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1.
Because stabilization of arsenite in water samples during transit and storage is troublesome, this work deals with a method to prevent this by on-site selective coprecipitation of arsenite with dibenzyldithiocarbamate and recovery of the coprecipitate by filtration through a 0.45-μm membrane filter. In the laboratory arsenic on the filter is quantitatively released by oxidation of arsenite to arsenate with H2O2 (6%) in alkaline medium (8 mmol L–1 NaOH) at elevated temperature (85?°C) for 30 min followed by ultratrace determination by routine HGAFS and ICP–MS. It is shown that arsenate contamination of the coprecipitate is so low that arsenate concentrations three orders of magnitude higher than the arsenite concentration do not interfere; this is essential, because arsenate is usually the dominant arsenic species in water. Because significant preconcentration can be achieved in the solution obtained from the leached filter (normally a factor 20 but easily increased to 100) very low detection limits can be obtained (only limited by the purity of the materials and the cleanliness of working); a realistic limit of determination is 0.01 μg L–1 arsenite. The procedure was used for the determination of arsenite in two ground waters from an ash depository site in the ?alek valley (Slovenia). The matrix contained some elements at very high levels but this did not impair the efficiency of arsenite coprecipitation. The results obtained by use of HGAFS and ICP–MS were not significantly different at the 5% level for sub-μg L–1 arsenite concentrations.  相似文献   

2.
The competitive sorption of carbonate and arsenic to hematite was investigated in closed-system batch experiments. The experimental conditions covered a pH range of 3-7, arsenate concentrations of 3-300 μM, and arsenite concentrations of 3-200 μM. Dissolved carbonate concentrations were varied by fixing the CO(2) partial pressure at 0.39 (atmospheric), 10, or 100 hPa. Sorption data were modeled with a one-site three plane model considering carbonate and arsenate surface complexes derived from ATR-FTIR spectroscopy analyses. Macroscopic sorption data revealed that in the pH range 3-7, carbonate was a weak competitor for both arsenite and arsenate. The competitive effect of carbonate increased with increasing CO(2) partial pressure and decreasing arsenic concentrations. For arsenate, sorption was reduced by carbonate only at slightly acidic to neutral pH values, whereas arsenite sorption was decreased across the entire pH range. ATR-FTIR spectra indicated the predominant formation of bidentate binuclear inner-sphere surface complexes for both sorbed arsenate and sorbed carbonate. Surface complexation modeling based on the dominant arsenate and carbonate surface complexes indicated by ATR-FTIR and assuming inner-sphere complexation of arsenite successfully described the macroscopic sorption data. Our results imply that in natural arsenic-contaminated systems where iron oxide minerals are important sorbents, dissolved carbonate may increase aqueous arsenite concentrations, but will affect dissolved arsenate concentrations only at neutral to alkaline pH and at very high CO(2) partial pressures.  相似文献   

3.
Partially graphitized ordered mesoporous carbons have been prepared with a soft template method using low-molecular-weight phenolic resol as a carbon source, triblock copolymer F127 as a template, and ferric citrate as a graphitization catalyst. N2 sorption and transmission electron microscopy analysis show that the ordered mesoporous carbons have been partially graphitized when the carbonization temperature is above 700 °C. The graphitic ordered mesoporous carbons exhibit better rate performance than amorphous ordered mesoporous carbons. The specific capacitance of the graphitic ordered mesoporous carbons (GOMCs) prepared at 700 °C reaches to 112 F g?1 at a scan rate of up to 1,000 mV s?1. Its capacitance retention ratio is 64 %, which is much higher than that of the amorphous ordered mesoporous carbons prepared at 600 °C (33 %). High electronic conductivity and ordered mesoporous structure lead to the high electrochemical performance of the partially graphitized ordered mesoporous carbons.  相似文献   

