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Sample records for acid doped polybenzimidazole

  1. Acid doped polybenzimidazoles, a new polymer electrolyte

    Wainright, J.S.; Wang, J.T.; Savinell, R.F.; Litt, M.; Moaddel, H.; Rogers, C. [Case Western Reserve Univ., Cleveland, OH (United States)

    1994-12-31

    Polybenzimidazole films doped with phosphoric acid are being investigated as potential polymer electrolytes for use in hydrogen/air and direct methanol fuel cells. The advantages of this electrolyte include good mechanical properties, and low vapor permeability. Combined, these factors allow for the use of thin (< 0.005 cm) membranes in fuel cells without excessive adverse effects from fuel gas crossover to the cathode compartment and subsequent cathode depolarization. In this paper the authors discuss experimental data on the proton conductivity, thermal stability and gas permeability of this material.

  2. Acid-doped polybenzimidazoles: A new polymer electrolyte

    Wainright, J.S.; Wang, J.T.; Weng, D.; Savinell, R.F.; Litt, M. [Case Western Reserve Univ., Cleveland, OH (United States)

    1995-07-01

    Polybenzimidazole films doped with phosphoric acid are being investigated as potential polymer electrolytes for use in hydrogen/air and direct methanol fuel cells. In this paper, the authors present experimental findings on the proton conductivity, water content, and methanol vapor permeability of this material, as well as preliminary fuel cell results. The low methanol vapor permeability of these electrolytes significantly reduces the adverse effects of methanol crossover typically observed in direct methanol polymer electrolyte membrane fuel cells.

  3. Durability Issues of High Temperature Proton Exchange Membrane Fuel Cells Based on Acid Doped Polybenzimidazole Membranes

    To achieve high temperature operation of proton exchange membrane fuel cells (PEMFC), preferably under ambient pressure, phosphoric acid doped polybenzimidazole (PBI) membrane represents an effective approach, which in recent years has motivated extensive research activities with great progress. As...

  4. Physicochemical properties of phosphoric acid doped polybenzimidazole membranes for fuel cells

    He, Ronghuan; Li, Qingfeng; Bach, Anders;

    2006-01-01

    Polybenzimidazole (PBI) membranes have been prepared with different molecular weights. The water and acid swelling, mechanical strength,gas permeability and proton conductivity were studied for the pristine and acid doped PBI membranes. When doped with 5 mol of phosphoric acid per mole repeat unit...

  5. Water Uptake and Acid Doping of Polybenzimidazoles as Electrolyte Membranes for Fuel Cells

    Qingfeng, Li; He, R.; Berg, Rolf W.; Hjuler, Hans Aage; Bjerrum, Niels J.

    Acid-doped polybenzimidazole (PBI) membranes have been demonstrated for fuel cell applications with advanced features such as high operating temperatures, little humidification, excellent CO tolerance, and promising durability. The water uptake and acid doping of PBI membranes have been studied...

  6. Proton conductivity of phosphoric acid doped polybenzimidazole and its composites with inorganic proton conductors

    He, Ronghuan; Qingfeng, Li; Gang, Xiao;

    2003-01-01

    Phosphoric acid doped polybenzimidazole (PBI) and PBI composite membranes have been prepared in the present work. The PBI composites contain inorganic proton conductors including zirconium phosphate (ZrP), (Zr(HPO4)2·nH2O), phosphotungstic acid (PWA), (H3PW12O40·nH2O) and silicotungstic acid (Si...

  7. Catalyst Degradation in High Temperature Proton Exchange Membrane Fuel Cells Based on Acid Doped Polybenzimidazole Membranes

    Cleemann, Lars Nilausen; Buazar, F.; Li, Qingfeng; Jensen, Jens Oluf; Pan, Chao; Steenberg, T.; Dai, S.; Bjerrum, Niels J.

    2013-01-01

    Degradation of carbon supported platinum catalysts is a major failure mode for the long term durability of high temperature proton exchange membrane fuel cells based on phosphoric acid doped polybenzimidazole membranes. With Vulcan carbon black as a reference, thermally treated carbon black and...

  8. Doping phosphoric acid in polybenzimidazole membranes for high temperature proton exchange membrane fuel cells

    He, Ronghuan; Li, Qingfeng; Jensen, Jens Oluf;

    2007-01-01

    Polybenzimidazole (PBI) membranes were doped in phosphoric acid solutions of different concentrations at room temperature. The doping chemistry was studied using the Scatchard method. The energy distribution of the acid complexation in polymer membranes is heterogeneous, that is, there are two...... different types of sites in PBI for the acid doping. The protonation constants of PBI by phosphoric acid are found to be 12.7 L mol(-1) (K-1) for acid complexing sites with higher affinity, and 0.19 L mol(-1) (K-2) for the sites with lower affinity. The dissociation constants for the complexing acid onto...... these two types of PBI sites are found to be 5.4 X 10(-4) and 3.6 X 10(-2), respectively, that is, about 10 times smaller than that of aqueous phosphoric acid in the first case but 5 times higher in the second. The proton conducting mechanism is also discussed....

  9. Water uptake and acid doping of polybenzimidazoles as electrolyte membranes for fuel cells

    Li, Qingfeng; He, Ronghuan; Berg, Rolf W.; Hjuler, Hans A.; Bjerrum, Niels J. [Department of Chemistry, Technical University of Denmark, DK-2800 Lyngby (Denmark)

    2004-03-15

    Acid-doped polybenzimidazole (PBI) membranes have been demonstrated for fuel cell applications with advanced features such as high operating temperatures, little humidification, excellent CO tolerance, and promising durability. The water uptake and acid doping of PBI membranes have been studied. The water uptake of PBI from the vapour phase is only slightly increased as the atmospheric humidity increases up to unity (100%). Little difference is observed for the water uptake from vapour and liquid phases, behaving very differently from Nafion membranes. When doped with phosphoric acid at low levels (<2), the active sites of the imidazole ring are preferably occupied by the doping acid and the water uptake is consequently lower. At higher acid doping levels, the water uptake is influenced by the excess of hygroscopic acid and higher water uptake than for Nafion membranes is observed. Upon doping, the acid is found to be concentrated inside the polymer. Only two molecules of phosphoric acid are bonded to each repeat unit of PBI, corresponding to the two nitrogen sites available. Infrared and Raman spectra show the presence of strong hydrogen bonds between phosphoric acid and nitrogen atoms of the imidazole rings. The excessive doping acid is 'free acid' that contributes to high conductivity but suffers from a fast washing out when adequate liquid is present.

  10. Phosphoric acid doped polybenzimidazole membranes: Physiochemical characterization and fuel cell applications [PEM fuel cells

    Qingfeng, Li; Hjuler, Hans Aage; Bjerrum, Niels

    2001-01-01

    A polymer electrolyte membrane fuel cell operational at temperatures around 150-200 degrees C is desirable for fast electrode kinetics and high tolerance to fuel impurities. For this purpose polybenzimidazole (PBI) membranes have been prepared and H/sub 3/PO/sub 4/-doped in a doping range from 30...

  11. Lowering the platinum loading of high temperature polymer electrolyte membrane fuel cells with acid doped polybenzimidazole membranes

    Fernandez, Santiago Martin; Li, Qingfeng; Jensen, Jens Oluf

    2015-01-01

    Membrane electrode assemblies (MEAs) with ultra-low Pt loading electrodes were prepared for high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) based on acid doped polybenzimidazole. With no electrode binders or ionomers, the triple phase boundary of the catalyst layer was...... established by the acid transfer from the acid doped membrane to the electrodes and can therefore be tailored by using catalysts with varied Pt to C ratios. With a loading of ca. 0.1 mgPtcm-2 on each electrode the best performance was obtained with electrodes prepared from 10 wt.% Pt/C due to the improved Pt...

  12. Porous polybenzimidazole membranes doped with phosphoric acid: Preparation and application in high-temperature proton-exchange-membrane fuel cells

    Highlights: • Porous polybenzimidazole membrane was prepared with glucose as porogen. • Phosphoric acid content was as high as 15.7 mol H3PO4 per PBI repeat unit. • 200 h Constant current density test was carried out at 150 °C. • Degradation was due to the gap between membrane and catalyst layer. - Abstract: In this paper, the preparation and characterization of porous polybenzimidazole membranes doped with phosphoric acid were reported. For the preparation of porous polybenzimidazole membranes, glucose and saccharose were selected as porogen and added into PBI resin solution before solvent casting. The prepared porous PBI membranes had high proton conductivity and high content of acid doping at room temperature with 15.7 mol H3PO4 per PBI repeat unit, much higher than pure PBI membrane at the same condition. Further, the performance and stability of the porous PBI membrane in high-temperature proton-exchange-membrane fuel cells was tested. It was found that the cell performance remained stable during 200 h stability test under a constant current discharge of 0.5 A cm−2 except for the last fifty hours. The decay in the last fifty hours was ascribed to the delamination between the catalyst layer and membrane increasing the charge-transfer resistance

  13. Development and characterization of acid-doped polybenzimidazole/sulfonated polysulfone blend polymer electrolytes for fuel cells

    Hasiotis, C.; Li, Qingfeng; Deimede, V.;

    2001-01-01

    Polymeric membranes from blends of sulfonated polysulfones (SPSF) and polybenzimidazole (PBI) doped with phosphoric acid were developed as potential high-temperature polymer electrolytes for fuel cells and other electrochemical applications. The water uptake and acid doping of these polymeric...... was found to be higher than 10/sup -2/ S cm/sup -1/. Much improvement in the mechanical strength is observed for the blend polymer membranes, especially at higher temperatures. Preliminary work has demonstrated the feasibility of these polymeric membranes for fuel-cell applications...... membranes were investigated. Ionic conductivity of the membranes was measured in relation to temperature, acid doping level, sulfonation degree of SPSF, relative humidity, and blend composition. The conductivity of SPSF was of the order of 10/sup -3/ S cm/sup -1/. In the case of blends of PBI and SPSF it...

  14. The effect of porosity on performance of phosphoric acid doped polybenzimidazole polymer electrolyte membrane fuel cell

    Celik Muhammet

    2016-01-01

    Full Text Available A polybenzimidazole (PBI based polymer electrolyte fuel cells, which called high temperature polymer electrolyte fuel cells (HT-PEMS, operate at higher temperatures (120-200°C than conventional PEM fuel cells. Although it is known that HT-PEMS have some of the significant advantages as non-humidification requirements for membrane and the lack of liquid water at high temperature in the fuel cell, the generated water as a result of oxygen reduction reaction causes in the degradation of these systems. The generated water absorbed into membrane side interacts with the hydrophilic PBI matrix and it can cause swelling of membrane, so water transport mechanism in a membrane electrode assembly (MEA needs to be well understood and water balance must be calculated in MEA. Therefore, the water diffusion transport across the electrolyte should be determined. In this study, various porosity values of gas diffusion layers are considered in order to investigate the effects of porosity on the water management for two phase flow in fuel cell. Two-dimensional fuel cell with interdigitated flow-field is modelled using COMSOL Multiphysics 4.2a software. The operating temperature and doping level is selected as 160°C and 6.75mol H3PO4/PBI, respectively.

  15. The effect of porosity on performance of phosphoric acid doped polybenzimidazole polymer electrolyte membrane fuel cell

    Celik, Muhammet; Genc, Gamze; Elden, Gulsah; Yapici, Huseyin

    2016-03-01

    A polybenzimidazole (PBI) based polymer electrolyte fuel cells, which called high temperature polymer electrolyte fuel cells (HT-PEMS), operate at higher temperatures (120-200°C) than conventional PEM fuel cells. Although it is known that HT-PEMS have some of the significant advantages as non-humidification requirements for membrane and the lack of liquid water at high temperature in the fuel cell, the generated water as a result of oxygen reduction reaction causes in the degradation of these systems. The generated water absorbed into membrane side interacts with the hydrophilic PBI matrix and it can cause swelling of membrane, so water transport mechanism in a membrane electrode assembly (MEA) needs to be well understood and water balance must be calculated in MEA. Therefore, the water diffusion transport across the electrolyte should be determined. In this study, various porosity values of gas diffusion layers are considered in order to investigate the effects of porosity on the water management for two phase flow in fuel cell. Two-dimensional fuel cell with interdigitated flow-field is modelled using COMSOL Multiphysics 4.2a software. The operating temperature and doping level is selected as 160°C and 6.75mol H3PO4/PBI, respectively.

