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1.
Olivine LiFePO4/C nanocomposite cathode materials with small-sized particles and a unique electrochemical performance were successfully prepared by a simple solid-state reaction using oxalic acid and citric acid as the chelating reagent and carbon source. The structure and electrochemical properties of the samples were investigated. The results show that LiFePO4/C nanocomposite with oxalic acid (oxalic acid: Fe2+= 0.75:1) and a small quantity of citric acid are single phase and deliver initial discharge capacity of 122.1 mAh/g at 1 C with little capacity loss up to 500 cycles at room temperature. The rate capability and cyclability are also outstanding at elevated temperature. When charged/discharged at 60 °C, this materials present excellent initial discharge capacity of 148.8 mAh/g at 1 C, 128.6 mAh/g at 5 C, and 115.0 mAh/g at 10 C, respectively. The extraordinarily high performance of LiFePO4/C cathode materials can be exploited suitably for practical lithium-ion batteries.  相似文献   

2.
Hydration of zirconium diphosphate (ZrP2O7) conduced to formation of active sites in solid/liquid interface. In ZrP2O7/NaClO4 0.5 M suspensions, active sites and their acidity constants are quite determined but the presence of some impurities is now studied. This work was conducted to determine the surface properties changes produced by oxalic and citric acid during the hydration process. Moreover the presence of organic acids with ZrP2O7 modified reveals an increase in uranium sorption constants. The zirconium diphosphate has been characterized using X-ray powder diffraction (XRD), Scanning electron microscopy (SEM) and Particle induced X-ray emission and Neutron (PIXE). Furthermore, the specific surface area, measured by the BET method, was 3.5 m2/g. The pH corresponding to the isoelectric point, determined by Zeta Potential measurements and mass titration was 3.6. The sites density calculated using titration curves was around of 5.37 s/nm2 for NaClO4 0.5 M, 13.71 s/nm2 for NaClO4 0.5 M/citric acid 0.1 M and 7.33 s/nm2 NaClO4 0.5 M/oxalic acid 0.1 M. The surface acidity constants and species distribution in surface were calculated by means of simulation of the titration curves with the FITEQL code (constant capacitance model), for ZrO and PO amphoteric sites of ZrP2O7. The uranyl sorption edge was determined for NaClO4 0.5 M. It spreads between pH 3 and 4.5 for complete sorption according to the previously published results. In the ZrP2O7–citrate modified surface, the uranyl sorption edge begin at pH 2 and was almost complete at pH 3.2 while ZrP2O7–oxalate modified surface edge started at 50% of sorption at pH of 1.5 and was complete at pH 3.  相似文献   

3.
Activated carbon samples of different porosities and other characteristic features have been prepared using bituminous coal–KOH feedstocks of different degrees of pre-drying. The feedstocks were subjected to thermogravimetric analysis from 30 to 1000 °C. Different weight loss profiles and carbon burnt-off were obtained. This was associated with different level of potassium intercalations in the coal matrix and concomitant different extent of reactions with carbon. Another set of feedstocks was carbonized at 600 or 800 °C to obtain samples of activated carbon. The activated carbons were characterized using BET surface area, SEM, FTIR and XRD. These reflected the effects of pre-drying on the products. The surface area and Vmeso/Vmicro ratio increase with increase in duration of pre-drying. XRD profiles indicated lower proportion of aromatic stacking in the sample with highest surface area (1994 m2/g) and Vmeso/Vmicro ratio (0.91) than in the other samples. The pre-drying could be used as a key variable for obtaining activated carbons of different porosities.  相似文献   

