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1

Tris(2,2prime-bipyridyl)ruthenium(II) Electrogenerated Chemiluminescence Sensor Based on Platinized Carbon Nanotube-Zirconia-Nafion Composite Films  

British Library Electronic Table of Contents (United Kingdom)

Mesoporous films of platinized carbon nanotube-zirconia-Nafion composite have been used for the immobilization of tris(2,2prime-bipyridyl)ruthenium (II) (Ru(bpy)32+) on an electrode surface to yield a solid-state electrogenerated chemiluminescence (ECL) sensor. The composite films of Pt-CNT-zirconia-Nafion exhibit much larger pore diameter (3.55 nm) than that of Nafion (2.82 nm) and thus leading to much larger ECL response for tripropylamine (TPA) because of the fast diffusion of the analyte within the films. Due to the conducting and electrocatalytic features of CNTs and Pt nanoparticles, their incorporation into the zirconia-Nafion composite films resulted in the decreased electron transfer resistance within the films. The present ECL sensor based on the Pt-CNT-zirconia-Nafion gave a lin...

2010-01-01

2

Tris(2,2'-bipyridyl)ruthenium(II) electrogenerated chemiluminescence sensor based on carbon nantube dispersed in sol-gel-derived titania-Nafion composite films  

International Nuclear Information System (INIS)

A highly sensitive and stable tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)_3 "2"+) electrogenerated chemiluminescence (ECL) sensor was developed based on carbon nanotube (CNT) dispersed in mesoporous composite films of sol-gel titania and perfluorosulfonated ionomer (Nafion). Single-wall (SWCNT) and multi-wall carbon nanotubes (MWCNT) can be easily dispersed in the titania-Nafion composite solution. The hydrophobic CNT in the titania-Nafion composite films coated on a glassy carbon electrode certainly increased the amount of Ru(bpy)_3 "2"+ immobilized in the ECL sensor by adsorption of Ru(bpy)_3 "2"+ onto CNT surface, the electrocatalytic activity towards the oxidation of hydrophobic analytes, and the electronic conductivity of the composite films. Therefore, the present ECL sensor based on the CNT-titania-Nafion showed improved ECL sensitivity for tripropylamine (TPA) compared to the ECL sensors based on ...

2006-04-13

3

Tris(2,2'-bipyridyl)ruthenium(II) electrogenerated chemiluminescence sensor based on carbon nantube dispersed in sol-gel-derived titania-Nafion composite films  

Energy Technology Data Exchange (ETDEWEB)

A highly sensitive and stable tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy){sub 3} {sup 2+}) electrogenerated chemiluminescence (ECL) sensor was developed based on carbon nanotube (CNT) dispersed in mesoporous composite films of sol-gel titania and perfluorosulfonated ionomer (Nafion). Single-wall (SWCNT) and multi-wall carbon nanotubes (MWCNT) can be easily dispersed in the titania-Nafion composite solution. The hydrophobic CNT in the titania-Nafion composite films coated on a glassy carbon electrode certainly increased the amount of Ru(bpy){sub 3} {sup 2+} immobilized in the ECL sensor by adsorption of Ru(bpy){sub 3} {sup 2+} onto CNT surface, the electrocatalytic activity towards the oxidation of hydrophobic analytes, and the electronic conductivity of the composite films. Therefore, the present ECL sensor based on the CNT-titania-Nafion showed improved ECL sensitivity for tripropylamine (TPA) ...

2006-04-13

4

Tris(2,2prime-bipyridyl)ruthenium(II) Electrogenerated Chemiluminescence Sensor Based on Sol-Gel-Derived V2O5/Nafion Composite Films  

British Library Electronic Table of Contents (United Kingdom)

Mesoporous V2O5/Nafion composite films have been used for the immobilization of tris(2,2prime-bipyridyl)ruthenium (II) (Ru(bpy)$\\rm{ {_{3}^{2+}}}$) on an electrode surface to yield a solid-state electrogenerated chemiluminescence (ECL) sensor. The electrochemical and ECL behavior of Ru(bpy)$\\rm{ {_{3}^{2+}}}$ ion-exchanged into the composite films has been characterized as a function of the amount of Nafion incorporated into the V2O5/Nafion composite. The composite film with 80% Nafion content has the largest pore diameter (4.19 nm) and yields the maximum ECL response for tripropylamine (TPA) because of the fast diffusion of analyte into the film with large pores. Due to the enlarged pore size and enhanced conductivity of the V2O5/Nafion composite, the present ECL sensor based on the compo...