4.
Batch experiments were conducted on aqueous solutions containing arsenite, arsenobetaine, methylarsonic acid or phenylarsonic acid in contact with natural zeolites to examine their interaction. The concentration of the arsenic species in the liquid phase at equilibrium before and after contact was measured by means of liquid chromatography coupled with inductively coupled plasma mass spectrometry detection. Clinoptilolites completely removed arsenobetaine from the solution and the resulting amounts of dimethylarsinic acid were detected. The methylarsonic acid maximum concentration diminution was reached at a mass—to volume V value of m/V = 0.2. Phenylarsonic acid solution decreased its concentration 75% after treatment with clinoptilolites. Untreated mordenites in contact with arsenite solutions led to the formation of arsenate, whereas acid‐washed mordenites practically removed arsenobetaine and were less effective for methylarsonic acid. To show the incompatibility of molecular dimensions with the zeolite windows, the molecular parameters of surface area, molecular volume, molecular length, and the width and depth of arsenite, arsenate and a series of ten organic arsenic compounds were calculated. Since sorption onto the external zeolite surface rather than a sieve process defined the interaction, an acid‐catalysed reaction mechanism is proposed to explain the transformation results. Copyright © 2001 John Wiley & Sons, Ltd.  相似文献   

5.
Highly ordered mesoporous C60 with a well‐ordered porous structure and a high crystallinity is prepared through the nanohard templating method using a saturated solution of C60 in 1‐chloronaphthalene (51 mg mL?1) as a C60 precursor and SBA‐15 as a hard template. The high solubility of C60 in 1‐chloronaphthalene helps not only to encapsulate a huge amount of the C60 into the mesopores of the template but also supports the oligomerization of C60 and the formation of crystalline walls made of C60. The obtained mesoporous C60 exhibits a rod‐shaped morphology, a high specific surface area (680 m2 g?1), tuneable pores, and a highly crystalline wall structure. This exciting ordered mesoporous C60 offers high supercapacitive performance and a high selectivity to H2O2 production and methanol tolerance for ORR. This simple strategy could be adopted to make a series of mesoporous fullerenes with different structures and carbon atoms as a new class of energy materials.  相似文献   

6.
Arsenite oxidation and arsenate determination by the molybdene blue method   总被引:3,自引:0,他引:3  
Based on the similarity in properties of arsenate and phosphate, the colorimetric method using the molybdene blue complex was tested in order to determine low As(V) concentration in waters. The influence of complex formation time, daylight, temperature and competitive anions (silicate and sulphate) upon complex formation was determined. Optimal complex formation was reached in 1 h at 20±1 °C and was slightly favoured when developed in daylight. The formation rate declined with decreasing reaction temperature and no influence of any of the competitive anions tested (at concentrations usually found in natural waters of granitic areas) was noted. The detection limit of this method was 20 μg As(V) l−1. This simple, fast and sensitive arsenic determination method is suitable for field analysis, especially for waters containing low levels of phosphate and organic matter. Through arsenate determination, this colorimetric method allowed the arsenite oxidation efficiency of five common industrial oxidants to be compared. H2O2 and MnO2(s) were not considered as effective oxidants as a high excess was necessary to ensure As(III) oxidation. NaOCl and KMnO4 were promising oxidants as they allowed complete arsenite oxidation with a small excess for NaOCl or even less than the electron stoichiometric ratio in the case of KMnO4. FeCl3 was the most effective oxidant among the reagents tested here.  相似文献   

7.
Mesoporous silica KIT-6 has novel three-dimensional gyroidal channel structure, space group of 1a-3d, and ordered tunable pores up to 10 nm. In this paper, such mesostructured silica was employed as hard template to prepare semicrystalline gyroidal mesoporous MnO2. The structure was investigated by XRD, TEM and HRTEM, and found to be of high quality 1a-3d symmetry, in good accordance with the template structure. The material has a BET surface of 118 m2·g^-1 and pore volume of 0.35 cm3·g^- 1 after eliminating template. Mesoporous MnO2 has shown good electrochemical property as supercapacitor material in 1 mol·L^-1 Na2SO4 and 1 mol·L^-1 LiClO4 solutions, but interesting pseudocapacitance behavior was observed in the case of 6 mol·L^-1 KOH. It was found that mesoporous MnO2 performed stable reversible electrochemical behavior with capacitance of 220 F·g^-1 in a potential range of -0.1-0.55 V vs. Hg/HgO in alkaline solution, demonstrating that it is a promising novel electrode material for the fabrication of electrochemical capacitors.  相似文献   