4.
The macroporous Li3V2(PO4)3/C composite was synthesized by oxalic acid-assisted carbon thermal reaction, and the common Li3V2(PO4)3/C composite was also prepared for comparison. These samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and electrochemical performance tests. Based on XRD and SEM results, the sample has monoclinic structure and macroporous morphology when oxalic acid is introduced. Electrochemical tests show that the macroporous Li3V2(PO4)3/C sample has a high initial discharge capacity (130 mAh g−1 at 0.1 C) and a reversible discharge capacity of 124.9 mAh g−1 over 20 cycles. Moreover, the discharge capacity of the sample is still 91.5 mAh g−1, even at a high rate of 2 C, which is better than that of the sample with common morphology. The improvement in electrochemical performance should be attributed to its improved lithium ion diffusion coefficient for the macroporous morphology, which was verfied by cyclic voltammetry and electrochemical impedance spectroscopy.  相似文献   

5.
The objective of the study was to determine the effects of molecular sizes of amylose (AM) and starch granules on the mechanical properties of thermoplastic starch (TPS) blend films. Leached amylose solution from cassava (CS_ AM) and mung bean (MB_AM), and two forms of amylopectin (AP) (granular; g and non-granular; ng) of waxy cassava (WxCS) starch were used. Four types of film matrices were fabricated and all TPS blend films contained same amount of AM and glycerol. Results displayed that molecular weight profiles of starch films and presence of granule remnants significantly controlled the film matrix formation, types of crystal formation, and percent of relative crystallinity (%RC) (p < 0.05). Tensile property of TPS films was controlled by %RC and presence of granule remnants. Percent elongation at break (%Eb) of TPS films increased when the films had a large range of molecular weight distribution (from 5.5 × 107 g/mol to 0.4 × 105 g/mol) and contained a high weight fraction (~58%) of starch molecules with Mw~0.4 × 105 g/mol.  相似文献   

6.
Research on the effects of the pre-injected lye on the microstructure of the surrounding rock is indispensable for H2S treatment during tunnel construction. In this study, limestone samples from the Huangjiagou tunnel in Guizhou Province in southwest China were pre-adsorbed with 500 ppm of H2S and soaked in 1 %, 3 %, and 5 % Na2CO3 solution for 12, 24, and 36 h. The changes in the pore structure and mineral composition, and the secondary precipitates formed on the rock surface after Na2CO3 solution injection were studied by using N2 gas adsorption, X-ray diffraction, and field-emission scanning electron microscopy. It is clearly shown that the average volumes of micro- and meso-pores in the samples after treated decreased by 66.17 % and 16.63 %, respectively, of the original values. This resulted in a significant decrease in the specific surface area and total pore volume. The average pore width increased linearly with increasing Na2CO3 concentration or soaking time, whereas the curve for the relationship with the specific surface area was parabolic, with a minimum at a concentration of approximately 3 % and soaking time of 24 h. Clay (e.g., illite and kaolinite) and feldspar are more easily dissolved than other minerals, and the released metal ions easily form carbonate secondary precipitates with CO32? ions. The mass dissolution of clay minerals and the blocking effect of secondary precipitation decreases the amounts of micropores and mesopores of diameter less than 10 nm, therefore the proportion of macropores increases and the fractal dimensions are simpler. The results of this study will be useful in strategy development and parameter selection for Na2CO3 solution injection for H2S treatment in tunnel engineering.  相似文献   

7.
This paper describes a highly sensitive and selective electrochemical sensing of folic acid (FA) using vanadium pentoxide decorated graphene carbon nitride covalently grafted polyvinyl alcohol modified GC electrode (V2O5/G-C3N4/PVA/GCE). The V2O5/G-C3N4/PVA nanocomposite was synthesized by an in-situ oxidative polymerization method and characterized by various techniques such as UV–visible, Raman, FE-SEM, XRD, FT-IR, EDX, HR-TEM, SAED, and electrochemical methods. The V2O5/G-C3N4/PVA nanocomposite modified GCE showed superior electrocatalytic activity towards the FA detection. The superior electrochemical activity of the catalyst is owing to good conductivity, high surface area and enhanced electron transfer efficiency of the nanocomposite. The amperometric (i-t) studies revealed that the V2O5/G-C3N4/PVA nanocomposite modified GCE performed well by attaining a linear response of FA from 0.01 to 60 µM with a lower detection limit 0.00174 µM and the sensitivity of 19.02 μA µM−1 cm−2. Meanwhile, the V2O5/G-C3N4/PVA nanocomposite modified GCE exhibited good selectivity, rapid and stable response towards FA. The proposed method has been successfully applied for the selective determination of FA in various real samples such as apple juice, green tea and tap water with samples with good recoveries.  相似文献   

