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1.
The corrosion behavior of mild steel and mild steel covered by electrochemically deposited (a) polyaniline (PANI) film, (b) epoxy coating and (c) PANI/epoxy coating system in 0.1 M sulfuric acid solution were investigated by electrochemical impedance spectroscopy (EIS). Electrochemical deposition of PANI film was performed from aqueous solution of 0.5 M sodium benzoate and 0.1 M aniline at constant current density of 1.5 mA cm−2. Epoxy coatings on mild steel and mild steel modified by PANI film were deposited at constant voltage. It was shown that thin PANI film had provided good corrosion protection of mild steel in 0.1 M sulfuric acid solution, and could be used for modification of mild steel prior to epoxy coating deposition. The increased corrosion protection of mild steel by PANI/epoxy coating system in the same solution was obtained.  相似文献   

2.
研究了硼砂电解电渗析制取硼酸和烧碱(EBS法)新工艺中阳极、阳离子膜及阴极碱浓度等因素的影响。结果表明,离子膜的选择对槽电压、电流效率以及电耗有着决定性的影响。较适宜于EBS体系的阳离子膜为Nafion901膜;PbO2/Ti阳极在EBS体系中性能稳定,消耗低,是一种实用的阳极。  相似文献   

3.
The experimental results of the separation of acetic acid (HA) from the sulfuric acid by the electro-electrodialysis (EED) method and the modeling of process have been presented. The Neosepta membranes CMX and ACM have been used. It has been found that the efficiency of retention of HA is high (>0.9) when the process is conducted below the limiting current density with respect to HSO4 or SO42− anions. The observed current efficiency of the H2SO4 removal was rather low (CES = ca. 0.7, when the initial concentration of H2SO4 in the mixture was 1 or 2 M) which was caused by the nonideal selectivity of the anion-exchange membrane. The experimental results have been described by the model based on the extended Nernst-Planck equation and the Donnan equilibrium. Since the efficiency of the process depended mainly on the selectivity of anion-exchange membrane (ACM), the concentration of fixed charges of that membrane, , and the ratio of volume fraction of pores to their squared tortuosity, Vp2, have been chosen as the main fitting parameters. It has been found that the fitting of the EED data depends mainly on , whereas in the modeling of diffusion experiment (or an EED experiment conducted at low current density) both parameters are important. The best fit has been obtained for , i.e. ca. one order smaller than that determined experimentally. The obtained optimal value of Vp2, equal to 0.013, is consistent with those previously obtained for other Neosepta anion-exchange membrane.  相似文献   

4.
A mix-valenced nickel oxide, NiOx, was prepared from nickel nitrate aqueous solution through a precipitation with sodium hydroxide and an oxidation by sodium hypochlorite. Further, pure nickel oxide was obtained from the NiOx by calcination at 300, 400 and 500 °C (labeled as C300, C400 and C500, respectively). They were characterized by thermogravimetry (TG), X-ray diffraction (XRD), nitrogen adsorption at −196 °C and temperature-programmed reduction (TPR). Their catalytic activities towards the degradation of phenol were further studied under continuous bubbling of air through the liquid phase. Also, the effects of pH, temperature and kinds of nickel oxide on the efficiency of the microwave-enhance catalytic degradation (MECD) of phenol have been investigated. The results indicated that the relative activity affected significantly with the oxidation state of nickel, surface area and surface acidity of nickel oxide, i.e., NiOx (>+2 and SBET = 201 m2 g−1)  C300 (+2 and SBET = 104 m2 g−1) > C400 (+2 and SBET = 52 m2 g−1) > C500 (+2 and SBET = 27 m2 g−1). The introduction of microwave irradiation could greatly shorten the time of phenol degradation.  相似文献   

