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1.
The kinetics of electrocatalytic reduction of nitrate on Pt(1 1 0) in perchloric acid was studied with cyclic voltammetry at a very low sweep rate of 1 mV s−1, where pseudo-steady state condition was assumed to be achieved at each electrode potential. Stationary current-potential curves in perchloric acid in the absence of nitrate showed two peaks at 0.13 V and 0.23 V (RHE) in the so-called adsorbed hydrogen region. The nitrate reduction proceeded in the potential region of the latter peak in the pH range studied. The reaction orders with respect to NO3 and H+ were observed to be close to 0 and 1, respectively. The former value means that the adsorbed NO3 at a saturated coverage is one of the reactants in the rate-determining step (rds). The latter value means that hydrogen species is also a reactant above or on the rds. The Tafel slope of nitrate reduction was −66 mV per decade, which is taken to be approximately −59 mV per decade, indicating that the rds is a pure chemical reaction following electron transfer. We discuss two possible reaction schemes including bimolecular and monomolecular reactions in the rds to explain the kinetics and suggest that the reactants in the rds are adsorbed hydrogen and adsorbed NO3 with the assistance of the results in our recent report for nitrate reduction on Pt(S)[n(1 1 1) × (1 1 1)] electrodes: the nitrate reduction mechanism can be classified within the framework of the Langmuir-Hinshelwood mechanism.  相似文献   

2.
We have investigated the adsorbed intermediates of ethanol electro-oxidation at Pt(1 1 1), Pt(1 0 0) and Pt(1 1 0) using FTIR and SFG spectroscopies. Mainly, we focus on the CO formation. The aim of the present work is to compare the responses coming from two different surface probes: FTIR spectroscopy and SFG spectroscopy. Between 1800 cm−1 and 2300 cm−1, our FTIR and SFG results are in good agreement. Specifically in the case of the ethanol/Pt(1 1 1) interface, the SFG spectroscopy presents higher sensibility to the interface response compared to the FTIR spectroscopy.  相似文献   

3.
The electrocatalytic oxidation of hydrazine has been studied on glassy carbon modified by electrodeposition of quinizarine, using cyclic voltammetry and chronoamperometry techniques. It has been shown that the oxidation of hydrazine to nitrogen occurs at a potential where oxidation is not observed at the bare glassy carbon electrode. The apparent charge transfer rate constant and transfer coefficient for electron transfer between the electrode surface and immobilized quinizarine were calculated as 4.44 s−1 and 0.66, respectively. The heterogenous rate constant for oxidation of hydrazine at the quinizarine modified electrode surface was also determined and found to be about 4.83 × 103 M−1 s−1. The diffusion coefficient of hydrazine was also estimated as 1.1 × 10−6 cm2 s−1 for the experimental conditions, using chronoamperometry.  相似文献   

4.
The adsorption of phosphate anions from phosphate solutions at poly-oriented and single-crystal platinum electrodes, primarily Pt(1 1 1), was studied over a wide range of pH by cyclic voltammetry. The features observed at the poly-oriented Pt electrode in phosphate solution may be related to the different crystalline facets, the (1 1 1) orientation presenting the most significant behavior in terms of phosphate adsorption. On the reversible hydrogen electrode (RHE) scale, the phosphate adsorption strength decreases with increasing alkalinity of the solution. Qualitatively, three different pH regions can be distinguished. At pH < 6 only a broad reversible peak is observed, corresponding to the adsorption of H2PO4 and further deprotonation to adsorbed HPO4. For 6 < pH < 11 a butterfly feature followed by one or two anodic peaks (depending on scan rate) is observed, ascribed to the adsorption of HPO4 followed by its subsequent deprotonation to adsorbed PO43−. The splitting into two or three voltammetric features, and the irreversibility of the two features at more positive potential, is ascribed to the deprotonation reaction leading to a surface species (i.e. phosphate) which needs to change its surface coordination. At pH > 11 a reversible pre-wave and a sharp spike are observed, ascribed to the co-adsorption of phosphate and hydroxide.  相似文献   

