Direct reduction of SO2 to elemental sulfur by the coupling of cold plasma and catalyst (I)

The direct reduction of SO2 to elemental sulfur in flue gas by the coupling of cold plasma and catalyst, being a new approach for SO2 reduction, was studied. In this process, CO2 can be disassembled to form CO, which acts as the reductant under the cold plasma. With the coupling of the cold plasma and the catalyst, sulfur dioxide was selectively reduced by CO to elemental sulfur with a byproduct of metal sulfate, e.g., FeSO4. In the present work, Fe2O3/gamma-Al2O3 was employed as the catalyst. The extent of desulfurization was more than 80%, and the selectivity of elemental sulfur is about 55%. The effects of water vapor, temperature, and the components of simulated flue gas were investigated. At the same time, the coupling of thermogravimetry and infrared method and a chemical analysis method were employed to evaluate the used catalyst. In this paper, we will focus on the discussion of the catalyst. The discussions of the detail of plasma will be introduced in another paper.

Preparation and characterization of PtSn/C anode electrocatalysts for direct ethanol fuel cell

Highly active PtSn/C catalyst was prepared by a polyol method. The catalyst was reduced in H-2/Ar atmosphere at 600 degreesC for 2 h in order to obtain different metallic phase. TEM images show uniform dispersion of spherical metal nanoparticles with average diameters of 1.8 and 3.9 nm for the as-prepared and treated catalysts, respectively. UV-vis spectrophotometry is employed to monitor the preparation process and the results indicate that Pt-Sn complex formed once the precursors of Pt and Sn were mixed together. The structure properties of the samples were characterized using X-ray diffraction. The results show that after reduction, the catalyst tends to form PtSn alloy. TPR experiment results show that Sn exists in multivalent state in the as-prepared sample while only zero-valence Sn was detected in the treated sample, while it could not be excluded that the multivalent tin existed in the treated sample. Cyclic voltammetry (CV) technique and single direct ethanol fuel cell (DEFC) tests indicate that the as-prepared catalyst possesses superior catalytic activity for ethanol oxidation to the treated sample. The results suggest that Pt and multivalent Sn are the active species for ethanol oxidation. (C) 2004 Elsevier B.V. All rights reserved.

Pt based anode catalysts for direct ethanol fuel cells

In the present work several Pt-based anode catalysts supported on carbon XC-72R were prepared with a novel method and characterized by means of XRD, TEM and XPS analysis. It was found that all these catalysts are consisted of uniform nanosized particles with sharp distribution and Pt lattice parameter decreases with the addition of Ru or Pd and increases with the addition of Sn or W. Cyclic voltammetry (CV) measurements and single direct ethanol fuel cell (DEFC) tests jointly showed that the presence of Sn, Ru and W enhances the activity of Pt towards ethanol electro-oxidation in the following order: Pt1Sn1/C > Pt1Ru1/C > Pt1W1/C > Pt1Pd1/C > Pt/C. Moreover, Pt1Ru1/C further modified by W and Mo showed improved ethanol electro-oxidation activity, but its DEFC performance was found to be inferior to that measured for Pt1Sn1/C. Under this respect, several PtSn/C catalysts with different Pt/Sn atomic ratio were also identically prepared and characterized and their direct ethanol fuel cell performances were evaluated. It was found that the single direct ethanol fuel cell having Pt1Sn1/C or Pt3Sn2/C or Pt2Sn1/C as anode catalyst showed better performances than those with Pt3Sn1/C or Pt4Sn1/C. It was also found that the latter two cells exhibited higher performances than the single cell using Pt1Ru1/C, which is exclusively used in PEMFC as anode catalyst for both methanol electro-oxidation and CO-tolerance. This distinct difference in DEFC performance between the catalysts examined here would be attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and additives. It is thought that an amount of -OHads, an amount of surface Pt active sites and the conductivity effect of PtSn/C catalysts would determine the activity of PtSn/C with different Pt/Sn ratios. At lower temperature values or at low current density regions where the electro-oxidation of ethanol is considered not so fast and its chemisorption is not the rate-determining step, the Pt3Sn2/C seems to be more suitable for the direct ethanol fuel cell. At 75 degreesC, the single ethanol fuel cell with Pt3Sn2/C as anode catalyst showed a comparable performance to that with Pt2Sn1/C, but at higher temperature of 90 degreesC, the latter presented much better performance. It is thought from a practical point of view that Pt2Sn1/C, supplying sufficient -OHads and having adequate active Pt sites and acceptable ohmic effect, could be the appropriate anode catalyst for DEFC. (C) 2003 Elsevier B.V. All rights reserved.

Preparation of highly active Pt/C cathode electrocatalysts for DMFCs by an improved aqueous impregnation method

An improved aqueous impregnation method was used to prepare 40 wt% Pt/C electrocatalysts. TEM analysis of the samples showed that the Pt particles impregnated for a short time have a very narrow size distribution in the range of 1-4 nm with an average size of 2.6 nm. UV-vis spectroscopy measurements verified that the redox reaction between PtCl62- and formaldehyde took place with a slow rate at ambient temperature via a two-step reaction path, where PtCl42- serves as an intermediate. The use of the short-time-impregnated 40 wt% Pt/C as cathode electrocatalysts in direct methanol fuel cells yields better performance than that of commercial 40 wt% Pt/C electrocatalyst. Experimental evidence provides clues for the fundamental understanding of elementary steps of the redox reactions, which helps in guiding the design and preparation of highly dispersed Pt catalyst for fuel cells.