  16. Acid-doped Polybenzimidazole Membranes as Electrolyte for Fuel Cells Operating Above 100°C

    Qingfeng, Li; Jensen, Jens Oluf; He, Ronhuan; Gang, Xiao; Gao, Ji-An; Berg, Rolf W.; Hjuler, Hans Aage; Hennesø, Erik; Bjerrum, Niels

    high operational temperatures, the development and evaluation of acid doped PBI membranes are reviewed, covering polymer synthesis, membrane casting, acid doping, physiochemical characterization and fuel cell tests. A high temperature PEMFC system operational at up to 200°C is demonstrated with no gas...

  17. Proton conductivity of phosphoric acid doped polybenzimidazole and its composites with inorganic protontic conductors

    Li, Qingfeng

    2003-01-01

    contain inorganic protonic conductors including zirconium phosphate (ZrP), (Zr(HPO4)2. nH2O); phosphotungstic acid (PWA), (H3PW12O40. nH2O); and silicotungstic acid (SiWA), (H4SiW12O40 . nH2O). The conductivity of phosphoric acid doped PBI and PBI composite membranes was found to be dependent on the acid...

  18. Thermal properties of phosphoric acid-doped polybenzimidazole membranes in water and methanol-water mixtures

    Nores-Pondal, Federico J.; Corti, Horacio R. [Grupo de Pilas de Combustible, Departamento de Fisica de la Materia Condensada, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica (CNEA), Av. General Paz 1499, B1650KNA San Martin, Buenos Aires (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Buera, M. Pilar [Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Departamento de Industrias, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Av. Cantilo s/n, Ciudad Universitaria (1428) Buenos Aires (Argentina)

    2010-10-01

    The thermal properties of phosphoric acid-doped poly[2-2'-(m-phenylene)-5-5' bi-benzimidazole] (PBI) and poly[2,5-benzimidazole] (ABPBI) membranes, ionomeric materials with promising properties to be used as electrolytes in direct methanol and in high temperature polymer electrolyte membrane (PEM) fuel cells, were studied by means of differential scanning calorimetry (DSC) technique in the temperature range from -145 C to 200 C. The DSC scans of samples equilibrated in water at different relative humidities (RH) and in liquid water-methanol mixtures were analyzed in relation to glass transition, water crystallization/melting and solvent desorption in different temperature regions. The thermal relaxation observed in the very low temperature region could be ascribed to the glass transition of the H{sub 3}PO{sub 4}-H{sub 2}O mixture confined in the polymeric matrix. After cooling the samples up to -145 C, frozen water was detected in PBI and ABPBI at different RH, although at 100% RH less amount of water had crystallized than that observed in Nafion membranes under the same conditions. Even more important is the fact that the freezing degree of water is much lower in ABPBI membranes equilibrated in liquid water-methanol mixtures than that observed for PBI and, in a previous study, for Nafion. Thus, apart from other well known properties, acid-doped ABPBI emerges as an excellent ionomer for applications in direct methanol fuel cells working in cold environments. (author)

  19. Performance Degradation Tests of Phosphoric Acid Doped Polybenzimidazole Membrane Based High Temperature Polymer Electrolyte Membrane Fuel Cells

    Zhou, Fan; Araya, Samuel Simon; Grigoras, Ionela;

    2015-01-01

    Degradation tests of two phosphoric acid (PA) doped PBI membrane based HT-PEM fuel cells were reported in this paper to investigate the effects of start/stop and the presence of methanol in the fuel to the performance degradation of the HT-PEM fuel cell. Continuous tests with pure dry H2 and meth......Degradation tests of two phosphoric acid (PA) doped PBI membrane based HT-PEM fuel cells were reported in this paper to investigate the effects of start/stop and the presence of methanol in the fuel to the performance degradation of the HT-PEM fuel cell. Continuous tests with pure dry H2...

  20. Performance Degradation Tests of Phosphoric Acid Doped Polybenzimidazole Membrane Based High Temperature Polymer Electrolyte Membrane Fuel Cells

    Zhou, Fan; Araya, Samuel Simon; Grigoras, Ionela; Andreasen, Søren Juhl; Kær, Søren Knudsen

    2015-01-01

    Degradation tests of two phosphoric acid (PA) doped PBI membrane based HT-PEM fuel cells were reported in this paper to investigate the effects of start/stop and the presence of methanol in the fuel to the performance degradation of the HT-PEM fuel cell. Continuous tests with pure dry H2 and...... performance during the H2 continuous tests, because of a decrease in the reaction kinetic resistance mainly in the cathode due to the redistribution of PA between the membrane and electrodes. The performance of both single cells decreased in the following tests, with highest performance decay rate in the...... corrosion of carbon support in the catalyst layer and degradation of the PBI membrane. During the continuous test with methanol containing H2 as the fuel the reaction kinetic resistance and mass transfer resistance of both single cells increased, which may be caused by the adsorption of methanol...

  1. Oxidative degradation of acid doped polybenzimidazole membranes and fuel cell durability in the presence of ferrous ions

    Liao, Jianhui; Yang, Jingshuai; Li, Qingfeng; Cleemann, Lars Nilausen; Jensen, Jens Oluf; Bjerrum, Niels J.; He, Ronghuan; Xing, Wei

    2013-01-01

    . In this study effects of phosphoric acid and ferrous ions were investigated by measurements of the weight loss, intrinsic viscosity and size exclusion chromatography (SEC) of the polymer membranes. Ferrous ions resulted in, as expected, catalytic formation of peroxide radicals and hence the...

  2. Cross-linked polybenzimidazole membranes for high temperature proton exchange membrane fuel cells with dichloromethyl phosphinic acid as a cross-linker

    Noye, Pernille; Li, Qingfeng; Pan, Chao; Bjerrum, Niels

    2008-01-01

    Phosphoric acid doped polybenzimidazole (PBI) membranes have been covalently cross-linked with dichloromethyl phosphinic acid (DCMP). FT-IR measurements showed new bands originating from bonds between the hydrogen bearing nitrogen in the imidazole group of PBI and the CH2 group in DCMP. The...

  3. Heterogeneous anion conducting membranes based on linear and crosslinked KOH doped polybenzimidazole for alkaline water electrolysis

    Aili, David; Hansen, Martin Kalmar; Renzaho, Richard Fulgence;

    2013-01-01

    Polybenzimidazole is a highly hygroscopic polymer that can be doped with aqueous KOH to give a material with high ion conductivity in the 10−2Scm−1 range, which in combination with its low gas permeability makes it an interesting electrolyte material for alkaline water electrolysis. In this study...... membranes based on linear and crosslinked polybenzimidazole were evaluated for this purpose. Extensive characterization with respect to spectroscopic and physicochemical properties during aging in 6molL−1 KOH at 85°C for up to 176 days indicated structural stability of the high molecular weight specialty...... polymer, however, with limitations with respect to hydrolytic stability. The gradual decay of the average molecular weight resulted in a severe deterioration of the mechanical properties over time. Membranes based on crosslinked polybenzimidazole showed better stability than the membranes based on their...

  4. Amino-Functional Polybenzimidazole Blends with Enhanced Phosphoric Acid Mediated Proton Conductivity as Fuel Cell Electrolytes

    Aili, David; Javakhishvili, Irakli; Han, Junyoung;

    2016-01-01

    the phosphoric acid uptake and to obtain mechanically robust membranes, the amino-functional polybenzimidazole derivative is blended with high molecular weight poly [2,2′-(m-phenylene)-5,5′-bisbenzimidazole] at different ratios. Due to the high acid uptake, the homogenous blend membranes show enhanced proton...

  5. Synthesis of proton conducting sulfonated and phosphonated polybenzimidazoles

    Ng, F.; Peron, J.; Salunke, A.; Jones, D.J.; Roziere, J. [Montpellier Univ., Montpellier (France). Lab. des Agregats Moleculaires et Materiaux Inorganiques

    2006-07-01

    A study was conducted in which a new flexible polybenzimidazoles (PBI) was synthesized with a proton conductivity higher than 10-3 S/cm at room temperature, in the absence of any unbound acid. Polybenzimidazoles are particularly robust polymers that are stable under various chemical and thermal environments. It is difficult to achieve direct sulfonation in solution of commercially available PBI, although alternative types of PBI with different solubility properties may be modified in this way. Reaction at high temperature of sulfuric acid-doped PBI membranes results in cross-linked and poorly conducting systems. Although acid-doped PBI membranes have high conductivity, acid loss occurs at temperature and load cycling in an operating fuel cell. Alternative approaches have been suggested, such as direct sulfonation and polycondensation reaction involving building blocks functionalized with protogenic groups that lead to new functionalized polybenzimidazoles with suitable properties for fuel cell application. The membrane microstructure can be modified by controlling the position, number and distribution of the sulfonic (phosphonic) acid groups along the backbone. This also affects membrane swelling and conductivity. This study also investigated the influence of the degree of protogenic group functionalization of polymer and membrane properties such as Tg, film forming properties, membrane water uptake and conductivity, and surface hydrophobic/philic properties. It was concluded that the polymer's conductivity depends on the ion exchange capacity and on the nature of the component diacids that give flexibility to the functionalized polybenzimidazole chains.

  6. A novel amperometric sensor for peracetic acid based on a polybenzimidazole-modified gold electrode

    Hua, Mu-Yi, E-mail: huamy@mail.cgu.edu.t [Green Research Center, Department of Chemical and Materials Engineering, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Biosensor Group, Biomedical Engineering Research Center, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Chen, Hsiao-Chien [Green Research Center, Department of Chemical and Materials Engineering, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Biosensor Group, Biomedical Engineering Research Center, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Tsai, Rung-Ywan [Electronics and Optoelectronics Research Laboratories, Industrial Technology Research Institute, 195, Sec. 4, Chung Hsing Rd., Hsinchu 31040, Taiwan (China); Lin, Yu-Chen [Green Research Center, Department of Chemical and Materials Engineering, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China); Biosensor Group, Biomedical Engineering Research Center, Chang Gung University, 259 Wen-Hwa 1st Rd., Kuei-Shan, Tao-Yuan 33302, Taiwan (China)

    2011-04-30

    We have developed a peracetic acid (PAA) sensor based on a polybenzimidazole-modified gold (PBI/Au) electrode. Fourier transform infrared and X-ray photoelectron spectroscopy indicated that PAA oxidized 69.4% of the imine in PBI to form PBI N-oxide, increasing the electrochemical reduction current during cyclic voltammetry. The chemical oxidation of the PBI/Au electrode by PAA, followed by its electrochemical reduction, allowed PAA to be detected directly and consecutively by assessing its reduction current. The PAA sensor had a broad linear detection range (3.1 {mu}M-1.5 mM) and a rapid response time (3.9 s) at an applied potential of -0.3 V. Potentially interfering substances, such as hydrogen peroxide, acetic acid, and oxygen, had no effect on the ability of the probe to detect PAA, indicating high selectivity of the probe. Furthermore, the detection range, response time, and sensitivity of the sensor could all be improved by modification of the smooth planar electrode surface to a porous three-dimensional configuration. When compared to the analytical characteristics of other PAA sensors operating under optimal conditions, the three-dimensional PBI/Au electrode offers a rapid detection time, a usable linear range, and a relatively low detection limit.