5.
Kinetics and mechanism of nitrate ion reduction on Pt(1 1 1) and Cu-modified Pt(1 1 1) electrodes have been studied by means of cyclic voltammetry, potentiostatic current transient technique and in situ FTIRS in solutions of perchloric and sulphuric acids to elucidate the role of the background anion. Modification of platinum surface with copper adatoms or small amount of 3D-Cu crystallites was performed using potential cycling between 0.05 and 0.3 V in solutions with low concentration of copper ions, this allowed us to vary coverage θCu smoothly. Following desorption of copper during the potential sweep from 0.3 to 1.0 V allowed us to estimate actual coverage of Pt surface with Cu adatoms. Another manner of the modification was also applied: copper was electrochemically deposited at several constant potentials in solutions containing 10−5 or 10−4 M Cu2+ and 5 mM NaNO3 with registration of current transients of copper deposition and nitrate reduction.It has been found that nitrate reduction at the Pt(1 1 1) surface modified by copper adatoms in sulphuric acid solutions is hindered as compared to pure platinum due to induced sulphate adsorption at E < 0.3 V. Sulphate blocks the adsorption sites on the platinum surface and/or islands of epitaxial Cu(1 × 1) monolayer thus hindering the adsorption of nitrate anions and their reduction. The extent of inhibition weakly depends on the copper adatom coverage. Deposition of a small amount of bulk copper does not affect noticeably the rate of nitrate reduction.Nitrate reduction on copper-modified Pt(1 1 1) electrodes in perchloric acid solutions occurs much faster as compared to pure platinum. The steady-state currents are higher by 4 and 2 orders of magnitude at the potentials of 0.12 and 0.3 V, respectively. The catalytic effect of copper adatoms is largely caused by the facilitation of nitrate adsorption on the platinum surface near Cuad and/or on the islands of the Cu(1 × 1) monolayer (induced nitrate adsorption).Hydrogen adatoms block the adsorption sites on platinum for NO3 anion adsorption and inhibit reactions of nitrate reduction even at moderate surface coverage.The products of nitrate reduction in sulphuric and perchloric acids are essentially the same (NO and ammonia) irrespective of the presence or absence of Cu on the platinum surface.  相似文献   

6.
A three-phase fluidized bed reactor (TFBR) was developed in this study with the objective to achieve high rates of oxygen transfer from the gas to the liquid phase in the presence of fluidized solid particles. With 2.9 m height, 0.605 m diameter, and a short residence time of 8 h, the TFBR is particularly suitable for industrial applications such as aerobic biodegradation of high-strength wastewaters including refractory compounds. Experiments with tap water and air show that the TFBR enables complete fluidization. With the water and air superficial velocities in the respective ranges of 0.005–0.203 and 0.8–2.0 cm/s, the volumetric oxygen transfer coefficient is 2.3 × 10−2 s−1, which is higher than that obtained in similar experimental studies on oxygen transfer carried out in the past. These results suggest that the developed TFBR could be very effective in industrial applications where short hydraulic time and high gas-to-liquid mass transfer rates are desirable.  相似文献   