2006-01-01

5

Tris(2,2prime-bipyridyl)ruthenium(II) electrogenerated chemiluminescence sensor based on carbon nantube dispersed in sol-gel-derived titania-Nafion composite films  

British Library Electronic Table of Contents (United Kingdom)

A highly sensitive and stable tris(2,2prime-bipyridyl)ruthenium(II) (Ru(bpy)32+) electrogenerated chemiluminescence (ECL) sensor was developed based on carbon nanotube (CNT) dispersed in mesoporous composite films of sol-gel titania and perfluorosulfonated ionomer (Nafion). Single-wall (SWCNT) and multi-wall carbon nanotubes (MWCNT) can be easily dispersed in the titania-Nafion composite solution. The hydrophobic CNT in the titania-Nafion composite films coated on a glassy carbon electrode certainly increased the amount of Ru(bpy)32+ immobilized in the ECL sensor by adsorption of Ru(bpy)32+ onto CNT surface, the electrocatalytic activity towards the oxidation of hydrophobic analytes, and the electronic conductivity of the composite films. Therefore, the present ECL sensor based on the CNT-...

2006-01-01

6

Intermediates to ethylene glycol: carbonylation of formaldehyde catalyzed by Nafion solid perfluorosulfonic acid resin  

Energy Technology Data Exchange (ETDEWEB)

Details of a series of reactions for the production of ethylene glycol using a catalyst of Nafion solid perfluorosulfonic acid resin was detailed. The reactions included the carbonylation of formaldehyde and esterification and then hydrogenation of the product of the carbonylation, glycolic acid. Other preparations included in the work included methyl glycolate, acetylglycolic acid, methyl acetylglycolate, and methyl methoxyacetate.

1983-01-01

7

High resolution neutron imaging of water in the polymer electrolyte fuel cell membrane  

Energy Technology Data Exchange (ETDEWEB)

Water transport in the ionomeric membrane, typically Nafion{reg_sign}, has profound influence on the performance of the polymer electrolyte fuel cell, in terms of internal resistance and overall water balance. In this work, high resolution neutron imaging of the Nafion{reg_sign} membrane is presented in order to measure water content and through-plane gradients in situ under disparate temperature and humidification conditions.

2009-01-01

8

Electron spin resonance probe for the solvation of ionomer membranes and other microscopically heterogeneous systems. Cu[sup 2+] in nafion, sephadex and silica gel  

Energy Technology Data Exchange (ETDEWEB)

Cu[sup 2+] is a sensitive electron spin resonance (ESR) probe for the penetration of various polar solvents in membranes made of Nafion and as an indicator for the replacement of one solvent by another. The ESR parameters (g and [sup 63]Cu hyperfine tensors) can be translated into a structure of the solvent around the cation. The replacement of a solvent in the membrane by another depends on the polarity of the two solvents. The solvent with the largest dielectric constant, N-methylformamide (NMF), can be replaced by water but not by methanol or acetonitrile (dielectric constants 182, 78.5, 32.7, and 37.5, respectively). Preferential solvation of the cation by water in three water/acetonitrile mixtures (9:1, 1:1, and 1:9 by volume) in contact with silica gel, Sephadex, and Nafion has been observed in various degrees. Nafion is most selective, followed by Sephadex and by silica gel. The selectivity appears to be related to ...