  7. Benzimidazole grafted polybenzimidazoles for proton exchange membrane fuel cells

    Yang, Jingshuai; Aili, David; Li, Qingfeng;

    2013-01-01

    High molecular weight polybenzimidazole (PBI) was synthesized and grafted with benzimidazole pendant groups. The high molecular weight of PBI resulted in good film-forming properties and superior tensile strength. With a phosphoric acid doping level (ADL) of 13.1, a tensile strength of 16 MPa was...... achieved at room temperature. Grafting of benzimidazole moieties onto the PBI macromolecular chain introduced additional basic sites which allowed the membrane to achieve higher phosphoric acid uptakes. A molar acid conductivity, defined as the specific conductivity of each mole of doping acid, was...

  8. Performance of a direct glycerol fuel cell using KOH doped polybenzimidazole as electrolyte

    Nascimento, Ana P.; Linares, Jose J., E-mail: joselinares@unb.br [Universidade de Brasilia (UnB), Brasilia, DF (Brazil). Instituto de Quimica

    2014-03-15

    This paper studies the influence of the operating variables (glycerol concentration, temperature and feed rate) for a direct glycerol fuel cell fed with glycerol using polybenzimidazole (PBI) impregnated with KOH as electrolyte and Pt/C as catalyst. Temperature displays a beneficial effect up to 75 °C due to the enhanced conductivity and kinetics of the electrochemical reactions. The optimum cell feed corresponds to 1 mol L{sup -1} glycerol and 4 mol L{sup -1} KOH, supplying sufficient quantities of fuel and electrolyte without massive crossover nor mass transfer limitations. The feed rate increases the performance up to a limit of 2 mL min{sup -1}, high enough to guarantee the access of the glycerol and the exit of the products. Finally, the use of binary catalysts (PtRu/C and Pt{sub 3}Sn/C) is beneficial for increasing the cell performance. (author)

  9. Crosslinked Hexafluoropropylidene Polybenzimidazole Membranes with Chloromethyl Polysulfone for Fuel Cell Applications

    Yang, Jingshuai; Li, Qingfeng; Cleemann, Lars Nilausen;

    2013-01-01

    Hexafluoropropylidene polybenzimidazole (F6PBI) was synthesized with excellent chemical stability and improved solubility. When doped with phosphoric acid, however, the F6PBI membranes showed plastic deformation at elevated temperatures. Further efforts were made to covalently crosslink F6PBI...... solutions, and improved mechanical strength, especially at elevated temperatures. The superior characteristics of crosslinked membranes allowed for higher acid doping levels and therefore increased proton conductivity as well as significantly improved fuel cell performance and durability, as compared...

  10. High Molecular Weight Polybenzimidazole Membranes for High Temperature PEMFC

    Yang, Jingshuai; Cleemann, Lars Nilausen; Steenberg, T.;

    2014-01-01

    Da with good solubility in organic solvents. Membranes fabricated from the polymers were systematically characterized in terms of oxidative stability, acid doping and swelling, conductivity, mechanical strength and fuel cell performance and durability. With increased molecular weights the polymer...... membranes showed enhanced chemical stability towards radical attacks under the Fenton test, reduced volume swelling upon the acid doping and improved mechanical strength at acid doping levels of as high as about 11 mol H3PO4 per molar repeat polymer unit. The PBI‐78kDa/10.8PA membrane, for example......High temperature operation of proton exchange membrane fuel cells under ambient pressure has been achieved by using phosphoric acid doped polybenzimidazole (PBI) membranes. To optimize the membrane and fuel cells, high performance polymers were synthesized of molecular weights from 30 to 94 k...

  11. High temperature proton exchange membranes based on polybenzimidazoles for fuel cells

    Li, Qingfeng; Jensen, Jens Oluf; Savinell, Robert F; Bjerrum, Niels J.

    2009-01-01

    To achieve high temperature operation of proton exchange membrane fuel cells (PEMFC), preferably under ambient pressure, acid–base polymer membranes represent an effective approach. The phosphoric acid-doped polybenzimidazole membrane seems so far the most successful system in the field. It has in recent years motivated extensive research activities with great progress. This treatise is devoted to updating the development, covering polymer synthesis, membrane casting, physicochemical characte...

  12. meta-PBI/methylated PBI-OO blend membranes for acid doped HT PEMFC

    Cho, Hyeongrae; Hur, Eun; Henkensmeier, Dirk; Jeong, Gisu; Cho, Eunae; Kim, Hyoung Juhn; Jang, Jong Hyun; Lee, Kwan Young; Hjuler, Hans Aage; Li, Qingfeng; Jensen, Jens Oluf; Cleemann, Lars Nilausen

    2014-01-01

    Methylation of polybenzimidazole leads to positively charged polymer backbones, and moveable anions. Ion exchange of methylated PBI-OO in phosphoric acid (PA) shows that the resulting polymers dissolve. meta-PBI, however, absorbs about 400wt% PA while remaining a self supported membrane. We inves...... the fuel cell, blend membranes show similar or better performance than meta-PBI. In the TGA, blends doped in 20% PA showed a stable plateau between 115 and 180°C, while meta-PBI lost weight continuously....

  13. High temperature proton exchange membranes based on polybenzimidazole and clay composites for fuel cells

    Plackett, David; Siu, Ana; Li, Qingfeng;

    2011-01-01

    , acid doping and swelling, tensile strength, conductivity and hydrogen permeability as well as by fuel cell tests. For the composite membranes, high acid doping levels were achieved with sufficient mechanical strength and improved dimensional stability or reduced membrane swelling. At an acid doping......dispersion of modified laponite clay was achieved in polybenzimidazole (PBI) solutions which, when cast and allowed to dry, resulted in homogeneous and transparent composite membranes containing up to 20 wt% clay in the polymer. The clay was organically modified using a series of ammonium and...... pyridinium salts with varying polarity and hydrogen-bonding capacity. Clay modification by ion-exchange reactions involving replacement of interlayer inorganic cations was confirmed using X-ray photoelectron and infrared spectroscopy techniques. The cast PBI membranes were characterized by their water uptake...

  14. Developments of new proton conducting membranes based on different polybenzimidazole structures for fuel cells applications

    Carollo, A.; Quartarone, E.; Tomasi, C.; Mustarelli, P.; Belotti, F.; Magistris, A. [Department of Physical Chemistry, IENI-CNR and INSTM, University of Pavia Via Taramelli 16, 27100 Pavia (Italy); Maestroni, F.; Parachini, M.; Garlaschelli, L.; Righetti, P.P. [Department of Organic Chemistry, University of Pavia Via Taramelli 12, 27100 Pavia (Italy)

    2006-09-29

    The current goal on PEMFCs research points towards the optimization of devices working at temperatures above 100{sup o}C and at low humidity levels. Acid-doped polybenzimidazoles are particularly appealing because of high proton conductivity without humidification and promising fuel cells performances. In this paper we present the development of new proton conducting membranes based on different polybenzimidazole (PBI) structures. Phosphoric acid-doped membranes, synthesized from benzimidazole-based monomers with increased basicity and molecular weight, are presented and discussed. Test of methanol crossover and diffusion were performed in order to check the membrane suitability for DMFCs. Both the acid doping level and proton conductivity remarkably increase with the membrane molecular weight and basicity, which strictly depend on the amount of NH-groups as well as on their position in the polymer backbone. In particular, a conductivity value exceeding 0.1Scm{sup -1} at RH=40% and 80{sup o}C was reached in the case of the pyridine-based PBI. (author)

  15. Phosphoric acid doped membranes based on Nafion®, PBI and their blends – Membrane preparation, characterization and steam electrolysis testing

    Aili, David; Hansen, Martin Kalmar; Pan, Chao;

    2011-01-01

    ® and polybenzimidazole blend membranes was developed. Homogeneous binary membranes covering the whole composition range were prepared and characterized with respect to chemical and physiochemical properties such as water uptake, phosphoric acid doping, oxidative stability, mechanical strength and proton conductivity....... An MEA based on phosphoric acid doped Nafion® was operated at 130 °C at ambient pressure with a current density of 300 mA cm−2 at 1.75 V, with no membrane degradation observed during a test of 90 h. The PBI based MEAs showed better polarization curves (500 mA cm−2 at 1.75 V) but poor durability....

  16. Ionic conducting poly-benzimidazoles; Polybenzimidazoles conducteurs ioniques

    Jouanneau, J

    2006-11-15

    Over the last years, many research works have been focused on new clean energy systems. Hydrogen fuel cell seems to be the most promising one. However, the large scale development of this technology is still limited by some key elements. One of them is the polymer electrolyte membrane 'Nafion' currently used, for which the ratio performance/cost is too low. The investigations we carried out during this thesis work are related to a new class of ionic conducting polymer, the sulfonated poly-benzimidazoles (sPBI). Poly-benzimidazoles (PBI) are aromatic heterocyclic polymers well-known for their excellent thermal and chemical stability. Ionic conduction properties are obtained by having strong acid groups (sulfonic acid SO{sub 3}H) on the macromolecular structure. For that purpose, we first synthesized sulfonated monomers. Their poly-condensation with an appropriate non-sulfonated co-monomer yields to sPBI with sulfonation range from 0 to 100 per cent. Three different sPBI structures were obtained, and verified by appropriate analytical techniques. We also showed that the protocol used for the synthesis resulted in high molecular weights polymers. We prepared ionic conducting membrane by casting sPBI solutions on glass plates. Their properties of stability, water swelling and ionic conductivity were investigated. Surprisingly, the behaviour of sPBI was quite different from the other sulfonated aromatic polymers with same amount of SO{sub 3}H, their stability was much higher, but their water swelling and ionic conductivity were quite low. We attributed these differences to strong ionic interactions between the sulfonic acid groups and the basic benzimidazole groups of our polymers. However, we managed to solve this problem synthesizing very highly sulfonated PBI, obtaining membranes with a good balance between all the properties necessary. (author)

  17. Ionic conducting poly-benzimidazoles

    Over the last years, many research works have been focused on new clean energy systems. Hydrogen fuel cell seems to be the most promising one. However, the large scale development of this technology is still limited by some key elements. One of them is the polymer electrolyte membrane 'Nafion' currently used, for which the ratio performance/cost is too low. The investigations we carried out during this thesis work are related to a new class of ionic conducting polymer, the sulfonated poly-benzimidazoles (sPBI). Poly-benzimidazoles (PBI) are aromatic heterocyclic polymers well-known for their excellent thermal and chemical stability. Ionic conduction properties are obtained by having strong acid groups (sulfonic acid SO3H) on the macromolecular structure. For that purpose, we first synthesized sulfonated monomers. Their poly-condensation with an appropriate non-sulfonated co-monomer yields to sPBI with sulfonation range from 0 to 100 per cent. Three different sPBI structures were obtained, and verified by appropriate analytical techniques. We also showed that the protocol used for the synthesis resulted in high molecular weights polymers. We prepared ionic conducting membrane by casting sPBI solutions on glass plates. Their properties of stability, water swelling and ionic conductivity were investigated. Surprisingly, the behaviour of sPBI was quite different from the other sulfonated aromatic polymers with same amount of SO3H, their stability was much higher, but their water swelling and ionic conductivity were quite low. We attributed these differences to strong ionic interactions between the sulfonic acid groups and the basic benzimidazole groups of our polymers. However, we managed to solve this problem synthesizing very highly sulfonated PBI, obtaining membranes with a good balance between all the properties necessary. (author)

  18. A Comparative Study of Phosphoric Acid-doped m-PBI Membranes

    Perry, Kelly A [ORNL; More, Karren Leslie [ORNL; Payzant, E Andrew [ORNL; Meisner, Roberta A [University of Tennessee (UTK) and Oak Ridge National Laboratory (ORNL); Sumpter, Bobby G [ORNL; Benicewicz, Brian [ORNL

    2014-01-01

    Phosphoric acid (PA)-doped m-polybenzimidazole (PBI) membranes used in high temperature fuel cells and hydrogen pumps were prepared by a conventional imbibing process and a sol-gel fabrication process. A comparative study was conducted to investigate the critical properties of PA doping levels, ionic conductivities, mechanical properties, and molecular ordering. This systematic study found that sol-gel PA-doped m-PBI membranes were able to absorb higher acid doping levels and to achieve higher ionic conductivities than conventionally imbibed membranes when treated in an equivalent manner. Even at similar acid loadings, the sol-gel membranes exhibited higher ionic conductivities. Heat treatment of conventionally imbibed membranes with 29wt% solids caused a significant reduction in mechanical properties; conversely, sol-gel membranes exhibited an enhancement in mechanical properties. From X-ray structural studies and atomistic simulations, both conventionally imbibed and sol-gel membranes exhibited d-spacings of 3.5 and 4.6 , which were tentatively attributed to parallel ring stacking and staggered side-to-side packing, respectively, of the imidazole rings in these aromatic hetercyclic polymers. An anisotropic staggered side-to-side chain packing present in the conventional membranes may be root to the reduction in mechanical properties.