5.
In this work, the elimination of p-nitrophenol (p-NPh) from aqueous solutions by electrochemical oxidation at Pb/PbO2 anodes was investigated. The process was studied under galvanostatic polarization mode in acidic and alkaline media, as a function of the temperature (20, 40 and 60 °C) and of the anodic current density (J = 10, 20 and 30 mA cm−2). In acidic media (0.5 M H2SO4), the oxidation process allowed a 94% p-NPh conversion in 7 h, at 20 °C and with J = 20 mA cm−2, with a wide distribution of degradation products (in particular: 39% p-benzoquinone and 26% hydroquinone, as given by a mass balance at the above electrolysis time). Under these conditions, the current efficiency for the substrate oxidation was 15.4% ([Ah L−1]exp = 7 versus [Ah L−1]theo = 1.08 Ah L−1). In alkaline media (0.1 M NaOH, pH 8.5), the most effective p-NPh elimination (97%) was obtained at 60 °C, 20 mA cm−2 and 420 min of electrolysis time, again with the production of p-benzoquinone and hydroquinone (52.7 and 15.1%, respectively). Under the latter conditions, an almost complete chemical oxygen demand (COD) abatement was attained, with a high level of p-NPh mineralization (>80%), a yield of p-NPh conversion greater than 95% and a scarce formation of aliphatic acids (most probably maleic acid). From the degradation curves ([p-NPh] versus t), in both acidic and alkaline media, the UV analyses and/or COD measurements, a complete oxidation of aliphatic acids to form CO2 could be predicted for electrolysis time >420 min, according to a suggested oxidation pathway.  相似文献   

6.
Natural clays were modified by means of the controlled attack of strong Brönsted acids in aqueous solution. The variations of the surface acidity of the solids, followed by IR of adsorbed pyridine and hammett indicators, indicated a population of Brönsted type sites above 800 μ mol/g, while the surface area increased from 23 up to 105 m2/g. A series of solids (ATZ-L, ATZ-A and ATZ-G) was activated using trifluoromethanesulfonic acid (CF3SO3H), then evaluated at the bench scale in a fixed bed reactor, both in liquid and gas phase, using an iC4/C4= molar ratio, which led to 5.5% trimethylpentanes (TMP) against 35.9% of C8= and 53.4% of heavier C9+ products for the catalysts (ATZ-L) having higher acid strength, i.e. Ho≈−9.3. For the solids having a moderate surface acid strength (Ho≈−4.4) the activation rate after 12 h runs was about 70%, but the solids having a higher acid strength, i.e. Ho=−5.6 and −9.3, showed a deactivation rate almost null after 24 h runs.  相似文献   

7.
USY (ultrastabilized Y) and Ce/USY (5 wt.% supported) zeolite acidities were characterized by microcalorimetric and adsorption studies of pyridine using liquid phase (Cal-Ad), thermogravimetry, and infrared analysis. The average adsorption enthalpies determined by microcalorimetry were −125.0 kJ mol−1 for USY and −97.2 kJ mol−1 for Ce/USY. A heterogeneous distribution of acid sites with heats of adsorption ranging from −134.0 (maximum heat value for USY) to −73.5 (minimum heat value for Ce/USY) kJ mol−1 was found for both zeolites. A two-site model was best fitted by the Cal-Ad method for HUSY (n1 = 0.1385 mmol g−1 with ΔH1 = −134.0 kJ mol−1, and n2 = 0.7365 mmol g−1 with ΔH2 = −101.5 kJ mol−1) and Ce/HUSY (n1 = 0.0615 mmol g−1 with ΔH1 = −117.6 kJ mol−1, and n2 = 0.7908 mmol g−1 with ΔH2 = −83.6 kJ mol−1). DRIFTS measurements after pyridine adsorption showed that USY zeolite possesses only Brønsted acidity and that cerium impregnation leads to the appearance of Lewis sites. Based on these results, three families of acid strength were distinguished: (i) strong Brønsted sites (ΔH > −130 kJ mol−1); (ii) Brønsted sites with intermediate strength (−100 < ΔH < −130); and (iii) weak Brønsted and Lewis sites (ΔH < −100). Thermogravimetric analysis showed that the strongest sites were able to retain pyridine up to 800 °C and that cerium incorporation leads to a more stable zeolite. A loss of strength was observed after impregnation. The total number of sites desorbed after gas adsorption (0.88 and 0.95 mmol for HUSY and Ce/HUSY, respectively) supports the Cal-Ad results (0.88 and 1.19 mmol for HUSY and Ce/HUSY, respectively) and indicates that not all Al sites are available to pyridine. The methodology used in this work for solid acid characterization (Cal-Ad) proved to be efficient in the evaluation of acid strength, total number and distribution of acid sites. XRPD, ICP-AES, 27Al NMR, and FTIR were used for additional structural characterization.  相似文献   