1992-01-01

9

Characterization of proton exchange membrane materials for fuel cells by solid state nuclear magnetic resonance  

Energy Technology Data Exchange (ETDEWEB)

Solid-state nuclear magnetic resonance (NMR) has been used to explore the nanometer-scale structure of Nafion, the widely used fuel cell membrane, and its composites. We have shown that solid-state NMR can characterize chemical structure and composition, domain size and morphology, internuclear distances, molecular dynamics, etc. The newly-developed water channel model of Nafion has been confirmed, and important characteristic length-scales established. Nafion-based organic and inorganic composites with special properties have also been characterized and their structures elucidated. The morphology of Nafion varies with hydration level, and is reflected in the changes in surface-to-volume (S/V) ratio of the polymer obtained by small-angle X-ray scattering (SAXS). The S/V ratios of different Nafion models have been evaluated numerically. It has been found that only the water channel ...

2010-03-15

10

Atomistic Simulation of Water Percolation and Proton Hopping in Nafion Fuel Cell Membrane  

Energy Technology Data Exchange (ETDEWEB)

We have performed a detailed analysis of water clustering and percolation in hydrated Nafion configurations generated by classical molecular dynamics simulations. Our results show that at low hydration levels H2O molecules are isolated and a continuous hydrogen-bonded network forms as the hydration level is increased. Our quantitative analysis has established a hydration level (?) between 5 and 6 H2O/SO3- as the percolation threshold of Nafion. We have also examined the effect of such a network on proton transport by studying the structural diffusion of protons using the quantum hopping molecular dynamics method. The mean residence time of the proton on a water molecule decreases by two orders of magnitude when the ? value is increased from 5 to 15. The proton diffusion coefficient in Nafion at a ? value of 15 is about 1.1x10-5 cm2/s in agreement with experiment. The results provide quantitative atomic-level evidence of ...

2010-11-04

11

Characterisation of a re-cast composite Nafion 1100 series of proton exchange membranes incorporating inert inorganic oxide particles  

International Nuclear Information System (INIS)

A series of cation exchange membranes was produced by impregnating and coating both sides of a quartz web with a Nafion solution (1100 EW, 10%wt in water). Inert filler particles (SiO_2, ZrO_2 or TiO_2; 5-20%wt) were incorporated into the aqueous Nafion solution to produce robust, composite membranes. Ion-exchange capacity/equivalent weight, water take-up, thickness change on hydration and ionic and electrical conductivity were measured in 1 mol dm"-"3 sulfuric acid at 298 K. The TiO_2 filler significantly impacted on these properties, producing higher water take-up and increased conductivity. Such membranes may be beneficial for proton exchange membrane (PEM) fuel cell operation at low humidification. The PEM fuel cell performance of the composite membranes containing SiO_2 fillers was examined in a Ballard Mark 5E unit cell. While the use of composite membranes offers a cost reduction, the unit cell performance was reduced, in practice, due ...

2010-09-01

12

Hygro-thermal mechanical behavior of Nafion during constrained swelling  

British Library Electronic Table of Contents (United Kingdom)

Durability is a major limitation of current proton exchange membrane fuel cells. Mechanical stress due to hygro-thermal cycling is one failure mechanism of the polymer electrolyte membrane. In previous work the cyclic rate, temperature, and hydration dependent elastic-viscoplastic mechanical behavior of Nafion has been extensively investigated in uniaxial and biaxial tension, serving as a data basis and means of validation for a three-dimensional constitutive model. Here, the important effect of loading via constrained swelling is studied. Specifically, two types of loading are investigated: partially constrained swelling via a bimaterial swelling test and hygro-thermal cycling within a fuel cell. The bimaterial swelling conditions are examined via experiments in conjunction with modeling....

2011-01-01

13

Conductivity studies on commercially available proton-conducting membranes with different equivalent weight  

Energy Technology Data Exchange (ETDEWEB)

Two perfluorosulfonic acid membranes, Nafion{sup R} 105 and Nafion{sup R} 115 with the same thickness but different equivalent weights (EW = 1000 g/eq. resp. 1100 g/eq.) were characterised by conductivity measurements at different water vapour activities in the temperature range of 25-70{sup o}C. The results demonstrate that a lower membrane equivalent weight opens the possibility to obtain the needed proton conductivity at lower water vapour activity. This is especially important for those fuel cell applications, in which the cell is operated without external humidification of the fuel gases. (author) 5 figs., 5 refs.