8.
Bead cellulose loaded with iron oxyhydroxide (BCF) with 47 mass% Fe content was prepared and was successfully applied to the elimination of arsenic from aqueous solutions. A clearer understanding of the arsenic removal mechanism will provide accurate prediction of the arsenic adsorptive properties of the new adsorbent. To study the mechanism of the adsorption process, we measured the extended X-ray absorption fine structure (EXAFS) spectra of arsenite and arsenate sorbed onto the adsorbent with different surface coverages. Both arsenite and arsenate were strongly and specifically adsorbed by akaganéite adsorptive centers on BCF by an inner-sphere mechanism. There was no change in oxidation state following interaction between the arsenic species and the BCF surface. The dominant complex of arsenic species adsorbed on akaganéite was bidentate binuclear corner-sharing ((2)C) between As(V) tetrahedra (or As(III) pyramids) and adjacent edge-sharing FeO(6) octahedra. On the basis of the results from EXAFS spectra, the adsorptive characteristics of arsenic, such as the effects of pH and competing anions, were satisfactorily interpreted.  相似文献   

9.
Pooled livers and pooled kidneys from rats or mice were homogenized and spiked with arsenite or arsenate in the concentration range 1.3–20 μmol dm?3. Methylarsenic and dimethylarsenic compounds were determined by the hydride generation technique in the homogenates after a 90 min incubation at 37°C. The rat homogenates methylated arsenite and arsenate more efficiently than the mouse homogenates. Monomethylated arsenic was present in larger amounts than dimethylated arsenic in the rat homogenates. In the absence of reduced glutathione (GSH), no methylation occurred. Addition of GSH promoted monomethylation and dimethylation, whereas dithiothreitol and mercaptoethanol (10 mmol dm?3) fostered only monomethylation. The amounts of monomethylated arsenic in the rat liver homogenates increased with increasing arsenite concentration (1.3–20 μmol dm?3) however, the percentage of arsenic that had been methylated decreased. A similar trend, but with much less monomethylarsenic formed, was observed for arsenate-spiked homogenates. Rat kidney homogenates methylated arsenite and arsenate to a much smaller extent than rat liver homogenates. The Km values for the monomethylation in rat liver homogenates were found to be 5.3 μmol dm?3 for arsenite and 59 μmol dm?3 for arsenate.  相似文献   

10.
A meostructured WO3/C composite with crystalline framework and high electric conductivity has been synthesized by a new in situ carbonization–replication route using the block copolymer (poly(ethylene glycol)‐block‐poly(propylene glycol)‐block‐poly(ethylene glycol)) present in situ in the pore channels of mesoporous silica template as carbon source. X‐ray diffraction, X‐ray photoelectron spectroscopy, transmission electron microscopy, thermogravimetry differential thermal analysis, and N2 adsorption techniques were adopted for the structural characterization. Cyclic voltammetry, chronoamperometry, and single‐cell test for hydrogen electrochemical oxidation were adopted to characterize the electrochemical activities of the mesoporous WO3/C composite. The carbon content and consequent electric conductivity of these high‐surface‐area (108–130 m2 g?1) mesostructured WO3/C composite materials can be tuned by variation of the duration of heat treatment, and the composites exhibited high and stable electrochemical catalytic activity. The single‐cell test results indicated that the mesostructured WO3/C composites showed clear electrochemical catalytic activity toward hydrogen oxidation at 25 °C, which makes them potential non‐precious‐metal anode catalysts in proton exchange membrane fuel cell.  相似文献   