7.
Ni + Mo + Si coatings were obtained by nickel deposition from a bath containing suspension of molybdenum and silicon powders. These coatings were obtained in galvanostatic conditions, at the current density of jdep = −0.100 A cm−2. For determination of the influence of phase composition and surface morphology of obtained coatings on changes of corrosion resistance, these coatings were modified in argon atmosphere by thermal treatment at the temperature of 1100 °C during 1 h. A scanning electron microscope was used for surface morphology characterization of the coatings. Chemical composition of obtained coatings was determined by X-ray fluorescence spectroscopy method. Phase composition investigations were conducted by X-ray diffraction method. It was found that the obtained coatings are composed of three phase structures, i.e., nickel, molybdenum and silicon. Phase composition for the Ni + Mo + Si coatings after thermal treatment is markedly different. The main peaks corresponding to the Ni and Mo coexist with the new ones corresponding to new phases: Mo5Si3, NiSi, Mo2Ni3Si and Ni6Mo6C1.06.Electrochemical corrosion resistance investigations were carried out in the 5 M KOH, using potentiodynamic and electrochemical impedance spectroscopy methods. On the basis of these investigations it was found that Ni + Mo + Si coatings after thermal treatment are more resistant in alkaline solution than Ni + Mo + Si as-deposited coatings. The reason of this is presence of silicides in the coatings.  相似文献   

8.
The aim of this work was to study the Fischer-Tropsch (FT) synthesis of a model biosyngas (33% H2, 17% CO and 50% N2) in a single tube fixed-bed FT reactor. The FT reactor consisted of a shell and tube with high-pressure boiling water circulating throughout the shell. A spherical unpromoted cobalt catalyst was used with the following reaction conditions: a wall temperature of 473 K, a pressure of 20 bars and a gas hour space velocity (GHSV) of 37 to 180 NmL.gcat− 1.h− 1. The performance of the FT reactor was also validated by developing a 2D pseudo-homogeneous model that includes transport equations and reaction rate equations. Good agreement between the model predictions and experimental results were obtained. This developed model was extended to predict and quantify the influence of the FT kinetics as well as determine the influence of the tube diameter and the wall temperature. The predicted behaviors for CO and H2 conversion, productivity of hydrocarbons (mainly CH4 and C5+) and fluid temperature along the axis of the reactor have been analyzed.  相似文献   

9.
The behaviours of irreversible adsorption (IRA) of Sn adatoms on Pt(1 0 0), Pt(1 1 1) and Pt(1 1 0) electrodes were characterized using cyclic voltammetry. It has revealed that Sn can adsorb irreversibly on Pt(1 0 0) and Pt(1 1 1), while not significantly on Pt(1 1 0) electrode. Quantitative analysis of the relationship between 1 − θH and θSn suggests that Sn adatoms may adsorb preferably on hollow sites of Pt(1 1 1) (threefold) and Pt(1 0 0) (fourfold) planes, which is in accordance respectively with the values 0.31 and 0.21 of coverage of IRA Sn adatoms in saturation adsorption determined on these electrodes. The IRA Sn adatoms on different basal planes of Pt single crystal yield different impact on the electrocatalytic oxidation of ethanol. It has revealed that the IRA Sn adatoms on Pt(1 0 0) electrode have declined the activity for ethanol oxidation, while IRA Sn adatoms on Pt(1 1 1) have enhanced remarkably the electrocatalytic activity with Sn coverage θSn between 0.09 and 0.18. The oxidation peak potential Ep and the current density jp of ethanol oxidation on Pt(1 1 1)/Sn were varied with θSn, and the highest jp (1258 μA cm−2) as well as the lowest Ep (0.20 V) were measured simultaneously at θSn around 0.14. In comparison with the data obtained on a bare Pt(1 1 1), the Ep was shifted negatively by 65 mV and the jp has been enhanced to about 1.7 times on the Pt(1 1 1)/Sn (θSn = 0.14), which is ascribed to hydroxyl species adsorption at relatively low potentials on Pt(1 1 1)/Sn surfaces. The current study is of importance in revealing the fundamental aspects of modification of the basal planes of Pt single crystal using Sn adatoms, and the impact of this modification on electrocatalytic activity towards ethanol oxidation.  相似文献   