Preparation and characterization of multiwalled carbon nanotube-supported platinum for cathode catalysts of direct methanol fuel cells

Multiwalled carbon nanotube-supported Pt (Pt/MWNT) nanocomposites were prepared by both the aqueous solution reduction of a Pt salt (HCHO reduction) and the reduction of a Pt ion salt in ethylene glycol solution. For comparison, a Pt/XC-72 nanocomposite was also prepared by the EG method. The Pt/MWNT catalyst prepared by the EG method has a high and homogeneous dispersion of spherical Pt metal particles with a narrow particle-size distribution. TEM images show that the Pt particle size is in the range of 2-5 nm with a peak at 2.6 nm, which is consistent with 2.5 nm obtained from the XRD broadening calculation. Surface chemical modifications of MWNTs and water content in EG solvent are found to be the key factors in depositing Pt particles on MWNTs. In the case of the direct methanol fuel cell (DMFC) test, the Pt/MWNT catalyst prepared by EG reduction is slightly superior to the catalyst prepared by aqueous reduction and displays significantly higher performance than the Pt/XC-72 catalyst. These differences in catalytic performance between the MWNT-supported or the carbon black XC-72-supported catalysts are attributed to a greater dispersion of the supported Pt particles when the EG method is used, in contrast to aqueous HCHO reduction and to possible unique structural and higher electrical properties when contrasting MWNTs to carbon black XC-72 as a support.

Direct determination of sialic acids in serum by capillary electrophoresis with UV detection

A novel method for the determination of N-acetylneuraminic acid (NANA) and N-glycolylneuraminic acid (NGNA) has been developed using high-performance capillary electrophoresis with UV detection at 195 nm, without pre or post-column derivatisation. The acids were separated in a 50-cm, fused-silica capillary (50 mu m i.d, 45.5-cm effective length) with Na2B4O7-Na2HPO4 buffer. The detection limit for NANA is a concentration of 9.6 x 10(-6) M or, in terms of mass: 3.879 x 10(-14) mol (39 fmol). This method is applicable to determination of NANA in normal human serum. The results were also compared with those of the colorimetrie method.

Sulfonated poly(ether ether ketone)/clay-SO3H hybrid proton exchange membranes for direct methanol fuel cells Journal of Power Sources

A new type of sulfonated clay (clay-SO3H) was prepared by the ion exchange method with the sulfanilic acid as the surfactant agent. The grafted amount of sulfanilic acid in clay-SO3H was 51.8 mequiv. (100 g)(-1), which was measured by thermogravimetric analysis (TGA). Sulfonated poly(ether ether ketone) (SPEEK)/clay-SO3H hybrid membranes which composed of SPEEK and different weight contents of clay-SO3H, were prepared by a solution casting and evaporation method. For comparison, the SPEEK/clay hybrid membranes were produced with the same method.

Nanocomposite based on depositing platinum nanostructure onto carbon nanotubes through a one-pot, facile synthesis method for amperometric sensing

Platinum nanoparticles (Pt NPs) were deposited onto multi-walled carbon nanotubes (MWNTs) through direct chemical reduction without any other stabilizing agents. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry were employed to characterize the morphology of the as-prepared nanocomposite (noted as Pt NPs-MWNTs) and further identify the Pt NPs on the surface of MWNTs. The nanocomposite demonstrated the ability to electrocatalyze the oxidation of hydrogen peroxide and substantially raises the response current. A sensitivity of 591.33 mu A mM(-1) cm(-2) was obtained at Pt NPs-MWNTs modified electrode. Thus, we immobilized glucose oxidase (GOD) as a model enzyme on the nanocomposite-based electrode with a thin layer of Nafion to fabricate a glucose biosensor, which showed sensitive and fast response to glucose. The influence of the GOD loading was investigated and the biosensor with an enzyme loading concentration of 10 mg/mL shows optimal performance for glucose detection, that is, a detection limit of 3 mu M and a response time of 3 s, respectively.

Direct synthesis of ordered N-methylimidazolium functionalized mesoporous silica as highly efficient anion exchanger of Cr(VI)

Ordered N-methylimidazolium functionalized mesoporous silica (SBA-15) anion exchangers were directly synthesized by co-condensation of tetraethoxysilane with 1-methyl-3(triethoxysilylpropyl)imidazolium chloride. The prepared samples with rod-like morphology showed high surface areas (> 400 m(2) g(-1)), well-ordered pores (> 58 angstrom), and excellent thermal stability up to 387 degrees C. The adsorption behaviors of Cr(VI) from aqueous solution on the anion exchangers were studied using the batch method. The anion exchangers had high adsorption capacity ranging from 50.8 to 90.5 mg g(-1), over a wider pH range (1-8) than amino functionalized mesoporous silica. The adsorption rate was fast, and the maximum adsorption was obtained at pH 4.6. The adsorption data for the anion exchangers were consistent with the Langmuir isotherm equation. Most active sites of the anion exchangers were easily accessible. The mixed solution of 0.1 mol L-1 NH3 center dot H2O and 0.5 mol L-1 NH4Cl was effective desorption solution, and 95% of Cr(VI) could be desorbed.