8.
The electrochemical properties of a glassy-carbon electrode modified with a polyvinylpyridine film with electrodeposited palladium were studied. Conditions were selected for preparing a composite film on a glassy-carbon surface. It was found that palladium particles deposited on the polyvinylpyridine film exhibited electrocatalytic activity in the oxidation of H2C2O4. Compared to an unmodified electrode, the oxidation potential of oxalic acid decreased and the current of its oxidation multiply increased. The catalytic current of oxalic acid oxidation was a linear function of its concentration in the range from 1 × 10–2 to 1 × 10–6 M.  相似文献   

9.
The production of oxalic acid by the catalytic oxidation of Douglas-fir (Psedotsuga menfiesii (Mirb) Franco) bark and subsequent pyrolysis of the residue to produce high density carbon pellets is discussed. Kinetic rate data are presented for oxalic acid production from Douglasfir bark. A maximum yield of 38 wt% oxalic acid has been obtained in 8 h at 80°C with 62.5 vol% HNO3 and 0.5 mg V2O5/g of bark. Additional oxalic acid can be produced by the conversion of pyrolytic oils and tars (obtained during carbonization of the residue) to increase the total yield to 45 wt%. An economic analysis based on the current cost of oxalic acid indicates the viability of the proposed process.  相似文献   

10.
In the present paper, we report the synthesis of tetrapropoxysilane (TPOS)-based silica aerogels with high surface area and large pore volume. The silica aerogels were prepared by a two-step sol-gel process followed by surface modification via a simple ambient pressure drying approach. In order to minimize drying shrinkage and obtain hydrophobic aerogels, the surface of the alcogels was modified using trichloromethylsilane as a silylating agent. The effect of the sol-gel compositional parameters on the polymerization of aerogels prepared by TPOS, one of the precursors belonging to the Si(OR)4 family, was reported for the first time. The oxalic acid and NH4OH concentrations were adjusted to achieve good-quality aerogels with high surface area, low density, and high transparency. Controlling the hydrolysis and condensation reactions of the TPOS precursor turned out to be the most important factor to determine the pore characteristics of the aerogel. Highly transparent aerogels with high specific surface area (938 m2/g) and low density (0.047 g/cm3) could be obtained using an optimized TPOS/MeOH molar ratio with appropriate concentrations of oxalic acid and NH4OH.  相似文献   

11.
In this paper, the disk-like and pumpkin-like hierarchical zeolite T aggregates consisted of primary nano-grains have been hydrothermally synthesized with and without the aid of the second template. The first template is used with tetramethylammonium hydroxide (TMAOH) and the second template is used with triethanolamine (TEA) or polyving akohol (PVA). A combination of characterization techniques, including XRD, SEM, TEM and N2 adsorption–desorption to examine the crystal crystallinity, morphology and surface properties of hierarchical zeolite T aggregates. In the single-template preparation process, the two-step varying-temperature treatment has been used to improve the meso-porosity of zeolite T aggregates. In the double-template preparation process, the amounts of PVA or TEA on the crystallinity, morphology and meso-porosity of zeolite T aggregates have been studied. It has been proved that the interstitial voids between the primary grains of aggregates are the origin of additional mesopores of samples. The micro- and meso-porosities of samples prepared with and without the second template have been contrasted in detail at last. In particular, the sample synthesized with the addition of PVA presents a hierarchical pore structure with the highest Sext value of 122 m2/g and Vmeso value of 0.255 cm3/g.  相似文献   