10.
Dissociative adsorption and oxidation of glycine on Au(1 1 1) single crystal electrodes in alkaline solutions were studied in the present paper using cyclic voltammetry (CV), in situ FTIR spectroscopy (FTIRS) and electrochemical quartz crystal microbalance (EQCM). In situ FTIRS results demonstrated that adsorbates derived from glycine dissociative adsorption are adsorbed cyanide anions (CNad). The CNad species are stable on Au(1 1 1) surface in the potential region from −0.8 to 0.0 V, and can be oxidized when electrode potential is increased above 0.1 V. The oxidation of CNad releases surface active sites for further glycine oxidation. The products of CNad oxidation were determined by in situ FTIRS as cyanate (OCN), aurous cyanide (AuCN) and aurous di-cyanide (Au(CN)2). The formation of Au(CN)2 may initiate a dissolution of Au(1 1 1) surface atoms, which has been confirmed by a loss of surface mass determined in EQCM studies. It has revealed also that at high electrode potential region glycine may be split on Au(1 1 1) surface to form AuCH2NH2 and AuCOO adsorbates. Further oxidation of these species yielded CO2 and -NH2, and the AuCH2NH2 may be also combined with surface Au oxide to form methylamine. The CO2 species produced in glycine oxidation are all retained in alkaline solutions to generate carbonate (CO32−) and bicarbonate (HCO3) species that were clearly determined by in situ FTIRS studies.  相似文献   

11.
Fluorine-containing polyimide with crosslinkable vinyl group (FPI) was synthesized from 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (PFMB), and 4-amino styrene (AS). The reinforced composite membranes based on semi-interpenetrating polymer networks (semi-IPN) were prepared via solution casting of FPI and Nafion®212, and crosslinking thereafter. The water uptake, swelling ratio, mechanical properties, thermal behavior, proton conductivity, and oxidative stability of the composite membranes were investigated. Compared with the recast Nafion® 212, the composite membrane shows better mechanical properties and improved dimensional stability. The tensile strength of the composite membranes ranges from 39.0 MPa to 80.0 MPa, which is higher than that of the recast Nafion® 212 membrane (26.6 MPa). The dimensional stability of the composite membranes increases with increasing FPI content in the membranes, whereas the proton conductivity decreases. The composite membranes show considerable proton conductivity from 2.0 × 10−2 S cm−1 to 8.9 × 10−2 S cm−1 at a temperature from 30 °C to 100 °C, depending on the FPI contents. The composite membranes with semi-IPN from FPI and Nafion®212 have considerable high proton conductivity, excellent mechanical properties, thermal and dimensional stabilities.  相似文献   

12.
A series of reinforced composite membranes were prepared from Nafion®212 and crosslinkable fluorine-containing polyimide (FPI) with various crosslinkers. The crosslinkable FPI reacts with the crosslinkers and forms semi-interpenetrating polymer networks (semi-IPN) structure with Nafion®212. The water uptake, swelling ratio, mechanical properties, thermal behavior, proton conductivity, and chemical oxidation stability of the composite membranes are studied. The degree of crosslinking is characterized by gel fraction of the composite membranes. Compared to pure Nafion®212, the composite membranes exhibit excellent thermal stability, improved mechanical properties and dimensional stability. The tensile strength of the composite membranes is in the range of 37.3-51.2 MPa. All the composite membranes exhibit high proton conductivity which ranges from 1.9 × 10−2 to 9.9 × 10−2 S cm−1. The proton conductivity of the composite membrane with 2-propene-1-sulfonic acid sodium salt (SAS) as the crosslinker is 9.9 × 10−2 S cm−1 at 100 °C which is similar to that of Nafion®212 under the same condition.  相似文献   