1999-08-01

14

In-plane resolved in-situ measurements of the membrane resistance in PEFCs  

Energy Technology Data Exchange (ETDEWEB)

The conductivity of the membrane is a limiting factor for the efficiency and power density of PEFCs. Because this conductivity is strongly dependent on the membrane hydration, water management is an important aspect of PEFC optimisation. Single cell model experiments were made in order to determine the in-plane hydration of a Nafion{sup R} membrane under fuel cell conditions as function of the gas humidities. (author) 4 fig., 3 refs.

1999-08-01

15

Proton exchange membrane materials for the advancement of direct methanol fuel-cell technology  

Science.gov (United States)

A new class of hybrid organic-inorganic materials, and methods of synthesis, that can be used as a proton exchange membrane in a direct methanol fuel cell. In contrast with Nafion.RTM. PEM materials, which have random sulfonation, the new class of materials have ordered sulfonation achieved through self-assembly of alternating polyimide segments of different molecular weights comprising, for example, highly sulfonated hydrophilic PDA-DASA polyimide segment alternating with an unsulfonated hydrophobic 6FDA-DAS polyimide segment. An inorganic phase, e.g., 0.5 5 wt % TEOS, can be incorporated in the sulfonated polyimide copolymer to further improve its properties. The new materials exhibit reduced swelling when exposed to water, increased thermal stability, and decreased O.sub.2 and H.sub.2 gas permeability, while retaining proton conductivities similar to Nafion.RTM.. These improved properties may allow direct methanol fuel cells to operate at ...

2006-04-04

16

Preparation of new proton exchange membrane based on self-assembly of poly(styrene-co-styrene sulfonic acid)-b-poly(methyl methacrylate)/poly(vinylidene fluoride) blend  

Energy Technology Data Exchange (ETDEWEB)

Amphiphilic block copolymers are synthesized by sulfonation of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) using acetyl sulfate, and are blended with poly(vinylidene fluoride) (PVDF) to prepare a new proton exchange membrane, in which PMMA is miscible with PVDF. The morphology and the transport properties of the membranes are investigated as functions of the degree of sulfonation as well as the blend ratio. Notable transition of phase-separated morphology is observed as the PVDF content of the blend is increased. Both the proton conductivity and the ion-exchange capacity (IEC) of the membrane increase with increasing the degree of sulfonation of PS-b-PMMA, and they are also enhanced as the phase-separated domains of blend membrane are well-ordered. Unlike the Nafion membrane, the proton conductivity of the blend membrane increases up to 90 C, indicating the blend membrane shows better thermal stability than the Nafion membrane. (author)

2009-03-01

17

Electrogenerated chemiluminescence sensor for metoclopramide determination based on Ru(bpy)32+-doped silica nanoparticles dispersed in Nafion on glassy carbon electrode  

British Library Electronic Table of Contents (United Kingdom)

A novel method for the determination of metoclopramide (MCP) using electrogenerated chemiluminescence (ECL) is presented. A tris(2,2prime-bipyridyl)dichlororuthenium(II) (Ru(bpy)32+)-doped silica (RuDS) nanoparticle/perfluoinated ion-exchange resin (Nafion) with nanocomposite membrane modified glassy carbon electrode (GCE) is used. The Ru(bpy)32+ encapsulation interior of the silica nanoparticle maintains its electrochemical activities and also reduces Ru(bpy)32+ leaching from the silica matrix when immersed in water due to the electrostatic interaction. The analytical performance of this ECL sensor for MCP is shown in detail. Under optimal experimental conditions, it has good linearity in the concentration range from 2x10-8mol/L to 1x10-5mol/L (R=0.9989) with a detection limit of 7x10-9mo...