12.
Micro–mesoporous materials combining the structural and sorption characteristics of a mesoporous molecular sieve (MMS) and zeolite BEA were obtained by the “dry gel conversion” method – partial zeolitization of silica MMS SBA-15 in the presence of tetraethylammonium hydroxide. The volume of the mesopores reaches 0.65 cm3/g, while that of the micropores is in the region of 0.1 cm3/g. The acidity of the obtained zeolitized materials differs from that of BEA; the total concentration of medium-strength acid centers (maximum thermal desorption of ammonia at ~315 °C) amounts to 0.15 mmol/g.  相似文献   

13.
Farzana Akter K  Chen Z  Smith L  Davey D  Naidu R 《Talanta》2005,68(2):406-415
The performance of capillary electrophoresis-ultraviolet detector (CE-UV), hydride generation-atomic absorption spectrometry (HG-AAS) and liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) have been compared for the speciation of arsenic (As) in groundwater samples. Two inorganic As species, arsenite (AsIII), arsenate (AsV) and one organo species dimethyl arsenic acid (DMA) were mainly considered for this study as these are known to be predominant in water. Under optimal analytical conditions, limits of detection (LD) ranging from 0.10 (AsIII, AsT) to 0.19 (DMA) μg/l for HG-AAS, 100 (AsIII, DMA) to 500 (AsV) μg/l for CE-UV and 0.1 (DMA, MMA) to 0.2 (AsIII, AsV) μg/l for LC-ICP-MS, allowed the determination of the above three species present in these samples. Results obtained by all the three methods are well correlated (r2 = 0.996*** for total As) with the precision of <5% R.S.D. except CE-UV. The effect of interfering ions (e.g. Fe2+, Fe3+, SO42− and Cl) commonly found in ground water on separation and estimation of As species were studied and corrected for. Spike recovery was tested and found to be 80-110% at 0.5 μg/l As standard except CE-UV where only 50% of the analyte was recovered. Comparison of these results shows that LC-ICP-MS is the best choice for routine analysis of As species in ground water samples.  相似文献   

14.
In this study, different polyanilines were synthesized and evaluated for the determination of three hormones, including 17-β-estradiol, 17-α-ethinylestradiol, and estrone, in urine using a novel methodology based on thin film solid-phase microextraction technique, employing the sampling well plate system. The extractor phases, designated as polyaniline doped with hydrochloric acid, polyaniline doped with oxalic acid, polyaniline-silica doped with hydrochloric acid, and polyaniline-silica doped with oxalic acid, were characterized by electrical conductivity measurements, scanning electron microscopy, and Fourier transform infrared spectroscopy. The optimized extraction conditions were composed of 1.5 mL of urine and pH adjusted to 10, with no need to dilute sample and the desorption step, 300 μL of acetonitrile was used. The calibration curves were performed in the sample matrix, with detection and quantification limits ranged from 0.30 to 3.03 μg L−1 and from 1.0 to 10.0 μg L−1, respectively, with r ≥ 0.9969. The relative recoveries ranged from 71% to 115%, and intraday precision showed values ≤12% and interday ≤20%. The applicability of the method was successfully evaluated, and six urine samples from female volunteers were analyzed. The analytes were not detected or were below the limits of quantification in these samples.  相似文献   

15.
A single-column ion chromatography (SCIC) for the simultaneous determination of alkali, alkaline earth and transition metal elements in UO2, ThO2 powders and sintered (Th, U) O2 pellet is described in this paper. Metrosep cation 1-2 analytical column containing poly butadiene-maleic acid (PBDMA) coated silica has been applied to the ion chromatographic separation of 12 cations (copper, lithium, sodium, ammonium, nickel, potassium, zinc, cobalt, manganese, magnesium, calcium and strontium) using an isocratic elution with tartaric acid and oxalic acid as mobile phase with non-suppressed conductivity detection. Mobile phase composition was optimized to 1 mM tartaric acid and 0.75 mM oxalic acid for the baseline separation of 12 cations. The calibration plots were linear in the range of 0.05–40 mg L−1 with regression coefficients better than 0.998. The relative standard deviations (RSDs) of the retention time, peak area and peak height were less than 1, 2.8 and 3.0%, respectively. The recoveries of the spiked samples for the cations were 94–110%. The method developed was validated by comparison with certified standards of UO2 and ThO2 powders.  相似文献   