13.
The adsorption behaviour of 2-thiothymine and 4-thiothymine on a Au(1 1 1) single crystal electrode has been studied using cyclic voltammetry and X-ray photo electron spectroscopy. For both thio derivatives the adsorption region is restricted due to the onset of reversible oxidization to 2,2′-bis(1H-5-methylpyrimidin-4-one-2-yl)-disulphide or 4,4′-bis(1H-5-methylpyrimidin-2-one-4-yl)-disulphide at anodic potentials. Two different orientations of adsorbed 2-thiothymine have been observed. Between −350 mV and −700 mV versus Ag/Ag+ the molecule is solely chemisorbed via its sulphur atom and adopts an upright orientation towards the surface. However at more negative potentials 2-thiothymine is reoriented into a slightly tilted position interacting via its S, N and O atoms with the surface. In contrast, 4-thiothymine exhibits only one adsorption geometry. Between −300 mV and −700 mV versus Ag/Ag+ it is chemisorbed via sulphur and nitrogen adopting a slightly tilted position. At −950 mV versus Ag/Ag+ 4-thiothymine is irreversibly reduced. The sulphur substituent is eliminated and covers the substrate.  相似文献   

14.
This paper is focused on the in situ radiotracer and voltammetric studies of the induced HSO4/SO42− adsorption at Pt(poly) and Pt(1 1 1) surfaces in 0.1 mol dm−3 HClO4 solution in the course of Cr(VI) electroreduction. Besides this, the sorption behavior of HSO4/SO42− ions on bare Pt(poly) and Pt(1 1 1) electrodes is compared and discussed. From the experimental results it can be stated that: (i) although the extent of bisulfate/sulfate adsorption is strongly dependent upon the crystallographic orientation of Pt surfaces, the maximum coverage on the Pt(1 1 1) does not exceed 0.2 monolayer; (ii) the Cr(VI) electroreduction on both poly- and (1 1 1) oriented platinum proceeds via a ce (chemical-electron-transfer) mechanism to yield Pt surfaces covered with intermediate surface adlayers containing Cr(VI) particles (and reduced Cr-containing adspecies) and ‘strongly bonded’ HSO4/SO42− ions; (iii) while the coverage of platinum surfaces by the intermediate complexes formed in the course of Cr(VI) electroreduction at E > 0.20 V is basically independent of the crystallographic orientation of the Pt electrode, the onset for rapid Cr(VI) reduction is highly affected by the nature and crystallographic orientation of the electrode.  相似文献   

15.
An investigation of isovaleraldehyde (ISOV) photocatalytic oxidation was conducted at initial concentrations ranging from 25 to 150 mg/m3 and different relative humidities (5–90% RH) in order to characterize the process performances close to indoor air conditions. Experiments were carried out in two different reactors: cylinder and flat-plate photoreactor (planar reactor) at different air gap (20–60 mm) and gas residence times (0.67–5.0 s). A plug flow reactor system was developed in order to perform kinetic studies of (i) isovaleraldehyde removal, (ii) selectivity of CO2, (iii) by-products formation and removal. It appears that ISOV removal efficiencies increased with lower inlet concentrations, lower air gap and higher gas residence times.  相似文献   

16.
Pre-combustion microbial desulphurization of coal containing total sulphur (3.90%) and pyritic sulphur (2.80%) has been evaluated in a coal slurry reactor. The coal slurry reactor operated at hydraulic retention time (HRT) of 96 h with a coal pulp density of 15 percent and remove 79 percent of pyritic sulphur and 76 percent of ash with an increase in the calorific value of coal from 4400 to 6800 kcal kg−1 at a pyritic load of 1.9 kg pyritic sulphur kg−1 MLSS d−1. The treated coal yield is 72 percent. The biochemical kinetic coefficients, viz. yield coefficient (Y) and decay coefficient (Kd) in the coal slurry reactor system are 0.178 and 0.007 d−1, respectively, while maximum growth rate (μmax) and half saturation rate constant (Ks) are 0.025 h−1 and 0.220 g l−1 as pyrite, respectively.  相似文献   

