal reference method (with Rh or In as internal reference element) was required to eliminate the matrix effects in the analysis of extracts and the concentrated solutions of mineralized heavy petroleum products. The detection limits (in original samples) were equal to, respectively, 10, 86, 3.3, 0.9 and 0.4 ng g 1 in procedures i–v with ETAAS detection and 10, 78, 1.1 and 0.5 ng g 1 in procedures i–iii and v with ICP-MS detection. The procedures recommended here were validated by recovery experiments, certified reference materials analysis and comparison of results, obtained for a given sample, in different ways. The Cu content in the analyzed samples was: 50–110 ng g 1 in crude oil, < 0.4–6 ng g 1 in gasoline, < 0.5–2 ng g 1 in atmospheric oil, < 6–100 ng g 1 in heavy vacuum oil and 140–300 ng g 1 in distillation residue.  相似文献   

14.
A heat-flow Calvet microcalorimeter was adapted for the measurement of sublimation enthalpies by the vacuum-drop method, with samples of masses in the range 1 mg to 5 mg. The electrically calibrated apparatus was tested by determining the enthalpies of sublimation of benzoic acid and ferrocene, at T =  298.15 K. The obtained results, ΔcrgHmo(C7H6O2)  =  (88.3  ±  0.5)kJ · mol  1and ΔcrgHmo(C10H10Fe) =  (73.3  ±  0.1)kJ · mol  1, are in excellent agreement with the corresponding values recommended in the literature. Subsequent application of the apparatus to the determination of the enthalpy of sublimation of η5-bis-pentamethylcyclopentadyenyl iron, at T =  298.15 K, led to ΔcrgHmo(C20H30Fe)  =  (96.8  ±  0.6)kJ · mol  1.  相似文献   

15.
Nano-sized insoluble iron, cobalt and nickel hexacyanoferrates (Mhcf) were prepared by a simple co-precipitation method. The potential of using these materials for supercapacitor was examined by cyclic voltammogram and constant charge/discharge. Due to the different types of the second metal (M), the Mhcf electrodes showed different electrochemical capacitive performances. The specific discharge capacitances of Fehcf, Nihcf and Cohcf electrodes at the current density of 0.2 A g−1 were 425 F g−1, 574.7 F g−1 and 261.56 F g−1, respectively. Meanwhile, the Mhcf electrodes showed good cyclic performance.  相似文献   

16.
Nano-sized nickel ferrite (NiFe2O4) was prepared by hydrothermal method at low temperature. The crystalline phase, morphology and specific surface area (BET) of the resultant samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and nitrogen physical adsorption, respectively. The particle sizes of the resulting NiFe2O4 samples were in the range of 5–15 nm. The electrochemical performance of NiFe2O4 nanoparticles as the anodic material in lithium ion batteries was tested. It was found that the first discharge capacity of the anode made from NiFe2O4 nanoparticles could reach a very high value of 1314 mAh g−1, while the discharge capacity decreased to 790.8 mAh g−1 and 709.0 mAh g−1 at a current density of 0.2 mA cm−2 after 2 and 3 cycles, respectively. The BET surface area is up to 111.4 m2 g−1. The reaction mechanism between lithium and nickel ferrite was also discussed based on the results of cycle voltammetry (CV) experiments.  相似文献   

17.
The Freundlich and Langmuir isotherms were used to describe the biosorption of Cu(II), Pb(II), and Zn(II) onto the saltbush leaves biomass at 297 K and pH 5.0. The correlation coefficients (R2) obtained from the Freundlich model were 0.9798, 0.9575, and 0.9963 for Cu, Pb, and Zn, respectively, while for the Langmuir model the R2 values for the same metals were 0.0001, 0.1380, and 0.0088, respectively. This suggests that saltbush leaves biomass sorbed the three metals following the Freundlich model (R2 > 0.9575). The KF values obtained from the Freundlich model (175.5 · 10−2, 10.5 · 10−2, and 6.32 · 10−2 mol · g−1 for Pb, Zn, and Cu, respectively), suggest that the metal binding affinity was in the order Pb > Zn > Cu. The experimental values of the maximal adsorption capacities of saltbush leaves biomass were 0.13 · 10−2, 0.05 · 10−2, and 0.107 · 10−2 mol · g−1 for Pb, Zn, and Cu, respectively. The negative ΔG values for Pb and the positive values for Cu and Zn indicate that the Pb biosorption by saltbush biomass was a spontaneous process.  相似文献   