Controllable synthesis of pd nanocatalysts for direct formic acid fuel cell (DFAFC) application: From pd hollow nanospheres to pd nanoparticles

The controllable synthesis of nanosized carbon-supported Pd catalysts through a surface replacement reaction (SRR) method is reported in this paper. Depending on the synthesis conditions the Pd can be formed on Co nanoparticles surface in hollow nanospheres or nanoparticles structures. Citrate anion acts as a stabilizer for the nanostructures, and protonation of the third carboxyl anion and hence the nanostructure and size of the resulting catalysts are controlled via the pH of the synthesis solution. Pd hollow nanospheres, containing smaller Pd nanoparticles, supported on carbon are formed under the condition of pH 9 reaction solution. Meanwhile, highly dispersed carbon-supported Pd nanoparticles can be formed with higher pH (pH >= 10). All catalysts prepared through the SRR method show enhanced activities for the HCOOH electro-oxidation reaction compared to catalysts reduced by NaBH4.

Synthesis of AgCl/PAN composite nanofibres using an electrospinning method

A new route based on electrospinning is designed for the preparation of silver chloride/polyacrylonitrile (AgCl/PAN) composite nanofibres. The AgCl nanoparticles uniform in size, were dispersed on the surfaces of the composite nanofibres. Transmission electron microscopy (TEM) images gave direct evidence of the structure. X-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD) confirmed the presence of AgCl crystals.

Electrochemiluminescence detection with integrated indium tin oxide electrode on electrophoretic microchip for direct bioanalysis of lincomycin in the urine

In this article, an antibiotic, lincomycin was determined in the urine sample by microchip capillary electrophoresis (CE) with integrated indium tin oxide (ITO) working electrode based on electrochemiluminescence (ECL) detection. This microchip CE-ECL system can be used for the rapid analysis of lincomycin within 40 s. Under the optimized conditions, the linear range was obtained from 5 to 100 muM with correlation coefficient of 0.998. The limit of detection (LOD) of 3.1 muM was obtained for lincomycin in the standard solution. We also applied this method to analyzing lincomycin in the urine matrix. The limit of detection of 9.0 muM was obtained. This method can determine lincomycin in the urine sample without pretreatment, which demonstrated that it is a promising method of detection of lincomycin in clinical and pharmaceutical area.

Direct patterning of polymer-based photo luminescent structures with a mask

We report a simple method to directly pattern polymer-based photo luminescent material, i.e. a prepatterned mask is placed a close distance above it. The final structure is a positive replica of the lateral structures in the mask with submicrometer resolution. The comparison of luminescence efficiency before and after patterning indicates almost no degradation in optical property of the material during the experiments. The mechanism of pattern formation is also discussed.

Direct electrochemistry and bioelectrocatalysis of horseradish peroxidase immobilized on active carbon

For the first time horseradish peroxidase (HRP) immobilized on the surface of active carbon powder modified at the surface of a glassy carbon electrode has been shown to undergo a direct quasi-reversible electrochemical reaction. Its formal potential, E-o/, is -0.363 V in phosphate buffer solution (pH 6.8) at a scan rate of 100 mV/s and is almost independent of the scan rate in the range of 50-700 mV/s. The dependence of E-o/ on the pH of the buffer solution indicated that the conversion of HRP-Fe(III)/HRP-Fe(II) is a one-electron-transfer reaction process coupled with one-proton-transfer. The experimental results also demonstrated that the immobilized HRP retained its bioelectrocatalytic activity to the reduction of H2O2. Furthermore, the HRP adsorbed oil the surface of the active carbon powder can be stored at 4 degreesC for several months without any loss of the enzyme activity. The method presented for immobilizing HRP can be easily extended to immobilize and obtain the direct electrochemistry of other enzymes.

Immobilization and direct electrochemistry of copper-containing enzymes on active carbon

Two typical and important copper-containing enzymes, laccase (Lac) and tyrosinase (Tyr), have been immobilized on the surface of active carbon with simple adsorption method. The cyclic voltammetric results indicated that the active carbon could promote the direct electron transfer of both Lac and Tyr and a pair of well-defined and nearly symmetric redox peaks appeared on the cyclic voltammograms of Lac or Tyr with the formal potential, E-0', independent on the scan rate. The further experimental results showed that the immobilized copper-containing oxidase displayed an excellent electrocatalytic activity to the electrochemical reduction of O-2. The immobilization method presented here has several advantages, such as simplicity, easy to operation and keeping good activity of enzyme etc., and could be further used to study the direct electrochemistry of other redox proteins and enzymes and fabricate the catalysts for biofuel cell.