17.
A low pressure plasma process working at 600-800 Pa was used to deposit from aqueous solution ZrO2-4 mol% Y2O3 (Yttria partially stabilized Zirconia-YpSZ) layers and stacks of Ta2O5/YpSZ layers for use as thermal barrier coatings (TBC). The observation of the cross section revealed a high porosity. The thermal diffusivity of the layers (1 × 10−7 m2 s−1) was measured by a laser flash technique and compared with values obtained on air plasma sprayed material (3 × 10−7 m2 s−1). The plasma reactor were also used to deposit ZrB2-ZrO2-SiC layers used as Ultra High Temperature Composite (UHTC) from aqueous solutions of zirconyl and Boron nitrates containing suspensions of SiC. Layers up to 100 μm thick were obtained on SiC substrates. XRD was used to study the crystallinity of the layer. The presence of ZrB2 and SiC phases was confirmed after the deposition. XRD analysis showed that heat treatment at 1073 K under oxidizing conditions led to the loss of ZrB2 and the appearance of ZrO2 phases. To understand the behaviour of the layers to interaction with atomic oxygen (combustion for TBC and spacecraft re-entry phase for UHTC), we have measured the atomic oxygen recombination coefficient to determine the number of adsorption sites on the surface of the coatings. This was accomplished by using a low pressure plasma reactor coupled with optical spectroscopic measurements as a diagnostic technique.  相似文献   

18.
This paper presents the results from 92 cycles of an anaerobic sequencing batch biofilm reactor containing biomass immobilized on inert support (mineral coal) applied for the treatment of an industrial wastewater containing high sulfate concentration. The pilot-scale reactor, with a total volume of 1.2 m3, was operated at sulfate loading rates ranging from 0.15 to 1.90 kgSO42−/cycle (48 h — cycle) corresponding to sulfate concentrations of 0.25 to 3.0 gSO42− l− 1. Domestic sewage and ethanol were utilized as electron donors for sulfate reduction. Influent sulfate concentrations were increased in order to evaluate the minimum COD/sulfate ratio at which high reactor performance could be maintained. The mean sulfate removal efficiency remained between the range of 88 to 92% at several sulfate concentrations. Temporal profiles along the 48 h cycles were carried out under stable operation at sulfate concentrations of 1.0, 2.0 and 3.0 gSO42− l− 1. Sulfate removal reached 99% for cycle times of 15, 25, and 30 h, and the effluents sulfate concentrations were lower than 8 mgSO42− l− 1. The results demonstrate the potential applicability of the anaerobic configuration for the biological treatment of sulfate-rich wastewaters.  相似文献   

19.
Mutual diffusion coefficients (interdiffusion coefficients) have been determined for aluminium chloride in water at 298.15, 303.15 and 310.15 K at concentrations from 0.002 to 0.010 mol dm−3 together with molar conductivity values. The diffusion coefficients were obtained by using a conductimetric open-ended capillary cell. The experimental data were discussed on the basis of the Onsager-Fuoss model. The Nernst diffusion coefficients derived from diffusion 1.208 × 10−9 and 1.701 × 10−9 m2 s−1 and from conductance 1.238 × 10−9 and 1.692 × 10−9 m2 s−1, at two temperatures 298.15 and 310.15 K, respectively, agree well each other.  相似文献   

20.
Near zero thermal expansion porous ceramics were fabricated by using SiC and LiAlSiO4 as positive and negative thermal expansion materials, respectively, bonded by glassy material. The microstructure, mechanical properties, and thermal expansion behavior of LAS/SiC porous ceramics with different particle sizes of LiAlSiO4 were investigated. The results indicated that the coefficient of thermal expansion of the LAS/SiC porous ceramics decreased from 0.5206×10−6 to −1.1053×10−6 K−1 with increasing the LiAlSiO4 particle size from ~45 µm to ~125 μm. It was attributed to the reduction in the reaction between LiAlSiO4 and SiO2 as the particle size of LiAlSiO4 increased. Young’s modulus increased from 36 MPa to 54 MPa as the sintering temperature increased from 850 °C to 950 °C because of the good bonding between the SiC grains and the glass materials.  相似文献   

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