  19. An H3PO4-doped polybenzimidazole/Sn0.95Al0.05P2O7 composite membrane for high-temperature proton exchange membrane fuel cells

    Jin, Y. C.; Nishida, M.; Kanematsu, W.; Hibino, T.

    2011-08-01

    A polybenzimidazole (PBI)/Sn0.95Al0.05P2O7 (SAPO) composite membrane was synthesized by an in situ reaction of SnO2 and Al(OH)3-mixed powders with an H3PO4 solution in a PBI membrane. The formation of a single phase of SAPO in the PBI membrane was completed at a temperature of 250 °C. Thermogravimetric analysis showed that the PBI membrane was not subject to a serious damage by the presence of SAPO until 500 °C. Scanning electron microscopy revealed that SAPO particles with a diameter of approximately 300 nm were homogeneously dispersed and separated from each other in the PBI matrix. Proton magic angle spinning nuclear magnetic resonance spectra confirmed the presence of new protons originating from the SAPO particles in the composite membrane. As a consequence of the interaction of protons in the SAPO with those in the free H3PO4, the H3PO4-doped PBI/SAPO composite membrane exhibited conductivities several times higher than those of an H3PO4-doped PBI membrane at room temperature to 300 °C, which could contribute to the improved performance of H2/O2 fuel cells.

  20. Synthesis and characterization of pyridine-based polybenzimidazoles for high temperature polymer electrolyte membrane fuel cell applications

    Xiao, L.; Zhang, H.; Jana, T.; Scanlon, E.; Chen, R.; Choe, E.W.; Ramanathan, L.S.; Yu, S.; Benicewicz, B.C. [NYS Center for Polymer Synthesis, Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, Troy, NY 12180 (United States)

    2005-04-01

    A series of polybenzimidazoles (PBIs) incorporating main chain pyridine groups were synthesized from the pyridine dicarboxylic acids (2,4-, 2,5-, 2,6- and 3,5-) and 3,3',4,4'-tetraaminobiphenyl, using polyphosphoric acid (PPA) as both solvent and polycondensation reagent. A novel process, termed the PPA process, has been developed to prepare phosphoric acid (PA) doped PBI membranes by direct-casting of the PPA polymerization solution without isolation or re-dissolution of the polymers. The subsequent hydrolysis of PPA to PA by moisture absorbed from the atmosphere usually induced a transition from the solution state to a gel-like state and produced PA-doped PBI membranes with a desirable suite of physiochemical properties. The polymer structure characterization included inherent viscosity (I.V.) determination as a measurement of polymer molecular weight and thermal stability assessment via thermogravimetric analysis. Physiochemical properties of the doped membrane were studied by measurements of the PA doping level, ionic conductivity and mechanical properties. The resulting pyridine-based polybenzimidazole membranes displayed high PA doping levels, ranging from 15 to 25 mol of PA per PBI repeat unit, which contributed to their unprecedented high proton conductivities of 0.1 to 0.2 S cm{sup -1} at 160 C. The mechanical property measurements showed that the pyridine-based PBI membranes were thermally stable and maintained mechanical integrity even at high PA doping levels. Preliminary fuel cell tests demonstrated the feasibility of the novel pyridine-based PBI (PPBI) membranes from the PPA process for operating fuel cells at temperatures in excess of 120 C without any external humidification. (Abstract Copyright [2005], Wiley Periodicals, Inc.)

  1. Durability of symmetrically and asymmetrically porous polybenzimidazole membranes for high temperature proton exchange membrane fuel cells

    Jheng, Li-Cheng; Chang, Wesley Jen-Yang; Hsu, Steve Lien-Chung; Cheng, Po-Yang

    2016-08-01

    Two types of porous polybenzimidazole (PBI) membranes with symmetric and asymmetric morphologies were fabricated by the template-leaching method and characterized by scanning electron microscope (SEM). Their physicochemical properties were compared in terms of acid-doping level, proton conductivity, mechanical strength, and oxidative stability. The durability of fuel cell operation is one of the most challenging for the PBI based membrane electrode assembly (MEA) used in high-temperature proton exchange membrane fuel cells (HT-PEMFCs). In the present work, we carried out a long-term steady-state fuel cell test to compare the effect of membrane structure on the cell voltage degradation. It has also been demonstrated that the asymmetrically porous PBI could bring some notable improvements on the durability of fuel cell operation, the fuel crossover problem, and the phosphoric acid leakage.

  2. Precursor polymer compositions comprising polybenzimidazole

    Klaehn, John R.; Peterson, Eric S.; Orme, Christopher J.

    2015-07-14

    Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

  3. Sythesis and investigation of m-carborane-containing polybenzimidazoles

    New m-carborane-containing polybenzimidazoles (PBI) have been obtained by chemical cyclization of m-carborane-containing polyaminoamides (PAA) with the N-methyl-2-pyrrolidone-sulphuric anhydride complex or polyphosphoric acid esters being used as the cyclodehydrating reagents. The obtained m-carborane-containing PAA and PBI have been tested for solubility, heat resistance and chemical stability. The structure of m-carborane-containing PBI has been determined by abalysis of their infrared spectra

  4. Synthesis and properties of random copolymers of functionalised polybenzimidazoles for high temperature fuel cells

    Mader, J.A.; Benicewicz, B.C. [Department of Chemistry and Biochemistry and USC Nanocenter, University of South Carolina, 631 Sumter St., Columbia, SC 29208 (United States)

    2011-04-15

    A series of polybenzimidazoles (PBIs) incorporating main chain sulphonic acid groups were synthesised as random copolymers with p-PBI in varying ratios using polyphosphoric acid (PPA) as both the polymerisation solvent and polycondensation reagent. The PPA process was used to produce high molecular weight phosphoric acid (PA) doped PBI gel membranes in a one-step procedure. These membranes exhibit excellent mechanical properties (0.528-2.51 MPa tensile stress and 130-300% tensile strain) even at high acid doping levels [20-40 mol PA/PRU (polymer repeat unit)] and high conductivities (0.148-0.291 S cm{sup -1}) at elevated temperatures (>100 C) with no external humidification, depending on copolymer composition. Fuel cell testing was conducted with hydrogen fuel and air or oxygen oxidants for all membrane compositions at temperatures greater than 100 C without external feed gas humidification. Initial studies showed a maximum fuel performance of 0.675 V for the 25 mol% s-PBI/75 mol% p-PBI random copolymer at 180 C and 0.2 A cm{sup -2} with hydrogen and air, and 0.747 V for the same copolymer at 180 C and 0.2 A cm{sup -2} with hydrogen and oxygen. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Soluble N-Substituted Organosilane Polybenzimidazoles

    Klaehn, J. R.; Luther, T. A.; Orme, C. J.; Jones, M. G.; Wertsching, A. K.; Peterson, E. S.

    2007-10-01

    Six organosilane derivatives were synthesized, and are more soluble in common organic solvents (tetrahydrofuran and chloroform) than the parent polybenzimidazole. Our polymer modification pathway provides a straightforward synthesis that can be carried out at room temperature and give reasonable yields. Solution 1H NMR spectra of both the parent and deprotonated polybenzimidazoles are reported. Based upon the NMR analysis in CDCl3, nearly all of the benzimidazole N-H positions are substituted by the organosilane moieties. Some of the modified polymers have similar thermal properties compared to the parent polymer, and the average molecular weights are higher for the substituted polybenzimidazoles than the parent PBI.

  6. Oxidative degradation of polybenzimidazole membranes as electrolytes for high temperature proton exchange membrane fuel cells

    Liao, J.H.; Li, Qingfeng; Rudbeck, H.C.;

    2011-01-01

    Polybenzimidazole membranes imbibed with acid are emerging as a suitable electrolyte material for high-temperature polymer electrolyte fuel cells. The oxidative stability of polybenzimidazole has been identified as an important issue for the long-term durability of such cells. In this paper the...... oxidative degradation of the polymer membrane was studied under the Fenton test conditions by the weight loss, intrinsic viscosity, size exclusion chromatography, scanning electron microscopy and Fourier transform infrared spectroscopy. During the Fenton test, significant weight losses depending on the...

  7. Polybenzimidazoles Via Aromatic Nucleophilic Displacement

    Connell, John W. (Inventor); Hergerrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

    1997-01-01

    Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

  8. Evaluation of polybenzimidazole glass-fabric laminates

    Mackay, H.A.

    1966-01-01

    Laminates prepared from polybenzimidazole and 1581-994S glass fabric have excellent short-time heat resistance to 800 deg F., and 100-hr. thermal stability at 600 deg F. These characteristics are based on mechanical-property strength retention and low resin weight loss. In spite of high cost and processing difficulties, polybenzimidazoles are being applied as laminates and adhesives for nose fairing, thermal insulation, aircraft leading edge, reentry nose cones, radomes, de-icer ducts, and in other areas where high temperature resistance is needed.

  9. Preparation of aromatic polyamidines and their transformation in polybenzimidazoles

    B. Ch. Kholkhoev

    2014-09-01

    Full Text Available Polymers with amidine groups –NH–C(=NH– in main chain were synthesized by two different approaches. The first strategy consists in polyaddition of dinitriles and diamines in acidic ionic liquids (ILs which act as catalyst and solvent, while the second approach is based on polycondensation of 4,4'-oxybis(benzoic acid diamide and diamines in Eaton’s reagent (ER. The resulting polyamidines (PADs with Mw up to 25 000 g/mol possess thermal stability on air up to 288°C, and good solubility in polar organic solvents. Moreover dehydrocyclization of obtained PADs into polybenzimidazoles (PBIs under the action of various oxidants was also studied in this work. The crosslinked films based on PBI and poly(amino imide resin (PAIR possess high mechanical characteristics. It has been proved that the crosslinked films based on PBI matrix are perspective materials for design the phosphoric acid electrolyte membranes for the medium temperature fuel cells.

  10. Vacuum thermal evaporation of polyaniline doped with camphor sulfonic acid

    Boyne, Devon; Menegazzo, Nicola; Pupillo, Rachel C.; Rosenthal, Joel; Booksh, Karl S., E-mail: kbooksh@udel.edu [Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716 (United States)

    2015-05-15

    Intrinsically conducting polymers belong to a class of organic polymers with intriguing electronic and physical properties specifically for electro-optical applications. Significant interest into doped polyaniline (PAni) can be attributed to its high conductivity and environmental stability. Poor dissolution in most solvents has thus far hindered the successful integration of PAni into commercial applications, which in turn, has led to the investigations of various deposition and acidic doping methods. Physical vapor deposition methods, including D.C. magnetron sputtering and vacuum thermal evaporation, have shown exceptional control over physical film properties (thickness and morphology). However, resulting films are less conductive than films deposited by conventional methods (i.e., spin and drop casting) due to interruption of the hyperconjugation of polymer chains. Specifically, vacuum thermal evaporation requires a postdoping process, which results in incorporation of impurities and oxidation of surface moieties. In this contribution, thermally evaporated films, sequentially doped by vacuum evaporation of an organic acid (camphorsulfonic acid, CSA) is explored. Spectroscopic evidence confirms the successful doping of PAni with CSA while physical characterization (atomic force microscopy) suggests films retain good morphology and are not damaged by the doping process. The procedure presented herein also combines other postpreparation methods in an attempt to improve conductivity and/or substrate adhesion.