8.
2-氯-5-三氯甲基吡啶(TCMP)选择性氢化脱氯制备2-氯-5-氯甲基吡啶(CCMP)或2-氯-5-甲基吡啶(CMP)在农药“吡虫啉”合成中具有重要应用价值。首先在弱酸性的甲醇/乙酸/水混合溶剂中研究了TCMP电化学脱氯合成CCMP或CMP的可行性;其次,研究了阴极材料和电解液组成对TCMP选择性脱氯反应的影响;最后,采用膜厚度极距的板框式电解槽分别研究了阴、阳极支持电解质对电解槽压和电流密度与底物浓度对脱氯反应效率的影响。实验结果表明,在弱酸性的甲醇/乙酸/水混合溶剂中,TCMP能在银网阴极上高选择性的氢化脱氯成CMP;CMP收率从高到低的阴极依次为:银> 铜> 锌> 铅> 钛> 石墨> 镍。阴阳极支持电解质从四丁基高氯酸铵分别换成乙酸锂和硫酸,电解槽压大幅度下降。降低电流密度和提高底物浓度有利于TCMP电化学氢化脱氯效率。在优化条件下(阴极液:含10%乙酸+5%水+0.2 mol·L-1乙酸锂的甲醇溶液;阴极:银网;电流密度:333 A·m-2;温度:30℃),0.2 mol·L-1 TCMP 能高效地转化为CMP(收率:91%),电流效率可达54%,电解槽压大约为3.0 V。  相似文献   

9.
A silica composite of a perfluorocarbonsulfonic acid resin, Aciplex, has been used as a solid acid catalyst for a variety of reactions concerning water. The Aciplex–SiO2 composite containing 20 wt% Aciplex has a surface area of 1.3 m2 g−1 and possesses an ion-exchanged capacity of 0.46 meq. g−1 after pretreatment at 423 K, which is higher than that of 13 wt% Nafion–SiO2 (0.12 meq. g−1). The acid strengths estimated from an initial heat of adsorption of NH3 were similar for these polymer resin composites. It was found that the Aciplex–SiO2 was more active than typical solid acids such as Cs2.5H0.5PW12O40, H-ZSM-5, and SO42−/ZrO2 for hydrolysis of ethyl acetate in excess water and esterification of acrylic acid with 1-butanol, while it was less active than Cs2.5H0.5PW12O40 for N-alkylation of acrylonitrile with 1-adamantanol and solid–solid hydrolysis of 2-naphthyl acetate. The Aciplex–SiO2 was superior in activity to Nafion–SiO2 for all the above reactions and in thermal stability. These results indicate that Aciplex–SiO2 is a promising solid acid catalyst for reactions involving liquid phase water.  相似文献   