2008-01-01

18

Photoassisted hydrogen generation by integrated electroactive SPE membrane system  

Energy Technology Data Exchange (ETDEWEB)

Incorporation of TiO{sub 2}, into perfluoroionomer membrane by treatment with TiC1{sub 4}-methanol has been described. Platinum was used as an electrocatalyst. In order to make the system electronically as well as ionically conducting, the electrode was modified with polypyrrole (PPy). Photopolymerisation of pyrrole was accomplished by immersing TiO{sub 2}-Pt-NaF in pyrrole solution. UV-visible and FT-IR Spectroscopic studies were preformed with regards to the formation of the TiO{sub 2}, Pt and PPy within Nafion matrix. We report the construction and evaluation of this integrated system and establish the feasibility of hydrogen generation thereof. (Author)

2000-04-01

19

Preparation of cost-effective Pt-Co electrodes by pulse electrodeposition for PEMFC electrocatalysts  

International Nuclear Information System (INIS)

Graphical abstract: - Abstract: Low loading platinum-cobalt (Pt-Co) cathode catalyst on a Nafion(Na+)-bonded carbon layer is fabricated by using galvanostatic pulse technique to show the advantage of electrodeposition for high utilization of catalyst in proton exchange membrane fuel cell (PEMFC). We observed that Pt-Co catalysts evenly exist on the surface of carbon electrode and its thickness is about 5.8 ?m, which is four times thinner than conventional Pt/C. Improved single cell power performance of Pt-Co cathode catalysts with a ratio of 3.2:1 compared with Pt/C is clearly presented.

2011-03-01

20

Electrolytic membrane formation of fluoroalkyl polymer using a UV-radiation-based grafting technique and sulfonation  

Science.gov (United States)

A sulfonated fluoroalkyl graft polymer (FGP) membrane was prepared as a polymer electrolyte. First, the FGP membrane was grafted with styrene under UV irradiation. The grafted FGP was then sulfonated to functionalize it for proton conductivity. The grafting degree of the membrane increased with increasing grafting time during UV irradiation. The proton conductivity of the membrane increased with increasing grafting degree. The swelling ratio was independent of the grafting time, however, the water uptake increased with increasing grafting degree. Based on these results, it was found that the UV-initiated styrene grafting occurred along the membrane thickness direction. Moreover, the membrane was embedded within the glass fibers of the composite. This composite electrolytic membrane had 1.15 times the proton conductivity of a Nafion 117 membrane.

2011-03-01

 
 
 
 
21

Isobutane/2-butene alkylation over potential heterogeneous catalysts in a slurry reactor  

Energy Technology Data Exchange (ETDEWEB)

The trend towards more effective use of fossil fuels and reduced environmental pollution represents a major task of improvement within the refinery processes. The highly isomerized and high octane paraffins produced from isobutane and light olefins by alkylation fulfill all the requirements for reformulated gasoline. This doctoral thesis discusses new catalyst systems because of their potential in alkylation. A slurry reactor apparatus for solid-acid catalysed isobutane/butene alkylation was developed and used to investigate the performance of various heterogeneous catalysts. The selected materials were mainly zeolite types with faujasite structures. The samples were characterized by various methods before alkylation. In general, the order of decreasing catalyst activity after 3 h of reaction at 80{sup o}C was found to be: H-EMT >> H-FAU, dealuminated H-FAU >> NS.500, TA-Y, CeY-98 > Nafion-H. The order of decreasing alkylate selectivity of the ...