  11. Fuel cell characteristics of the membrane electrode assemblies using phosphoric acid-doped poly membranes

    Fang, Liang; Sheng, Li; Guo, Xiaoxia; Fang, Jianhua; Ma, Zi-Feng

    2011-01-15

    Recently, there has been extensive research in the development of polymer electrolyte membrane fuel cells (PEMFCs) for transportation and portable power applications. Nafion has been widely used as electrolyte membranes, but it has several limitations. Thus intensive efforts have been devoted to the development of low-cost proton-conducting electrolytes used at elevated temperatures to reduce the impurities poisoning. Promising candidates are the PA-doped polybenzimidazoles, which can function at higher temperature under non-humidification conditions to eliminate the water management, promote the fuel impurities tolerance, increase the electrode kinetics and facilitate the heat recovery. In this study, the novel PA-doped OPBI membrane was chosen as the electrolyte, and one molecular weight mPBI was synthesized as the binder in catalyst layers. This optimized membrane electrode assemblies (MEAs) exhibited desirable performances in the electrochemical tests up to 160 degree C. This investigation opened up a new way to develop the practical proton-conducting fuel cell systems working at elevated temperatures.

  12. The Electrochemical Behavior of Phosphoric-Acid-Doped Poly(perfluorosulfonic Acid) Membranes

    Aili, David; Savinell, Robert F; Jensen, Jens Oluf;

    2014-01-01

    Highly conductive phosphoric-acid-doped poly(perfluorosulfonic acid) membranes have long been known to malfunction in fuel cells. This is investigated and found to be due to failure of the anode, in which a limiting current is observed in the very low current-density range. It is proposed...... that the strongly acidic sulfonic acid groups protonate the phosphoric acid under anhydrous conditions, forming excess proton defects that are involved in proton conduction by means of the vehicle mechanism. The slow back-diffusion of phosphoric acid molecules as proton carriers thus limits the long...

  13. Performance Evaluation of Polybenzimidazole for Potential Aerospace Applications

    Iqbal, H.M.S.

    2014-01-01

    With the increasing use of polymer based composite materials, there is an increasing demand of polymeric resins with high glass transition temperature, high thermal stability and excellent mechanical properties at high temperature. Polybenzimidazole (PBI) is a recently emerged high performance polymer. It has the highest glass transition temperature of any commercially available organic polymer, high decomposition temperature, good oxidation resistance and it maintains excellent strength at c...

  14. Hydroxyl pyridine containing polybenzimidazole membranes for proton exchange membrane fuel cells

    Yang, Jingshuai; Xu, Yixin; Zhou, Lu;

    2013-01-01

    , but also benefited the proton conduction, which was proved by the results of acid conductivities of the membranes with comparable acid doping levels. At an acid doping level of 8.6, i.e. 8.6mol acids per molar repeat unit of the polymer, the OHPyPBI membrane exhibited a proton conductivity of 0.102Scm...

  15. Quartz crystal microbalance and spectroscopy measurements for acid doping in polyaniline films

    Mohamad M Ayad and Eman A Zaki

    2008-01-01

    Full Text Available We investigated the doping of thin polyaniline (PANI films, prepared by the chemical oxidation of aniline, with different acids. The initial step in the investigation is the preparation of PANI films from aqueous hydrochloric acid solution. This is followed by dedoping with ammonia to obtain a PANI base, which is subsequently doped with strong acids (e.g. hydrochloric, sulfuric, phosphoric and trichloroacetic acids and with a weak acid (acetic acid. The dopant weight fraction (w, which is connected with the gain of mass during the doping of PANI, was determined in situ using a quartz crystal microbalance (QCM. The behavior of PANI upon doping with different anions derived from strong acids indicates that both proton and the anion uptake into the polymer chains occur sharply, rapidly, completely, and reversibly. However the uptake in the case in acetic acid is characterized by slow diffusion. The doping was studied at different concentrations of acetic acid. A second cycle of dedoping–redoping was also performed. The kinetics of the doping reaction is dominated by Fickian diffusion kinetics. The diffusion coefficients (D of the dopant ions into the PANI chains were determined using the QCM and by UV–Vis absorption spectroscopy in the range of (0.076–1.64× 10−15 cm2 s−1. It was found that D in the second cycle of doping is larger than that evaluated from the first cycle of doping for high concentrations of acetic acid. D for the diffusion and for the dopant ion expulsion from the PANI chains was also determined during the redoping process. It was found that D for acetic acid ions in the doping process is larger than that calculated for the dedoping process.

  16. Phosphoric acid doped AB-PBI membranes and its applications in high temperature PEMFC

    He, Ronghuan; Qingfeng, Li; Bjerrum, Niels

    2005-01-01

    Poly(2,5-benzimidazole) (ab-PBI) was prepared from 3,4-diaminobenzoic acid via a polymerisation reaction. The obtained polymer exhibits excellent thermal stability in a temperature range ….. The membrane of ab-PBI when doped with phosphoric acid at room temperaturepresents high proton conductivity......C with phosphoric acid doped ab-PBI as the electrolyte under atmospheric pressure at 200°C without humidification....

  17. Phosphoric acid doped imidazolium polysulfone membranes for high temperature proton exchange membrane fuel cells

    Yang, Jingshuai; Li, Qingfeng; Jensen, Jens Oluf;

    2012-01-01

    A novel acid–base polymer membrane is prepared by doping of imidazolium polysulfone with phosphoric acid for high temperature proton exchange membrane fuel cells. Polysulfone is first chloromethylated, followed by functionalization of the chloromethylated polysulfone with alkyl imidazoles i.......e. methyl (MePSU), ethyl (EtPSU) and butyl (BuPSU) imidazoliums, as revealed by 1H NMR spectra. The imidazolium polysulfone membranes are then doped with phosphoric acid and used as a proton exchange membrane electrolyte in fuel cells. An acid doping level of about 10–11mol H3PO4 per mole of the imidazolium...

  18. Porous poly(benzimidazole) membrane for all vanadium redox flow battery

    Luo, Tao; David, Oana; Gendel, Youri; Wessling, Matthias

    2016-04-01

    Porous poly(benzimidazole) (PBI) membranes of low vanadium ions permeability are described for an all vanadium redox flow battery (VRFB). The PBI membrane was prepared by a water vapour induced phase inversion process of a PBI polymer solution. The membrane has a symmetrical cross-sectional morphology. A low water permeability of 16.5 L (m2 h bar)-1 indicates the high hydraulic resistance stemming from a closed cell morphology with nanoporous characteristics. The PBI membrane doped with 2.5 M H2SO4 shows a proton conductivity of 16.6 mS cm-1 and VO2+ permeability as low as 4.5 × 10-8 cm2 min-1. The stability test of dense PBI membrane in VO2+ solution indicates good chemical stability. An all vanadium redox flow battery (VRFB) operated with the porous PBI membrane shows 98% coulombic efficiency and more than 10% higher energy efficiency compared to VRFB operated with Nafion 112 at applied current densities of 20-40 mA cm-2. High in situ stability of the porous PBI membrane was confirmed by about 50 cycles of continuous charge and discharge operation of the battery.

  19. Highly efficient sulfonated polybenzimidazole as a proton exchange membrane for microbial fuel cells

    Singha, Shuvra; Jana, Tushar; Modestra, J. Annie; Naresh Kumar, A.; Mohan, S. Venkata

    2016-06-01

    Although microbial fuel cells (MFCs) represent a promising bio-energy technology with a dual advantage (i.e., electricity production and waste-water treatment), their low power densities and high installation costs are major impediments. To address these bottlenecks and replace highly expensive Nafion, which is a proton exchange membrane (PEM), the current study focuses for the first time on membranes made from an easily synthesizable and more economical oxy-polybenzimidazole (OPBI) and its sulfonated analogue (S-OPBI) as alternate PEMs in single-chambered MFCs. The S-OPBI membrane exhibits better properties, with high water uptake, ion exchange capacity (IEC) and proton conductivity and a comparatively smaller degree of swelling compared to Nafion. The membrane morphology is characterized by atomic force microscopy, and the bright and dark regions of the S-OPBI membrane reveals the formation of ionic domains in the matrix, forming continuous water nanochannels when doped with water. These water-filled nanochannels are responsible for faster proton conduction in S-OPBI than in Nafion; therefore, the power output in the MFC with S-OPBI as the PEM is higher than in other MFCs. The open circuit voltage (460 mV), current generation (2.27 mA) and power density profile (110 mW/m2) as a function of time, as well as the polarization curves, exhibits higher current and power density (87.8 mW/m2) with S-OPBI compared to Nafion as the PEM.

  20. On the existence of ethylenediaminetetraacetic acid (EDTA) doped zinc sulphate heptahydrate crystal

    Srinivasan, Bikshandarkoil R.

    2015-01-01

    It is argued that the ethylenediaminetetraacetic acid (EDTA) doped zinc sulphate heptahydrate crystal reported by Raja et al Spectrochim Acta 99A (2012) 23 is the well known zinc sulphate heptahydrate.

  1. Growth and characterization studies of pure and tartaric acid doped benzilic acid crystals

    Gilda, M. J. Jarald Brigit; Devarajan, Prem Anand

    2016-04-01

    The organic nonlinear optical crystals of pure benzilic acid (PBA) and tartaric acid doped benzilic acid (TADBA) single crystals were grown by using slow evaporation method utilizing dimethyl formamide (DMF) as a solvent. Transparent single crystals of PBA and TADBA of dimensions 9×4×1 mm3 and 7×5×2 mm3 were grown after thirty days. Lattice parameters and space groups of PBA and TADBA were evaluated using single crystal X-ray diffraction analysis. Employing Fourier transform infrared spectral analysis, various functional groups in pure and doped crystals were ascertained. 1H and C13 nuclear magnetic resonance spectral analysis suggests the presence of hydrogen- and carbon-bonded network. Optical transparency of PBA and TADBA was investigated using ultraviolet-visible (UV-vis) spectral analysis whereas thermal properties of the grown crystals were studied by thermogravimetric and differential scanning calorimetry analyses. Second harmonic generation efficiency of PBA and TADBA was found to be 2.2 and 2.7 times higher than that of potassium dihydrogen phosphate.

  2. Doping optimization of polypyrrole with toluenesulfonic acid using Box-Behnken design

    Syed Draman, Sarifah Fauziah; Daik, Rusli [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia); El-Sheikh, Said M. [Nanostructured Materials and Nanotechnology Division, Central Metallurgical Research and Development Institute,11421 Cairo (Egypt); Latif, Famiza Abdul [Faculty of Applied Sciences, Universiti Teknologi MARA Malaysia 40450 Shah Alam, Selangor (Malaysia)

    2013-11-27

    A three-level Box-Behnken design was employed in doping optimization of polypyrrole with toluenesulfonic acid (TSA-doped PPy). The material was synthesized via chemical oxidative polymerization using pyrrole, toluenesulfonic acid (TSA) and ammonium persulfate (APS) as monomer, dopant and oxidant, respectively. The critical factors selected for this study were concentration of dopant, molar ratio between dopant to monomer (pyrrole) and concentration of oxidant. Obtaining adequate doping level of TSA-doped PPy is crucial because it affects the charge carriers for doped PPy and usually be responsible for electronic mobility along polymeric chain. Furthermore, the doping level also affects other properties such as electrical and thermal conductivity. Doping level was calculated using elemental analysis. SEM images shows that the prepared TSA-doped PPy particles are spherical in shape with the diameters of about. The range of nanoparticles size is around 80-100 nm. The statistical analysis based on a Box–Behnken design showed that 0.01 mol of TSA, 1:1 mole ratio TSA to pyrrole and 0.25 M APS were the optimum conditions for sufficient doping level.