10.
The degradation of herbicide chlortoluron in aqueous medium by electro-Fenton process using a carbon felt cathode and a platinum anode was studied. The great oxidation ability of this process is due to the large production of hydroxyl radical (OH) by electrochemically induced Fenton's reagent. Hydroxyl radicals are very powerful oxidizing agents which react on organics up to complete mineralization. The influence of some experimental parameters such as initial concentration, current intensity and processing time on the degradation and mineralization rate of chlortoluron by hydroxyl radicals has been investigated. The evolution of chlortoluron concentration with processing time shows a pseudo first order kinetics (kabs = (4.8 ± 0.2) × 109 mol−1 L s−1). A Doehlert matrix was applied for determination of the optimal working conditions. Optimal parameters for maximum mineralization efficiency (TOC removal ratio of 98%) was achieved after 8 h of treatment using a chlortoluron initial concentration of 0.125 mM and an applied current of 300 mA. The mineralization of aqueous chlortoluron solutions was confirmed by identification of the end-products such as carboxylic acids and inorganic ions. Their evolution during electro-Fenton treatment was studied.  相似文献   

11.
Oxidation of primary hydroxyl groups of potato starch to the corresponding carboxylic acids was performed in a fluidized bed using N2-diluted NO2 as oxidant. FT-IR spectrum of the oxidized starch show the presence of two absorption bands at 1743 and 1379 cm−1. The absorption at 1743 cm−1 which normally attributed to carbonyl absorption vanishes after washing the oxidized starch by water. Then two new absorption bands appeared at 1650 and 1400 cm−1 corresponding to the ionized carboxyl groups.

The presence of nitrate favor the un-ionized form of carboxyl groups and then the band at 1743 cm−1 can be observed. Furthermore, the ionized carboxyl absorption (1600, 1400 cm−1) are replaced by carbonyl absorption at 1743 cm−1 by adding DCl. By means of 13C NMR analysis, oxidized starch, show a band around 200 ppm attributed to carboxylic acid, no formic acid was detected indicating that no cleavage took place under the applied reactions conditions.  相似文献   


12.
A methodology for the electroless deposition (ED) of PtCl62− using dimethylamine borane (DMAB) on a Rh-seeded carbon support has been developed for electrochemical and fuel cell applications. This procedure required seeding the carbon with a Rh-precursor catalyst via wet impregnation prior to the exposure of an aqueous ED bath containing PtCl62−, DMAB, and sodium citrate (complexing/stabilizing agent). Kinetic parameters that affect the extent and rate of PtCl62− deposition include concentrations of PtCl62−, DMAB, and sodium citrate as well as pH and concentrations of Rh seed sites. A linear relationship between rate and extent of PtCl62− deposition and DMAB and Rh concentrations was found while the citrate concentration had little effect on rate and a modest effect on extent. Lastly, extent of PtCl62− deposition showed a maximum with respect to pH. Characterization of the Rh-seeded, carbon support by transmission electron microscopy (TEM) shows that the Rh particle diameters remain constant at 33–43 Å as the Rh weight loading increases from 0.4% to 2.2% to 4.4%. Further, after deposition of similar loadings of Pt, TEM analysis shows Pt particle diameters decrease with increasing Rh loading, since equal amounts of Pt were deposited on greater numbers of Rh seed particles. This pattern suggests a shell-core geometry, where Pt is deposited more or less uniformly around a Rh core.  相似文献   

13.
Pyroelectric hybrid materials were prepared from 4,5-dihydroxy-3-(phenyldiazenyl)naphthalene-2,7-disulfonic acid (C.I. Acid Red 29) and Nb or Ta alkoxides via a sol–gel process. The hybrid materials were analyzed and characterized using infrared spectrometry, atom force microscopy and thermal gravimetry differential thermal analysis. The dye was covalently linked to the inorganic network and organic–inorganic hybrid films had excellent pyroelectric character (average pyroelectric coefficient 1.79 × 10−6 C cm−2 K−1) and high thermal stability; no phase separation was observed in the films.  相似文献   