1996-12-31

22

Physicochemical study of poly(ether ether ketone) electrolyte membranes sulfonated with mixtures of fuming sulfuric acid and sulfuric acid for direct methanol fuel cell application  

International Nuclear Information System (INIS)

Sulfonated poly(ether ether ketone) (SPEEK) membranes with various degrees of sulfonation (DS) have been prepared as a potential membrane material for proton exchange membrane by sulfonation process using mixtures of (15-30% concentration) fuming sulfuric acid and (95-98%) concentrated sulfuric acid as the sulfonating agent. The sulfonation process was conducted at room temperature by varying the acid ratio and reaction time. The produced membranes were then characterized by evaluating the ion exchange capacity (IEC), water uptake, thermal stability, proton conductivity and methanol permeability as a function of degree of sulfonation. The proton conductivity of the sulfonated PEEK membranes with various DS was within the magnitude of 10"-"3 and 10"-"2 S cm"-"1 at room temperature and the methanol permeability was in the range of 3.45 x 10"-"7 to 2.73 x 10"-"6 cm"2 s"-"1. The overall membrane performance of the SPEEK membrane with 80% DS was six times higher than ...

2007-07-15

23

Sol-gel-immobilized Tris(2,2'-bipyridyl)ruthenium(II) electrogenerated chemiluminescence sensor for high-performance liquid chromatography  

International Nuclear Information System (INIS)

The sol-gel-immobilized Tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)_3 "2"+] electrogenerated chemiluminescence (ECL) sensor was applied to the reversed-phase high-performance liquid chromatography (HPLC) determination of phenothiazine derivatives (promazine, chlorpromazine, triflupromazine, thioridazine, and trifluoperazine) and erythromycin in human urine samples. In this method, Ru(bpy)_3 "2"+ was immobilized in sol-gel-derived titania (TiO_2)-Nafion nanocomposite films coated on a dual platinum electrode. This method eliminates an extra pump needed for the delivery of Ru(bpy)_3 "2"+ reagent into a reaction/observation zone in front of photomultiplier tube because the immobilized-Ru(bpy)_3 "2"+ is recycled on the electrode surface by an applied potential at +1.3 V versus Ag/AgCl (3 M NaCl) reference electrode. The resulting analytical performances such as detection limit, working range, sensitivity, and measurement precision were slightly worse than those obtained ...

2005-06-13

24

Sol-gel-immobilized Tris(2,2'-bipyridyl)ruthenium(II) electrogenerated chemiluminescence sensor for high-performance liquid chromatography  

Energy Technology Data Exchange (ETDEWEB)

The sol-gel-immobilized Tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy){sub 3} {sup 2+}] electrogenerated chemiluminescence (ECL) sensor was applied to the reversed-phase high-performance liquid chromatography (HPLC) determination of phenothiazine derivatives (promazine, chlorpromazine, triflupromazine, thioridazine, and trifluoperazine) and erythromycin in human urine samples. In this method, Ru(bpy){sub 3} {sup 2+} was immobilized in sol-gel-derived titania (TiO{sub 2})-Nafion nanocomposite films coated on a dual platinum electrode. This method eliminates an extra pump needed for the delivery of Ru(bpy){sub 3} {sup 2+} reagent into a reaction/observation zone in front of photomultiplier tube because the immobilized-Ru(bpy){sub 3} {sup 2+} is recycled on the electrode surface by an applied potential at +1.3 V versus Ag/AgCl (3 M NaCl) reference electrode. The resulting analytical performances such as detection limit, working range, sensitivity, and measurement ...

2005-06-13

25

Probing anodic reaction kinetics and interfacial mass transport of a direct formic acid fuel cell using a nanostructured palladium-gold alloy microelectrode  

International Nuclear Information System (INIS)

The anodic reaction kinetics and interfacial mass transport of a direct polymer electrolyte membrane formic acid fuel cell have been investigated in an all solid-state electrochemical cell using a highly active nanostructured palladium-gold alloy microelectrode as an in situ probe. Well-defined 'S-shaped' steady-state cyclic voltammograms exhibiting current-rising region at lower overpotentials and limiting current region at higher overpotentials have been first obtained for the electrochemical oxidation of formic acid at varying temperature. The 'S-shaped' steady state polarization curves and chronoamperometric curves enable convenient measurements of the anodic reaction kinetics and interfacial mass transport of formic acid under real polymer electrolyte membrane conditions. It is encouragingly found that formic acid can be directly oxidized to CO2 with the first electron transfer being the likely rate-determining step and the formation of surface poison can be neglected. The ...

2009-07-30