  3. Ammonia Gas Sensing Behavior of Tanninsulfonic Acid Doped Polyaniline-TiO2 Composite

    Venu Gopal Bairi; Bourdo, Shawn E.; Nicolas Sacre; Dev Nair; Berry, Brian C.; Biris, Alexandru S; Tito Viswanathan

    2015-01-01

    A highly active tannin doped polyaniline-TiO2 composite ammonia gas sensor was developed and the mechanism behind the gas sensing activity was reported for the first time. A tanninsulfonic acid doped polyaniline (TANIPANI)-titanium dioxide nanocomposite was synthesized by an in situ polymerization of aniline in the presence of tanninsulfonic acid and titanium dioxide nanoparticles. X-ray diffraction and thermogravimetric analysis were utilized to determine the incorporation of TiO2 in TANIPAN...

  4. Exceptionally crystalline and conducting acid doped polyaniline films by level surface assisted solution casting approach

    Puthirath, Anand B.; Methattel Raman, Shijeesh; Varma, Sreekanth J.; Jayalekshmi, S.

    2016-04-01

    Emeraldine salt form of polyaniline (PANI) was synthesized by chemical oxidative polymerisation method using ammonium persulfate as oxidant. Resultant emeraldine salt form of PANI was dedoped using ammonia solution and then re-doped with camphor sulphonic acid (CSA), naphthaline sulphonic acid (NSA), hydrochloric acid (HCl), and m-cresol. Thin films of these doped PANI samples were deposited on glass substrates using solution casting method with m-cresol as solvent. A level surface was employed to get homogeneous thin films of uniform thickness. Detailed X-ray diffraction studies have shown that the films are exceptionally crystalline. The crystalline peaks observed in the XRD spectra can be indexed to simple monoclinic structure. FTIR and Raman spectroscopy studies provide convincing explanation for the exceptional crystallinity observed in these polymer films. FESEM and AFM images give better details of surface morphology of doped PANI films. The DC electrical conductivity of the samples was measured using four point probe technique. It is seen that the samples also exhibit quite high DC electrical conductivity, about 287 S/cm for CSA doped PANI, 67 S/cm for NSA doped PANI 65 S/cm for HCl doped PANI, and just below 1 S/cm for m-cresol doped PANI. Effect of using the level surface for solution casting is studied and correlated with the observed crystallinity.

  5. Studies on biphenyl disulphonic acid doped polyanilines: Synthesis, characterization and electrochemistry

    Chepuri R K Rao; R Muthukannan; M Vijayan

    2012-06-01

    In this article, we report on the results obtained for the efforts we made to bring processability to the conducting polyaniline and substituted polyanilines by designing and synthesizing a new disulphonic acid with a biphenyl moiety as spacer group, viz. 4,4'-biphenyldisulphonic acid (BPSA). When doped, the disulphonic acid acts as a spacer group between the polyaniline chains and facilitates increase in solubility and conductivity. The spacing effect is maximized when BPSA is used as doping agent in in situ polymerization reactions. The conductivity of polyaniline doped by BPSA is 4 S/cm and for the substituted polyanilines it ranged from 2 × 10-5 to 8 × 10-4 S/cm.

  6. Refractive index modulation in polymer film doped with diazo Meldrum's acid

    Zanutta, Alessio; Villa, Filippo; Bertarelli, Chiara; Bianco, Andrea

    2016-08-01

    Diazo Meldrum's acid undergoes a photoreaction induced by UV light and it is used as photosensitizer in photoresists. Upon photoreaction, a change in refractive index occurs, which makes this system interesting for volume holography. We report on the sublimation effect at room temperature and the effect of photoirradiation on the refractive index in thin films of CAB (Cellulose acetate butyrate) doped with different amount of diazo Meldrum's acid. A net modulation of the refractive index of 0.01 is achieved with 40% of doping ratio together with a reduction of the film thickness.

  7. Sterically Stabilized Poly(3,4-ethylenedioxythiophene) Colloidal Dispersions Doped with Different Sulfonic Acids

    Tie Jun WANG; Ping CHEN; Xiu Jie HU; Shu Yun ZHOU

    2006-01-01

    The preparation of sterically stabilized poly(3, 4-ethylenedioxythiophene)(PEDOT)colloidal dispersions doped with different sulfonic acids is described. Three different sulfonic acids, i.e., p-toluenesulfonic acid, β-naphthalenesuffonic acid and D-camphor-10-sulfonic acid are used, facilitating the preparation of sterically stable PEDOT colloidal particles. The influences of the dopants and concentration of polymeric stabilizer on the yields, morphologies and electrical properties of the resultant colloidal particles were investigated. The colloidal particles with the size ranging from 172 to 334 nm have been obtained in good yields. The compressed pellet conductivity was as high as 4.5 Scm-1.

  8. Performance Degradation Tests of Phosphoric Acid Doped PBI Membrane Based High Temperature PEM Fuel Cells

    Zhou, Fan; Araya, Samuel Simon; Grigoras, Ionela;

    2014-01-01

    Degradation tests of two phosphoric acid (PA) doped PBI membrane based HT-PEM fuel cells were reported in this paper to investigate the effects of start/stop and the presence of methanol in the fuel to the performance degradation. Continuous tests with H2 and simulated reformate which was composed...

  9. Evaluation of the acid properties of porous zirconium-doped and undoped silica materials

    Fuentes-Perujo, D.; Santamaría-González, J.; Mérida-Robles, J.; Rodríguez-Castellón, E.; Jiménez-López, A.; Maireles-Torres, P.; Moreno-Tost, R.; Mariscal, R.

    2006-07-01

    A series of porous silica and Zr-doped silica molecular sieves, belonging to the MCM-41 and MSU families, were prepared and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N 2 adsorption at 77 K. Their acid properties have been evaluated by NH 3-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FT-IR spectroscopy and the catalytic tests of isopropanol decomposition and isomerization of 1-butene. The acidity of purely siliceous solids were, in all cases, very low, while the incorporation of Zr(IV) into the siliceous framework produced an enhancement of the acidity. The adsorption of basic probe molecules and the catalytic behaviour revealed that Zr-doped MSU-type silica was more acidic than the analogous Zr-MCM-41 solid, with a similar Zr content. This high acidity observed in the case of Zr-doped silica samples is due to the presence of surface zirconium atoms with a low coordination, mainly creating Lewis acid sites.

  10. New Polymer Electrolyte Membranes Based on Acid Doped PBI For Fuel Cells Operating above 100°C

    Li, Qingfeng

    The technical achievement and challenges for the PEMFC technology based on perfluorosulfonic acid (PFSA) polymer membranes (e.g. Nafion®) are briefly discussed. The newest development for alternative polymer electrolytes for operation above 100°C. As one of the successful approaches to high...... operational temperatures, the development and evaluation of acid doped PBI membranes are reviewed, covering polymer synthesis, membrane casting, acid doping, physiochemical characterization and fuel cell tests....

  11. UV assisted photoelectrocatalytic oxidation of phthalic acid using spray deposited Al doped zinc oxide thin films

    Mahadik, M.A.; Shinde, S.S.; Hunge, Y.M.; Mohite, V.S.; Kumbhar, S.S.; Moholkar, A.V.; Rajpure, K.Y.; Bhosale, C.H., E-mail: chbhosale@gmail.com

    2014-10-25

    Highlights: • Nanostructured undoped and AZO thin films prepared by chemical spray pyrolysis. • Effect of Al doping on the structural, morphological and photoluminance properties. • Photocatalytic degradation of phthalic acid under UV light illumination. • Reaction kinetics and mineralization of phthalic acid. - Abstract: Undoped and Al doped ZnO (AZO) thin films are successfully prepared by spray pyrolysis technique at optimised substrate temperature of 400 °C onto amorphous and F:SnO{sub 2} coated glass substrates. Effect of Al doping on structural, morphological and optical properties of ZnO thin films is studied. Deposited films are polycrystalline with a hexagonal (wurtzite) crystal structure having (0 0 2) preferred orientation. The PEC characterization shows that, short circuit current (I{sub sc}) and open circuit voltage (V{sub oc}) are (I{sub sc} = 0.38 mA and V{sub oc} = 421 mV) relatively higher at the 3 at.% Al doping. SEM images show deposited thin films are compact and uniform with seed like grains. All films exhibit average transmittance of about 82% in the visible region and a sharp absorption onset at 375 nm corresponding to 3.3 eV. The photocatalytic activities of the large surface area (64 cm{sup 2}) Al-doped ZnO photocatalyst samples were evaluated by photoelectrocatalytic degradation of phthalic acid under UV light irradiation. The results show that the 3 at.% AZO thin film photocatalyst exhibited degradation of phthalic acid up to about 45% within 3 h with significant reduction in COD and TOC values.

  12. The Research on the Stability of TiO2,MoO3,PEO Doped Four-member Tungstic Acid Sols

    Kai RAO; Xiang Kai FU; Xiao Ping RAO

    2004-01-01

    The TiO2, MoO3, PEO doped four-member tungstic acid sols were prepared for the first time.The stability of different doped content sols were investigated and optimized with rotational viscometer.The four-member doped tungstic acid sol was very stable which could be stored more than two months at room temperature.The WO3 electrochromic film prepared from this doped four- member tungstic acid sol had excellent performance and longevity of service.

  13. Sonocatalytic degradation of Acid Blue 92 using sonochemically prepared samarium doped zinc oxide nanostructures.

    Khataee, Alireza; Saadi, Shabnam; Vahid, Behrouz; Joo, Sang Woo; Min, Bong-Ki

    2016-03-01

    Pure and Sm-doped ZnO nanoparticles were synthesized applying a simple sonochemical method. The nanocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) techniques which confirmed the successful synthesis of the doped sonocatalyst. The sonocatalytic degradation of Acid Blue 92 (AB92), a model azo dye, was more than that with sonolysis alone. The 6% Sm-doped ZnO nanoparticles had a band gap of 2.8 eV and demonstrated the highest activity. The degradation efficiency (DE%) of sonolysis and sonocatalysis with undoped ZnO and 6% Sm-doped ZnO was 45.73%, 63.9%, and 90.10%, after 150 min of treatment, respectively. Sonocatalytic degradation of AB92 is enhanced with increasing the dopant amount and catalyst dosage and with decreasing the initial AB29 concentration. DE% declines with the addition of radical scavengers such as chloride, carbonate, sulfate, and tert-butanol. However, the addition of enhancers including potassium periodates, peroxydisulfate, and hydrogen peroxide improves DE% by producing more free radicals. The results show adequate reusability of the doped sonocatalyst. Degradation intermediates were recognized by gas chromatography-mass spectrometry (GC-MS). Using nonlinear regression analysis, an empirical kinetic model was developed to estimate the pseudo-first-order constants (kapp) as a function of the main operational parameters, including the initial dye concentration, sonocatalyst dosage, and ultrasonic power. PMID:26584981

  14. 3D Polyaniline Architecture by Concurrent Inorganic and Organic Acid Doping for Superior and Robust High Rate Supercapacitor Performance

    Gawli, Yogesh; Banerjee, Abhik; Dhakras, Dipti; Deo, Meenal; Bulani, Dinesh; Wadgaonkar, Prakash; Shelke, Manjusha; Ogale, Satishchandra

    2016-02-01

    A good high rate supercapacitor performance requires a fine control of morphological (surface area and pore size distribution) and electrical properties of the electrode materials. Polyaniline (PANI) is an interesting material in supercapacitor context because it stores energy Faradaically. However in conventional inorganic (e.g. HCl) acid doping, the conductivity is high but the morphological features are undesirable. On the other hand, in weak organic acid (e.g. phytic acid) doping, interesting and desirable 3D connected morphological features are attained but the conductivity is poorer. Here the synergy of the positive quality factors of these two acid doping approaches is realized by concurrent and optimized strong-inorganic (HCl) and weak-organic (phytic) acid doping, resulting in a molecular composite material that renders impressive and robust supercapacitor performance. Thus, a nearly constant high specific capacitance of 350 F g-1 is realized for the optimised case of binary doping over the entire range of 1 A g-1 to 40 A g-1 with stability of 500 cycles at 40 A g-1. Frequency dependant conductivity measurements show that the optimized co-doped case is more metallic than separately doped materials. This transport property emanates from the unique 3D single molecular character of such system.