11.
A novel synthesis method for ordered mesoporous carbons is presented. The inverse replication of a silica template was achieved using the carbonization of sucrose within mesoporous KIT‐6. Instead of liquid acid etching, as in classical nanocasting, a novel dry chlorine etching procedure for template removal is presented for the first time. The resultant ordered mesostructured carbon material outperforms carbons obtained by conventional hard templating with respect to high specific micro‐ and mesopore volumes (0.6 and 1.6 cm3 g?1, respectively), due to the presence of a hierarchical pore system. A high specific surface area of 1671 m2 g?1 was achieved, rendering this synthesis route a highly convenient method to produce ordered mesoporous carbons.  相似文献   

12.
An ordered mesoporous WO3 material with a highly crystalline framework was synthesized by using amphiphilic poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymers as a structure‐directing agent through a solvent‐evaporation‐induced self‐assembly method combined with a simple template‐carbonization strategy. The obtained mesoporous WO3 materials have a large uniform mesopore size (ca. 10.9 nm) and a high surface area (ca. 121 m2 g?1). The mesoporous WO3‐based H2S gas sensor shows an excellent performance for H2S sensing at low concentration (0.25 ppm) with fast response (2 s) and recovery (38 s). The high mesoporosity and continuous crystalline framework are responsible for the excellent performance in H2S sensing.  相似文献   

13.
A new asymmetric capacitor concept is proposed providing high energy storage capacity for only one charging direction. Size‐selective microporous carbons (w<0.9 nm) with narrow pore size distribution are demonstrated to exclusively electrosorb small anions (BF4?) but size‐exclude larger cations (TBA+ or TPA+), while the counter electrode, an ordered mesoporous carbon (w>2 nm), gives access to both ions. This architecture exclusively charges in one direction with high rectification ratios (RR=12), representing a novel capacitive analogue of semiconductor‐based diodes (“CAPode”). By precise pore size control of microporous carbons (0.6 nm, 0.8 nm and 1.0 nm) combined with an ordered mesoporous counter electrode (CMK‐3, 4.8 nm) electrolyte cation sieving and unidirectional charging is demonstrated by analyzing the device charge‐discharge response and monitoring individual electrodes of the device via in situ NMR spectroscopy.  相似文献   

14.
The facile synthesis of a porous carbon material that is doped with iron‐coordinated nitrogen active sites (FeNC‐70) is demonstrated by following an inexpensive synthetic pathway with a zeolitic imidazolate framework (ZIF‐70) as a template. To emphasize the possibility of tuning the porosity and surface area of the resulting carbon materials based on the structure of the parent ZIF, two other ZIFs, that is, ZIF‐68 and ZIF‐69, are also synthesized. The resulting active carbon material that is derived from ZIF‐70, that is, FeNC‐70, exhibits the highest BET surface area of 262 m2 g?1 compared to the active carbon materials that are derived from ZIF‐68 and ZIF‐69. The HR‐TEM images of FeNC‐70 show that the carbon particles have a bimodal structure that is composed of a spherical macroscopic pore (about 200 nm) and a mesoporous shell. X‐ray photoelectron spectroscopy (XPS) reveals the presence of Fe‐N‐C moieties, which are the primary active sites for the oxygen‐reduction reaction (ORR). Quantitative estimation by using EDAX analysis reveals a nitrogen content of 14.5 wt. %, along with trace amounts of iron (0.1 wt. %), in the active FeNC‐70 catalyst. This active porous carbon material, which is enriched with Fe‐N‐C moieties, reduces the oxygen molecule with an onset potential at 0.80 V versus NHE through a pathway that involves 3.3–3.8 e? under acidic conditions, which is much closer to the favored 4 e? pathway for the ORR. The onset potential of FeNC‐70 is significantly higher than those of its counterparts (FeNC‐68 and FeNC‐69) and of other reported systems. The FeNC‐based systems also exhibit much‐higher tolerance towards MeOH oxidation and electrochemical stability during an accelerated durability test (ADT). Electrochemical analysis and structural characterizations predict that the active sites for the ORR are most likely to be the in situ generated N? FeN2+2/C moieties, which are distributed along the carbon framework.  相似文献   