16.
Dou  Junqing  Kang  Xueya  Wumaier  Tuerdi  Hua  Ning  Han  Ying  Xu  Guoqing 《Journal of Solid State Electrochemistry》2012,16(5):1925-1931
LiFePO4/C composite is synthesized by oxalic acid-assisted rheological phase method. Fe2O3 and LiH2PO4 are chosen as the starting materials, sucrose as carbon sources, and oxalic acid as the additive. The crystalline structure and morphology of the products are characterized by X-ray diffraction and field emission scanning electron microscopy. The charge–discharge kinetics of LiFePO4 electrode is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. It is found that the introduction of appropriate amount of oxalic acid leads to smaller particle sizes, more homogeneous size distribution, and some Fe2P produced in the final products, resulting in reduced polarization, impedance, and improved Li+ ion diffusion coefficient. The best cell performance is delivered by the sample with R = 1.5 (R of the molar ratio of oxalic acid to LiH2PO4). Its discharge capacity is 154 mAh g−1 at 0.2 C rate and 120 mAh g−1 at 5.0 C rate. At the same time, it exhibits an excellent cycling stability; no obvious decrease even after 1,000 cycles at 1.0 C rate.  相似文献   

17.
The production of extracellular and mycelia-associated penicillin G acylase (maPGA) with Mucor griseocyanus H/55.1.1 by surface-adhesion fermentation using Opuntia imbricata, a cactus, as a natural immobilization support was studied. Enzyme activity to form 6-aminopencillanic acid (6-APA) from penicillin G was assayed spectrophotometrically. The penicillin G hydrolysis to 6-APA was evaluated at six different times using PGA samples recovered from the skim milk medium at five different incubation times. Additionally, the effect of varying the penicillin G substrate concentration level on the PGA enzyme activity was also studied. The maximum reaction rate, V max, and the Michaelis constant, K M, were determined using the Michaelis–Menten model. The maximum levels for maPGA and extracellular activity were found to be 2,126.50 international unit per liter (IU/l; equal to 997.83 IU/g of support) at 48 h and 755.33 IU/l at 60 h, respectively. Kinetics of biomass production for total biomass showed a maximum growth at 60 h of 3.36 and 2.55 g/l (equal to 0.012 g of biomass per gram of support) for the immobilized M. griseocyanus biomass. The maPGA was employed for the hydrolysis of penicillin G to obtain 6-APA in a batch reactor. The highest quantity of 6-APA obtained was 226.16 mg/l after 40-min reaction. The effect of substrate concentration on maPGA activity was evaluated at different concentrations of penicillin G (0–10 mM). K M and V max were determined to be 3.0 × 10−3 M and 4.4 × 10−3 mM/min, respectively.  相似文献   

18.
This study investigated the occurrence of tetracyclines (TCs), namely minocycline (MIN), TC, and its epimer epitetracycline (ETC), and doxycycline (DC), in four hospital wastewater effluents and its fate in municipal wastewater treatment plants (WWTPs), in Coimbra, Portugal. Analytical determination was carried out by solid-phase extraction followed by liquid chromatography with fluorescence detection. A gradient system with a mobile phase containing oxalic acid 0.02 M and acetonitrile was used. After postcolumn derivatization with magnesium reagent, TCs were detected at λ exc 386 nm and λ em 500 nm. The proposed method allowed good sensitivity, accuracy, and precision. LOQs were 0.5 μg l−1 for ETC and TC and 15 and 5 μg l−1 for MIN and DC, respectively. The recovery values ranged between 66.4% and 117.1%, and intraday and interday repeatability was lower than 6.8%. The method was successfully used to determine the presence of the above-mentioned TCs in 24 wastewater composite samples obtained from hospital effluents and from influent and effluent of the WWTP located in Coimbra, Portugal. MIN and TC were found in 41.7% of the samples; ETC and DC were found in 25% and 8.3% of the samples, respectively. The levels found ranged from 6 to 531.7 μg l−1 in hospital effluents, while its concentrations in WWTP ranged from 95.8 to 915.3 μg l−1. A seasonal influence in the concentrations found has also been observed, the levels found in samples collected during spring being higher than those observed in samples collected during autumn; however, these are only preliminary results. The WWTP removal rate ranged between 89.5% and 100%.  相似文献   