14.
The production and decay of singlet molecular oxygen (1O2) in TiO2 photocatalysis were investigated by monitoring its phosphorescence under various reaction conditions. First, the effects of additives such as KBr, KSCN, KI, H2O2, and ethanol on the amount of 1O2 produced by photo excitation of P25 TiO2 were measured. The same additives were employed to investigate the effect on the amount of O2 produced. Comparison between the effects on 1O2 and O2 suggested that 1O2 is formed by the electron transfer mechanism, the reduction of molecular oxygens to O2 by photogenerated electrons and the subsequent oxidation of O2 to 1O2 by photogenerated holes. The formation of 1O2 decreased at pH < 5 and pH > 11, indicating that the intermediate O2 is stabilized at the terminal OH site of the TiO2 surface in the pH range of 5 < pH < 11. Eighteen commercially available TiO2 photocatalysts were compared on the formation of 1O2 and O2 in an aqueous suspension system. The formation of 1O2 was increased with decreasing size of TiO2 particles, indicating that a large specific surface area causes a higher possibility of reduction producing O2 and then a large amount of 1O2 is formed. The difference in the crystal phase (rutile and anatase) did not affect the formation of 1O2.  相似文献   

15.
Adsorption of dihydrogen onto the zeolites Na-ZSM-5 and K-ZSM-5 renders the fundamental H–H stretching mode infrared active. The corresponding infrared absorption bands were found at 4101 and 4112 cm−1 for H2/Na-ZSM-5 and H2/K-ZSM-5, respectively. Thermodynamic characterization of the adsorbed state was carried out by means of variable-temperature infrared spectroscopy; simultaneously measuring integrated band intensity, temperature and equilibrium pressure of the gas phase. For the H2/Na-ZSM-5 system, the standard adsorption enthalpy and entropy resulted to be Δ = −10.3 (±0.5) kJ mol−1 and Δ = −121 (±10) J mol−1 K−1. For H2/K-ZSM-5 corresponding values were −9.1 (±0.5) kJ mol−1 and −124 (±10) J mol−1 K−1, respectively.  相似文献   

16.
Nitrous and nitric acids form in aqueous solutions exposed to a gliding arc discharge burning in humid air. The anions interfere when the concentration of particular solutes such as pollutants must be determined. In particular they falsify the COD measurements and spectral investigations and thus the efficiency of the plasma treatment in pollutant abatement. The nitrite anions must be thus removed, which require specific reagents. The influence of parameters such as solution pH and [reducers]/[NO2] ratio on the reduction reaction was evaluated. The reduction of nitrite into N2 either by sulfamic acid or sodium azide is a first-order pH-dependant reaction with regard to nitrite and reducers (k1 = 2.93 × 10−1 m3 kmol−1 s−1; k2 = 6.21 × 10−1 m3 kmol−1 s−1, respectively). Sodium azide is thus more reactive than sulfamic acid.  相似文献   

17.
The electrochemical behavior of folic acid at the Keggin-type phosphomolybdate (PMo12) doped polypyrrole (PPy) film modified glassy carbon electrode (PMo12-PPy/GCE) was studied. PMo12 doped PPy modified electrodes were achieved during the electrochemical preparation of the polymer films in aqueous solution. The redox behavior of the modified electrode was described by cyclic voltammetry. The electrochemical behavior of folic acid at PMo12-PPy/GCE was studied by 0.5 order differential voltammetry. Numerous factors affecting the reduction peak currents of folic acid at PMo12-PPy/GCE were optimized to maximize the sensitivity. The results showed that folic acid had high inhibitory activity toward the reduction of modified electrode in 0.01 M H2SO4. The reduction peak currents were directly proportional to the concentration of folic acid from 1.0 × 10−8 to 1 × 10−7 M with correlation coefficient of 0.9976, a detection limit of 1.0 × 10−10 M of folic acid was estimated. From the inhibitory effect of folic acid on PMo12-PPy/GCE, the apparent formation constant of folic acid with the modified film was estimated. This modified electrode showed excellent sensitivity and stability for the determination of folic acid. The response mechanism of folic acid at PMo12-PPy/GCE was discussed in detail.  相似文献   