18.
We calculated IR, nonresonance Raman spectra and vertical electronic transitions of the zigzag single-walled and double-walled boron nitride nanotubes ((0,n)-SWBNNTs and (0,n)@(0,2n)-DWBNNTs). In the low frequency range below 600 cm−1, the calculated Raman spectra of the nanotubes showed that RBMs (radial breathing modes) are strongly diameter-dependent, and in addition the RBMs of the DWBNNTs are blue-shifted reference to their corresponding one in the Raman spectra of the isolated (0,n)-SWBNNTs. In the high frequency range above ∼1200 cm−1, two proximate Raman features with symmetries of the A1g (∼1355 ± 10 cm−1) and E2g (∼1330 ± 25 cm−1) first increase in frequency then approach a constant value of ∼1365 and ∼1356 cm−1, respectively, with increasing tubes’ diameter, which is in excellent agreement with experimental observations. The calculated IR spectra exhibited IR features in the range of 1200–1550 cm−1 and in mid-frequency region are consistent with experiments. The calculated dipole allowed singlet–singlet and triplet–triplet electronic transitions suggesting a charge transfer process between the outer- and inner-shells of the DWBNNTs as well as, upon irradiation, the possibility of a system that can undergo internal conversion (IC) and intersystem crossing (ISC) processes, besides the photochemical and other photophysical processes.  相似文献   

19.
A continuous fixed bed (column) study was carried out by using seed husk of Bengal gram (Cicer arietinum) (SHBG) as a biosorbent for the removal of direct dye, Congo red (CR) from aqueous solutions. The effects of important factors, such as the value of initial pH, the flow rate, the influent concentration of CR, bed depth, particle size of SHBG, foreign ions and regeneration of CR were studied. The effect of similar type of direct dyes like direct turquoise blue 86 (DTB) and direct black 38 (DB) on the adsorption of CR in column containing SHBG is also studied by keeping other parameters constant. The studies confirmed that the breakthrough curves were dependent on flow rate, initial dye concentration, size of SHBG, initial pH of solution of CR and bed depth. The bed depth service time analysis (BDST) model was applied at different bed depths to predict the breakthrough curves. The model is found suitable for describing the biosorption process of the dynamic behaviour of the SHBG column and the data were in good agreement with BDST model. When the flow rate was 0.67 mL/min and the influent concentration of CR was mg L−1, the column capacity was 6.572 mg g−1. The removal capacity of SHBG was more in case of CR (6.572 mg g−1) compared to other similar direct dyes of DTB (1.984 mg g−1) and DB (1.612 mg g−1). The removal of CR was enhanced in the presence of foreign ion potassium (8.308 mg g−1) and decreased in the presence of calcium (5.58 mg g−1). 120 ml of acetone is required for the completion of regeneration of the column and the total amount of CR recovered in this case. All the results suggested SHBG as a potential adsorbent for removal of CR from aqueous solution so that the rate of bio-sorption process is rapid.  相似文献   

20.
The main aim of this study was to test the efficiency of biochar for Cu removal from synthetic and soil solutions, respectively.The biochar was produced from brewers draff via pyrolysis. Additionally, the prepared biochar was also activated using 2 M KOH to enhance its sorption efficiency to remove Cu from both solutions. Two different aqueous solutions were prepared for these experiments: (i) a synthetic using Cu-nitrate salt with 0.01 M NaNO3 and (ii) soil solution obtained from a Cu-contaminated soil using 0.01 M CaCl2 leaching procedure. Batch sorption and column experiments were used to evaluate the efficiency of both biochar (BC) and activated biochar (BCact) to remove Cu from the solutions.Results showed that both biochar samples are pure amorphous carbon and the Cu sorption is thus mainly a result of physical sorption on the biochar surface. Next, chemical activation, using 2 M KOH, significantly increased the total volume of all pores in biochar (from 0.01 ± 0.002 to 8.74 ± 0.18 mL g−1). On the other hand, the BET surface area was similar for both sorbents (BC = 9.80 ± 0.62 m2 g−1 and BCact = 11.6 ± 0.4 m2 g−1). Results also demonstrate enhanced sorption efficiency of the BCact (10.3 mg g−1) in comparison with the BC (8.77 mg g−1). Additionally, enhanced Cu removal during column retention test was observed for the BCact in both synthetic and soil solutions, respectively.In summary, the results showed that biochar prepared from brewers draff was able to remove Cu from both aqueous solutions.  相似文献   

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