15.
Flow injection analysis (FIA) and high-performance liquid chromatography double-focusing sector field inductively coupled plasma mass spectrometry (HPLC-DF-ICP-MS) were used for total arsenic determination and arsenic speciation of xylem sap of cucumber plants (Cucumis sativus L.) grown in hydroponics containing 2 μmol dm−3 arsenate or arsenite, respectively. Arsenite [As(III)], arsenate [As(V)] and dimethylarsinic acid (DMA) were identified in the sap of the plants. Arsenite was the predominant arsenic species in the xylem saps regardless of the type of arsenic treatment, and the following concentration order was determined: As(III) > As(V) > DMA. The amount of total As, calculated taking into consideration the mass of xylem sap collected, was almost equal for both treatments. Arsenite was taken up more easily by cucumber than arsenate. Partial oxidation of arsenite to arsenate (<10% in 48 h) was observed in the case of arsenite-containing nutrient solutions, which may explain the detection of arsenate in the saps of plants treated with arsenite.  相似文献   

16.
Molybdenum disulfide (MoS2) is a promising candidate as a high‐performing anode material for sodium‐ion batteries (SIBs) due to its large interlayer spacing. However, it suffers from continued capacity fading. This problem could be overcome by hybridizing MoS2 with nanostructured carbon‐based materials, but it is quite challenging. Herein, we demonstrate a single‐step strategy for the preparation of MoS2 coupled with ordered mesoporous carbon nitride using a nanotemplating approach which involves the pyrolysis of phosphomolybdic acid hydrate (PMA), dithiooxamide (DTO) and 5‐amino‐1H‐tetrazole (5‐ATTZ) together in the porous channels of 3D mesoporous silica template. The sulfidation to MoS2, polymerization to carbon nitride (CN) and their hybridization occur simultaneously within a mesoporous silica template during a calcination process. The CN/MoS2 hybrid prepared by this unique approach is highly pure and exhibits good crystallinity as well as delivers excellent performance for SIBs with specific capacities of 605 and 431 mAhg?1 at current densities of 100 and 1000 mAg?1, respectively, for SIBs.  相似文献   

17.
Due to the excellent biocompatibility and the capability to load and release drugs, ordered mesoporous carbons (OMCs) have been highly prospective and valuable in drug delivery system. In this contribution, synthesis of OMCs with tailored pore sizes from 4.1 to 3.4 nm was achieved by employing SBA‐15 as template and furfuryl alcohol (FA) as carbon precursors. An array of OMCs with controlled structures and morphologies by incipient wetness with FA was analyzed by powder X‐ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), and Raman spectroscopy. The resulting carbon replicas retained the hexagonal symmetry of the silica templates SBA‐15 with p6mm space group, although the framework suffered shrinkage in the replicated process. The pore size distribution, uniformity and pore volume of the mesopores in the OMCs were affected by structural properties of the SBA‐15 templates as shown by N2 sorption and XRD pattern analysis. The process had the advantage that the textural parameters of the obtained OMCs were tunable simply by varying aging temperature of the silica template and the ratio of carbon precursor.  相似文献   