18.
The aim of this work is to study the viability of the H2O2 Promoted Catalytic Wet Air Oxidation (PP-CWAO) process, using activated carbon (AC) as catalyst, to increase the biodegradability of phenolic aqueous solutions. Seventy-two hours experiments were performed in a trickle bed reactor at 140 °C and 2 bar of oxygen partial pressure. Feed concentrations, in terms of theoretical chemical oxygen demand (ThCOD), were 11.8 g COD l−1 for phenol, 12.6 g COD l−1 for o-cresol and 8.0 g COD l−1 for p-nitrophenol. Air was used as main oxidant and 20% of the stoichiometric amount of H2O2 needed for pollutant complete mineralisation was added as oxidation promoter. Adding H2O2 to the CWAO process not only increases pollutant removal but also leads to higher mineralisation of the remaining oxidation products. For instance, removal of phenol, o-cresol and p-nitrophenol increase from 45, 33 and 15% in the CWAO process to 64, 64 and 49% in the PP-CWAO process. In addition, the PP-CWAO process leads to better biodegradability enhancements, when compared to CWAO, as demonstrated by the respirometric tests. However, it is still necessary to improve the oxidation step in order to assure more biodegradable effluents that could be combined with a subsequent biological wastewater plant.  相似文献   

19.
The possibility of using acridine yellow G (AYG) as solar photocatalyst for wastewater treatment has been examined in this paper. A phenolic compound, namely ferulic acid, has been employed as target pollutant. The effect of pH, concentration of the substrate and photocatalyst has been investigated. Control of pH is critical in the process, as rate constants obtained at pH 3 (k = 0.020 min−1) were one order of magnitude higher than in basic media (k = 0.002 min−1 at pH 9), due to differences in the absorption spectrum in the UVA–vis region. Under acidic conditions, 80% removal of the substrate was achieved after 3 h irradiation, although TOC decrease was moderate (around 20%). Nevertheless important detoxification of the solution was measured, and the remaining organic matter showed an enhanced biodegradability. For this reason, a combination of AYG-driven solar photocatalysis with biological treatment seems a good approach to deal with these effluents. Experimental data are consistent with an electron transfer mechanism between the excited photocatalyst and the substrate: involvement of hydroxyl radicals can be ruled out, and photophysical measurements indicate a quenching of the fluorescence of AYG in the presence of ferulic acid. The rate constant for this process was obtained from the Stern–Volmer equation (kq = 4.4 × 109 M−1 s−1). Finally, based on the Rehm–Weller equation, a ΔG = −22.8 kcal/mol was calculated, indicating that the process is thermodynamically favourable.  相似文献   

20.
The electrodeposition of metallic rhodium on pyrolytic graphite from 10 mM Na3RhCl6 + 0.5 M NaCl aqueous solution was studied by potentiostatic method with the use of a double-pulse technique involving nucleation and growth pulses. Physico-chemical properties of Rh deposits were investigated by electrochemical methods and scanning electron microscopy. The activity of Rh-modified graphite electrodes towards nitrate reduction in neutral medium was demonstrated, the activation energy of nitrate reduction and NO3 Langmuir adsorption constant on Rh deposits were determined.

The use of double-pulse technique resulted in enhanced surface coverage in comparison with usual potentiostatic deposition and in decreasing the mean particle size down to 30 nm, while the specific catalyst surface area attains 32 m2 g−1. The increase in the nucleation pulse duration from 20 to 100 ms enhances the mass catalytic activity towards NO3 reduction, which reaches 175 A g−1 for the best samples. Irrespectively of electrodeposition parameters, only NH3 and NO2 were detected as nitrate reduction products. The rate of NO3 destruction was equal to which is much higher than that of most of Pd/Cu-based nitrate hydrogenation systems and Ag/TiO2 photocatalysts.  相似文献   


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