  15. Enhancing proton conduction via doping of supramolecular liquid crystals (4-alkoxybenzoic acids) with imidazole

    Liang, Ting; Wu, Yong; Tan, Shuai; Yang, Xiaohui; Wei, Bingzhuo

    2015-09-01

    Enhancing proton conduction via doping was first achieved in hydrogen-bonded liquid crystals consisting of benzoic acids. Supramolecular liquid crystals formed by pure 4-alkoxybenzoic acids (nAOBA, n = 8, 10, 12) exhibited the maximum proton conductivity of 5.0 × 10-8 S cm-1. Doping of nAOBA with 25 mol% imidazole (Im0.25) had little impact on mesomorphism but increased proton conductivities by at least 3 orders of magnitude. The liquid crystals formed by nAOBA-Im0.25 exhibited the maximum proton conductivity of 1.9 × 10-4 S cm-1. It was proposed that structure diffusion of imidazole bridged interdimer proton transfer to form continuous conducting pathways in mesomorphic nAOBA-Im0.25.

  16. PHOTO-INDUCED DOPED POLYANILINE BY THE VINYLIDENE CHLORIDE AND METHYL ACRYLATE COPOLYMER AS PHOTO ACID GENERATOR

    LI Suzhen; WAN Meixiang

    1997-01-01

    The emeraldine base form of polyaniline (PANI) can be doped by a photo-induced doping method. In this method a copolymer of vinylidene chloride and methyl acrylate (VCMAC) was used as photo acid generator which can release proton when it is exposed to ultraviolet light (λ = 254 nm). The structure of PANI-VCMAC system before and after irradiation was characterized by elemental analysis, IR, XPS, and SEM images. Results obtained indicate that the photo-induced doping characteristics, such as doping position and type of charge carriers, are similar to that of PANI doped with HCl. The poor roomtemperature conductivity (~ 10-5S/cm) of PANI-VCMAC system after irradiation may be due to low doping degree (~pH= 3) and the difference in morphology as compared with PANI-HCl film.

  17. Carbon doping of MgB{sub 2} by toluene and malic-acid-in-toluene

    Bohnenstiehl, S.D., E-mail: bohnenstiehl.1@osu.ed [Center for Superconducting and Magnetic Materials, Department of Materials Science and Engineering, Ohio State University, Columbus, OH (United States); Susner, M.A.; Yang, Y.; Collings, E.W.; Sumption, M.D. [Center for Superconducting and Magnetic Materials, Department of Materials Science and Engineering, Ohio State University, Columbus, OH (United States); Rindfleisch, M.A.; Boone, R. [Hyper Tech Research, Inc., 539 Industrial Mile Road, Columbus, OH 43228 (United States)

    2011-02-15

    Research highlights: {yields} Both toluene and malic acid contribute carbon to MgB{sub 2}. {yields} Toluene is more effective than malic acid for transport properties. {yields} Total carbon can be measured by LECO carbon analysis. - Abstract: The decomposition of malic acid (C{sub 4}H{sub 6}O{sub 5}) in the presence of Mg and B was studied using Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) which revealed that malic acid reacted with Mg but not B. Also, the addition of toluene (C{sub 7}H{sub 8}) to dissolve malic acid followed by subsequent drying resulted in no reaction with Mg, indicating that the malic acid had decomposed during the dissolution/drying stage. The total carbon contributed by toluene versus a toluene/5 wt.% malic acid mixture was measured using a LECO CS600 carbon analyzer. The toluene sample contained {approx}0.4 wt.% C while the toluene/malic acid mixture had {approx}1.5 wt.% C, demonstrating that the toluene contributed a significant amount of carbon to the final product. Resistivity measurements on powder-in-tube MgB{sub 2} monofilamentary wires established that the toluene/malic acid doped sample had the highest B{sub c2}. However, the toluene-only sample had the highest transport J{sub c} over most of the magnetic field range (0-9 T), equaled only by that of toluene/malic-acid sample in fields above 9 T.

  18. Synthesis and luminescence properties of dye-doped deoxyribonucleic acid films

    Dye-doped deoxyribonucleic acids (DNA)–tetradecyltrimethylammonium (TTA) films have been prepared. Rhodamine 6G, known as laser dyes, can be spontaneously doped by immersing the DNA–TTA film in rhodamine 6G-acetonitrile solutions. It is surmised that rhodamine 6G monomers and dimers diffuse within the hydrophobic TTA sites, and then monomers presumably intercalate between adjacent base pairs of DNA. Optical absorption spectra reveal that rhodamine 6G molecules in the sample undergo an unusual transformation from the dimer state to the monomer state with the elapse of time. Rhidamine 6G molecules doped in DNA–TTA show enhanced photostability and concentration quenching than those in PMMA. The environment, conformation and chemical stability of rhodamine 6G are different between DNA–TTA and PMMA, and are presumably modified by the intercalation. - Highlights: ► Rhodamine 6G can be spontaneously doped into DNA films by the immersion method. ► Rhodamine 6G molecules undergo an unusual transformation from the dimer to monomer state. ► Rhodamine 6G molecules in DNA films show enhanced photostability and concentration quenching than those in PMMA.

  19. Synthesis and luminescence properties of dye-doped deoxyribonucleic acid films

    Kitazawa, N., E-mail: nkita@nda.ac.jp [Department of Materials Science and Engineering, National Defense Academy, 1-10-20 Hashirimizu, Yokosuka, Kanagawa 239-8686 (Japan); Aroonjaeng, W.; Aono, M.; Watanabe, Y. [Department of Materials Science and Engineering, National Defense Academy, 1-10-20 Hashirimizu, Yokosuka, Kanagawa 239-8686 (Japan)

    2012-06-15

    Dye-doped deoxyribonucleic acids (DNA)-tetradecyltrimethylammonium (TTA) films have been prepared. Rhodamine 6G, known as laser dyes, can be spontaneously doped by immersing the DNA-TTA film in rhodamine 6G-acetonitrile solutions. It is surmised that rhodamine 6G monomers and dimers diffuse within the hydrophobic TTA sites, and then monomers presumably intercalate between adjacent base pairs of DNA. Optical absorption spectra reveal that rhodamine 6G molecules in the sample undergo an unusual transformation from the dimer state to the monomer state with the elapse of time. Rhidamine 6G molecules doped in DNA-TTA show enhanced photostability and concentration quenching than those in PMMA. The environment, conformation and chemical stability of rhodamine 6G are different between DNA-TTA and PMMA, and are presumably modified by the intercalation. - Highlights: Black-Right-Pointing-Pointer Rhodamine 6G can be spontaneously doped into DNA films by the immersion method. Black-Right-Pointing-Pointer Rhodamine 6G molecules undergo an unusual transformation from the dimer to monomer state. Black-Right-Pointing-Pointer Rhodamine 6G molecules in DNA films show enhanced photostability and concentration quenching than those in PMMA.

  20. Structure and properties of polybenzimidazole/silica nanocomposite electrolyte membrane: influence of organic/inorganic interface.

    Singha, Shuvra; Jana, Tushar

    2014-12-10

    Although increased number of reports in recent years on proton exchange membrane (PEM) developed from nanocomposites of polybenzimidazole (PBI) with inorganic fillers brought hope to end the saga of contradiction between proton conductivity and variety of stabilities, such as mechanical, thermal,chemical, etc.; it still remains a prime challenge to develop a highly conducting PEM with superior aforementioned stabilities. In fact the very limited understanding of the interactions especially interfacial interaction between PBI and inorganic filler leads to confusion over the choice of inorganic filler type and their surface functionalities. Taking clue from our earlier study based on poly(4,4'-diphenylether-5,5'-bibenzimidazole) (OPBI)/silica nanocomposites, where silica nanoparticles modified with short chain amine showed interfacial interaction-dependent properties, in this work we explored the possibility of enhanced interfacial interaction and control over the interface by optimizing the chemistry of the silica surface. We functionalized the surface of silica nanoparticles with a longer aliphatic chain having multiple amine groups (named as long chain amine modified silica and abbreviated as LAMS). FTIR and (13)C solid-state NMR provided proof of hydrogen bonding interactions between the amine groups of modifier and those of OPBI. LAMS nanoparticles yielded a more distinguished self-assembly extending all over the OPBI matrix with increasing concentrations. The crystalline nature of these self-assembled clusters was probed by wide-angle X-ray diffraction (WAXD) studies and the morphological features were captured by transmission electron microscope (TEM). We demonstrated the changes in storage modulus and glass transition temperature (Tg) of the membranes, the fundamental parameters that are more sensitive to interfacial structure using temperature dependent dynamic mechanical analysis (DMA). All the nanocomposite membranes displayed enhanced mechanical, thermal

  1. Polypyrrole electrodes doped with sulfanilic acid azochromotrop for electrochemical supercapacitors

    Chen, S.; Zhitomirsky, I.

    2013-12-01

    In this work we demonstrate the feasibility of deposition of polypyrrole (PPy) films by electropolymerization on stainless steel substrates and fabrication of PPy powders by chemical polymerization using sulfanilic acid azochromotrop (SPADNS) as a new anionic dopant. The problem of low adhesion of PPy films to stainless steel substrates is addressed by the use of SPADNS, which exhibits chelating properties, promoting film formation. The use of fine particles, prepared by the chemical polymerization method, allows impregnation of Ni foams and fabrication of porous electrodes with high materials loading for electrochemical supercapacitors (ES). PPy films and Ni foam based PPy electrodes show capacitive behaviour in Na2SO4 electrolyte. The electron microscopy studies, impedance spectroscopy data and analysis of the SPADNS structure provide an insight into the factors, controlling capacitive behaviour. The Ni foam based electrodes offer advantages of improved capacitive behaviour at high materials loadings and good cycling stability. The area normalized and volume normalized specific capacitances are as high as 5.43 F cm-2 and 93.6 F cm-3, respectively, for materials loading of 35.4 mg cm-2. The capacitance retention of Ni foam based electrodes is 91.5% after 1000 cycles. The Ni foam based PPy electrodes are promising for application in ES.

  2. Catalytic reduction of NO by methane using a Pt/C/polybenzimidazole/Pt/C fuel cell

    Petrushina, Irina; Cleemann, Lars Nilausen; Refshauge, Rasmus;

    2007-01-01

    The catalytic NO reduction by methane was studied using a (NO,CH4,Ar),Pt|polybenzimidazole(PBI)–H3PO4|Pt,(H2,Ar) fuel cell at 135 and 165°C. It has been found that, without any reducing agent (like CH4), NO can be electrochemically reduced in the (NO, Ar), Pt/C|PBI–H3PO4|Pt/C, (H2,Ar) fuel cell...

  3. Polybenzimidazole-decorated carbon nanotube: A high-performance proton conductor

    Majedi, Fatemeh Sadat [Laboratoire de Microsystemes (LMIS4), Ecole Polytechnique Federale de Lausanne (EPFL), Lausanne (Switzerland); Department of Biomedical Engineering, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Hasani-Sadrabadi, Mohammad Mahdi [Laboratoire de Microsystemes (LMIS4), Ecole Polytechnique Federale de Lausanne (EPFL), Lausanne (Switzerland); Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Dashtimoghadam, Erfan [Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Haghighi, Amir Hossein [Faculty of Engineering, Islamic Azad University, Shiraz Branch, Shiraz, Fars (Iran, Islamic Republic of); Bertsch, Arnaud; Renaud, Philippe [Laboratoire de Microsystemes (LMIS4), Ecole Polytechnique Federale de Lausanne (EPFL), Lausanne (Switzerland); Moaddel, Homayoun [Hydrogen and Fuel Cell Inc., Arcadia, CA (United States)

    2012-07-15

    Interaction between negatively charged Nafion {sup registered} and a positively charged polybenzimidazole-decorated carbon nanotube leads to the formation of an ionic complex with high charge density for proton conduction, which can lead to an improvement in transport properties. Here we investigate the high-temperature and low-humidity proton conductivity of this nanocomposite membrane as a potential membrane for fuel cell applications. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  4. Electrochemical promotion of oxidative coupling of methane on platinum/polybenzimidazole catalyst

    Petrushina, Irina; Bandur, Viktor; Bjerrum, Niels;

    2002-01-01

    The electrochemical promotion of catalytic methane oxidation was studied using a (CH4,O-2,Ar), Pt\\polybenzimidazole (PBI)-H3PO4\\Pt,(H-2,Ar) fuel cell at 135degreesC. It has been found that C2H2, CO2, and water are the main oxidation products. Without polarization the yield of C2H2 was 0.9% and the...