18.
Chlorella vulgaris was cultivated in a growth medium containing arsenate concentration of <0.01, 10, 100 and 1000 mg l?1. Illumination was carried out in 12 h cycles for 5 days. The health status of the culture was monitored by continuous pH and dissolved oxygen (DO) readings. Destructive sampling was used for the determination of biomass, chlorophyll, total arsenic and arsenic species. The chlorophyll a content, the DO and pH cycles were not significantly different for the different arsenate concentrations in the culture. In contrast, biomass production was significantly (p < 0.05) increased for the arsenic(V) treatment at 1000 mg l?1 compared with 100 mg l?1. The arsenic concentration in the algae increased with the arsenate concentration in the culture. However, the bioconcentration factor decreased a hundred‐fold with increase of arsenate from the background level to 1000 mg l?1. The arsenic species were identified by using strong anion‐exchange high‐performance liquid chromatography–inductively coupled plasma mass spectrometry analysis after methanol/water (1 : 1) extraction. The majority (87–100%) of the extractable arsenic was still arsenate; arsenite was found to be between 1 and 6% of total extractable arsenic in the algae. In addition to dimethylarsinic acid, one unknown arsenical (almost co‐eluting with methylarsonic acid) and three different arsenosugars have been identified for the first time in C. vulgaris growing in a culture containing a mixture of antibiotics and believed to be axenic. The transformation to arsenosugars in the algae is not dependent on the arsenate concentration in the culture and varies between 0.2 and 5% of total accumulated arsenic. Although no microbiological tests for bacterial contamination were made, this study supports the hypothesis that algae, and not associated bacteria, produce the arsenosugars. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

19.
In this work three mild extraction agents for determination of plant-available fractions of elements in soil were evaluated for arsenic speciation in soil samples. Pepper (Capsicum annum, L.) var. California Wonder was cultivated in pots, and aqueous solutions of arsenite, arsenate, methylarsonic acid, and dimethylarsinic acid, at a concentration of 15 mg As kg–1 soil, were added at the beginning of the experiment. Control pots (untreated) were also included. Deionized water, 0.01 mol L–1 CaCl2, and 0.05 mol L–1 (NH4)2SO4 were used to extract the plant-available fraction of the arsenic compounds in soil samples collected during the vegetation period of the plants. Whereas in control samples the extractable arsenic fraction did not exceed 1% of total arsenic content, soil amendment by arsenic compounds resulted in extraction of larger amounts, which varied between 1.4 and 8.1% of total arsenic content, depending on soil treatment and on the extracting agent applied. Among arsenic compounds determined by HPLC–ICPMS arsenate was predominant, followed by small amounts of arsenite, methylarsonic acid, and dimethylarsinic acid, depending on the individual soil treatment. In all the experiments in which methylarsonic acid was added to the soil methylarsonous acid was detected in the extracts, suggesting that the soil bacteria are capable of reducing methylarsonic acid before a further methylation occurs. No significant differences were observed between analytical data obtained by using different extraction procedures.  相似文献   

20.
An improvement in the photodegradation performance for dyes due to interaction between carbon and titania in a self‐assembled mesoporous C? TiO2 composite catalyst, even for the difficult degradation of azo dyes, is reported herein. The dye removal process involves adsorption of the dye from water by the mesoporous carbon–titania, followed by photodegradation on the separated dye‐loaded solid. Such adsorption–catalysis cycles can be carried out more than 80 times without discernible loss of photocatalytic activity or the anatase content of the composite. In each run, about 120 mg dye per g catalyst can be degraded. The mesoporous carbon–titania catalyst also exhibits a high capacity for converting methyl orange in aqueous solution under visible light. Characterization by XRD, TEM, and N2 sorption techniques has revealed that the self‐assembled composite catalyst has an ordered mesostructure, uniform mesopores (4.3 nm), a large pore volume (0.30 cm3 g?1), and a high surface area (348 m2 g?1). The pore walls are composed of amorphous carbon and anatase nanoparticles of size 4.2 nm, which are well dispersed and confined. X‐ray photoelectron spectroscopy (XPS), surface photovoltage spectroscopy (SPS), and UV/Vis absorption results indicate doping of carbon into the anatase lattice and a change in the bandgap of the semiconductor. The synergistic improvement in the composite catalyst can be attributed to the following features: (1) carbon doping of the anatase lattice modifies its bandgap and enhances its activity under visible light; (2) confinement within carbon pore walls prevents aggregation of tiny anatase nanoparticles, improving their activity and stability; (3) the mesopores provide a confined space for photocatalysis; and (4) the strong adsorption ability of porous carbon for organic substances ensures that large quantities can be processed and inhibits further diffusion of the adsorbed organic substances, thereby enhancing the mineralization on anatase.  相似文献   

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