19.
The synthesis, spectroscopic, and electrochemical properties of seven new PVmeso‐triarylcorroles ( 1 – 7 ) are reported. Compounds 1 – 7 were prepared by heating the corresponding free‐base corroles with POCl3 at reflux in pyridine. Hexacoordinate PV complexes of meso‐triarylcorroles were isolated that contained two axial hydroxy groups, unlike the PV complex of 8,12‐diethyl‐2,3,7,13,17,18‐hexamethylcorrole, which was pentacoordinate, or the PV complex of meso‐tetraphenylporphyrin, which was hexacoordinate with two axial chloro groups. 1H and 31P NMR spectroscopy in CDCl3 indicated that the hexacoordinated PVmeso‐triarylcorroles were prone to axial‐ligand dissociation to form pentacoordinated PVmeso‐triarylcorroles. However, in the presence of strongly coordinating solvents, such as CH3OH, THF, and DMSO, the PVmeso‐triarylcorroles preferred to exist in a hexacoordinated geometry in which the corresponding solvent molecules acted as axial ligands. X‐ray diffraction of two complexes confirmed the hexacoordination environment for PVmeso‐triarylcorroles. Their absorption spectra in two coordinating solvents revealed that PVmeso‐triarylcorroles showed a strong band at about 600 nm together with other bands, in contrast to PV–porphyrins, which showed weak bands in the visible region. These compounds were easier to oxidize and more difficult to reduce compared to PV–porphyrins. These compounds were brightly fluorescent, unlike the weakly fluorescent PV–porphyrins, and the quantum yields for selected PV–corroles were as high as AlIII and GaIII corroles, which are the best known fluorescent compounds among oligopyrrolic macrocycles.  相似文献   

20.
meso-2,3-Butanediol (meso-2,3-BDO) is essential for the synthesis of various economically valuable biosynthetic products; however, the production of meso-2,3-BDO from expensive carbon sources is an obstacle for industrial applications. In this study, genes involved in the synthesis of 2,3-BDO in Klebsiella pneumoniae were identified and used to genetically modify Escherichia coli for meso-2,3-BDO production. Two 2,3-BDO biosynthesis genes—budA, encoding acetolactate, and meso-budC, encoding meso-SADH—from K. pneumoniae were cloned into the pUC18 plasmid and introduced into E. coli. In 2 l batch culture, the SGSB03 E. coli strain yielded meso-2,3-BDO at 0.31 g/gglucose (with a maximum of 15.7 g/lculture after 48 h) and 0.21 g/gcrude glycerol (with a maximum of 6.9 g/lculture after 48 h). Batch cultures were grown under optimized conditions (aerobic, 6% carbon source, 37 °C, and initial pH 7). To find the optimal culture conditions for meso-2,3-BDO production, we evaluated the enzyme activity of meso-SADH and the whole cell conversion yield (meso-2,3-BDO/acetoin) of the E. coli SGSB02, which contains pSB02. meso-SADH showed high enzyme activity at 30–37 °C and pH 7 (30.5–41.5 U/mg of protein), and the conversion yield of SGSB02 E. coli was highest at 37–42 °C and a pH of 7 (0.25–0.28 g meso-2,3-BDO/gacetoin).  相似文献   

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