  5. Dielectric properties of solution-grown-undoped and acrylic-acid-doped ethyl cellulose

    P K Khare; Sandeep K Jain

    2000-02-01

    Dielectric capacities and losses were measured, in the temperature (50–170°C) and frequency (01–100 kHz range), for undoped and acrylic acid (AA) doped ethyl cellulose (EC) films (thickness about 20 m) with progressive increase in the concentration of dopant in the polymer matrix. The variation of capacity with temperature is attributed to thermal expansion in the lower temperature region to the orientation of dipolar molecules in the neighbourhood of glass transition temperature () and random thermal motion of molecules above . The dielectric losses exhibit a broad peak. Doping with AA is found to affect the magnitude and position of the peak. AA is found to have a two-fold action. Firstly, it enhances the chain mobility and secondly, it increases the dielectric loss by forming charge transfer complexes.

  6. EPR investigations of silicon carbide nanoparticles functionalized by acid doped polyaniline

    Karray, Fekri [Laboratoire des materiaux Ceramiques Composites et Polymeres, Faculte des Sciences de Sfax, BP 802, 3018 Sfax (Tunisia); Kassiba, Abdelhadi, E-mail: kassiba@univ-lemans.fr [Institute of Molecules and Materials of Le Mans (I3M), UMR-CNRS 6283, Universite du Maine, 72085 Le Mans (France)

    2012-06-15

    Nanocomposites (SiC-PANI) based on silicon carbide nanoparticles (SiC) encapsulated in conducting polyaniline (PANI) are synthesized by direct polymerization of PANI on the nanoparticle surfaces. The conductivity of PANI and the nanocomposites was modulated by several doping levels of camphor sulfonic acid (CSA). Electron paramagnetic resonance (EPR) investigations were carried out on representative SiC-PANI samples over the temperature range [100-300 K]. The features of the EPR spectra were analyzed taking into account the paramagnetic species such as polarons with spin S=1/2 involved in two main environments realized in the composites as well as their thermal activation. A critical temperature range 200-225 K was revealed through crossover changes in the thermal behavior of the EPR spectral parameters. Insights on the electronic transport properties and their thermal evolutions were inferred from polarons species probed by EPR and the electrical conductivity in doped nanocomposites.

  7. Synthesis and properties of segmented block copolymers of functionalised polybenzimidazoles for high-temperature PEM fuel cells

    Mader, J.A.; Benicewicz, B.C. [Department of Chemistry and Biochemistry and USC Nanocenter, University of South Carolina, 631 Sumter St., Columbia, SC 29208 (United States)

    2011-04-15

    A series of novel segmented block copolymers of sulphonated polybenzimidazole (PBI) (s-PBI) and p-PBI were prepared with various polymer ratios (10-90 mol% s-PBI; 90-10 mol% p-PBI). A two-step synthesis of oligomeric species, followed by combination and further polymerisation was used via the polyphosphoric acid (PPA) process. The membranes showed improved high-temperature proton conductivities and fuel cell performance over previous literature reports, with moderate incorporation of s-PBI into the copolymer showing the best results. The non-humidified fuel cell performance was extensively studied with various fuels and oxidants and showed excellent properties. Block copolymers that incorporated 40, 50 or 60 mol% s-PBI and the corresponding 60, 50 or 40 mol% p-PBI, at 0.2 A cm{sup -2} and 160 C, had hydrogen-air performances of 0.661-0.666 V, depending on composition. The performance was improved using hydrogen-oxygen, with voltages between 0.734 and 0.742 V at 0.2 A cm{sup -2} and 160 C. Fuel cells operating on a reformed hydrocarbon gas showed decreased performance (0.622-0.627 V, same conditions), especially at lower temperatures, but was significantly improved over previous literature reports of sulphonated PBI membranes operating at high temperatures. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. High performance B doped BiVO4 photocatalyst with visible light response by citric acid complex method.

    Wang, Min; Zheng, Haoyan; Liu, Qiong; Niu, Chao; Che, Yinsheng; Dang, Mingyan

    2013-10-01

    A B-doped BiVO4 photocatalyst was synthesized by citric acid complex method and using H3BO3 as the dopant source, and the photocatalyst was characterized with XPS, XRD, SEM, BET and UV-Vis DRS. The photocatalytic activity was evaluated by the photocatalytic degradation of a methyl orange (MO) solution under visible light. This assay revealed that both the pure BiVO4 and all of the B doped samples were the monoclinic phase. Doping the BiVO4 with B increased the number of V(4+) and oxygen vacancies, which led to the red shift of the absorbing boundary of the B-doped BiVO4 but had little influence on the morphology and crystal size. The B doping improved the photocatalytic activity, and the highest photocatalytic degradation rate of 98% occurred with a B dopant concentration of 0.04. PMID:23751222

  9. PEM steam electrolysis at 130 °C using a phosphoric acid doped short side chain PFSA membrane

    Hansen, Martin Kalmar; Aili, David; Christensen, Erik;

    2012-01-01

    Steam electrolysis test with a phosphoric acid doped Aquivion™ membrane was successfully conducted and current densities up to 775 mA cm-2 at 1.8 V was reached at 130 ºC and ambient pressure. A new composite membrane system using a perfluorosulfonic acid membrane (Aquivion™) as matrix and phospho......Steam electrolysis test with a phosphoric acid doped Aquivion™ membrane was successfully conducted and current densities up to 775 mA cm-2 at 1.8 V was reached at 130 ºC and ambient pressure. A new composite membrane system using a perfluorosulfonic acid membrane (Aquivion™) as matrix...... and phosphoric acid as proton conducting electrolyte was developed. Traditional perfluorosulfonic acid membranes do not possess sufficient dimensional stability and proton conductivity to be used at elevated temperatures and ambient pressures. The elevated temperature, high potentials and acidic conditions...

  10. Copper- or manganese-doped ZnS quantum dots as fluorescent probes for detecting folic acid in aqueous media

    3-Mercaptopropionic acid-capped core/shell ZnS:Cu/ZnS and ZnS:Mn/ZnS doped quantum dots (QDs) prepared through hydrothermal methods exhibit high photoluminescence intensity as well as good photostability. These water-dispersible nanoparticles exhibit high fluorescence sensitivity to folic acid due to the high affinity of the carboxylate groups and nitrogen atoms of folic acid towards the Zn surface atoms of the doped dots. Quenching of the fluorescence intensity of the QDs allows the detection of folic acid concentrations as low as 11 μM, thus affording a very sensitive system for the sensing of this biologically active molecule in aqueous solution. The possible quenching mechanism is discussed. - Graphical abstract: A sensitive method for the detection of folic acid based on the fluorescence quenching of Mn- or Cu-doped ZnS quantum dots was developed. Highlights: ► Quenching of the fluorescence intensity of doped ZnS QDs in the presence of folic acid. ► New fluorescent sensors for folic acid. ► Detection of folic acid concentrations as low as 11 μM in aqueous solution. ► The Perrin model and fluorescence lifetimes of ZnS:Mn QDs demonstrate a static quenching mechanism. ► Quenching efficiency of ZnS:Cu QDs correlates with the Stern-Volmer model.

  11. Simultaneous Chronoamperometric Sensing of Ascorbic Acid and Acetaminophen at a Boron-Doped Diamond Electrode

    Ciprian Radovan; Codruţa Cofan

    2008-01-01

    Cyclic voltammetry (CV) and chronoamperometry (CA) have been used to sense and determine simultaneously L-ascorbic acid (AA) and acetaminophen (AC) at a boron-doped diamond electrode (BDDE) in a Britton-Robinson buffer solution. The calibration plots of anodic current peak versus concentration obtained from CV and CA data for both investigated compounds in single and di-component solutions over the concentration range 0.01 mM – 0.1 mM proved to be linear, with very good correlation param...

  12. Magnetic resonance and electrical properties of p-toluene sulphonic acid doped polyaniline

    Arora, Manju; Arya, S. K.; Barala, Sunil Kumar; Saini, Parveen

    2013-06-01

    p-Toluene Sulphonic Acid (PTSA) doped polyaniline (PANI) analogues were synthesized by oxidative chemical polymerization method and characterized by TGA FTIR and EPR spectroscopic techniques. FTIR spectra indicates the formation of PTSA doped PANI and also revealed the dopant ions mediated interactions between polymeric chain through weak hydrogen bonding. TGA plots revealed that there is systematic variation in the weight loss at ˜300 °C from ˜4% to ˜38% with increase in dopant concentration from 0.01 N to 1.0 N. Magnetic resonance spectra of polaron charge carriers exhibit the single Lorentzian line signal with the Dysonian contribution indicating formation of metal-like domains. The polarons are localized in these domains by strong interaction between the neighboring conducting chains, in which the charge is transferred by quasi-three-dimensional (Q3D) delocalized electron. In higher concentration analogue some of polarons merge into diamagnetic bipolarons and this reduces intensity of EPR signal. The electrical conductivity of the 1.0 N PTSA doped sample was ˜4.5 S/cm which satisfies the EMI shielding criteri.

  13. Fabrication of folic acid sensor based on the Cu doped SnO2 nanoparticles modified glassy carbon electrode

    A novel folic acid biosensor has been fabricated using Cu doped SnO2 nanoparticles (NPs) synthesized by a simple microwave irradiation method. Powder XRD and TEM studies confirmed that both the pure and Cu doped SnO2 (Cu: 0, 10, 20wt%) crystallized in tetragonal rutile-type structure with spherical morphology. The average crystallite size of pure SnO2 was estimated to be around 16 nm. Upon doping, the crystallite sizes decreased to 9 nm and 5 nm for 10 and 20wt% Cu doped SnO2 respectively. XPS studies confirmed the electronic state of Sn and Cu to be 4+ and 2+ respectively. Cu (20wt%) doped SnO2 NPs are proved to be a good sensing element for the determination of folic acid (FA). Cu-SnO2 NPs (20wt%) modified glassy carbon electrode (GCE) exhibited the lowest detection limit of 0.024 nM over a wide folic acid concentration range of 1.0 × 10−10 to 6.7 × 10−5 M at physiological pH of 7.0. The fabricated sensor is highly selective towards the determination of FA even in the presence of a 100 fold excess of common interferent ascorbic acid. The sensor proved to be useful for the estimation of FA content in pharmaceutical sample with satisfactory recovery. (paper)

  14. Structure and gelation properties of casein micelles doped with curcumin under acidic conditions.

    Khanji, Aya N; Michaux, Florentin; Jasniewski, Jordane; Petit, Jeremy; Lahimer, Emna; Cherif, Mohamed; Salameh, Dominique; Rizk, Toufic; Banon, Sylvie

    2015-12-01

    In this study, the ability of micellar casein (MC) to interact with curcumin during acidification and to produce acid gel was investigated. Steady-state fluorescence spectroscopy of curcumin variation and fluorescence quenching of caseins upon binding with curcumin molecules were evidenced. Increasing the temperature from 20 to 35 °C enhanced MC-curcumin interactions as reflected by the increase in the binding constant from 0.6 ± 0.3 × 10(4) to 6.6 ± 0.6 × 10(4) M(-1). From changes in entropy, enthalpy and Gibbs free energy, hydrophobic interactions were proposed as major binding forces. Static fluorescence MC quenching was demonstrated for the MC-curcumin complex during acidification. From pH 7.4 to pH 5.0, the binding site numbers varied in the range from 1.25 ± 0.05 to 1.49 ± 0.05 and the binding constant kb varied from 3.9 ± 0.4 × 10(4) to 7.5 ± 0.7 × 10(4) M(-1). Small angle X-ray scattering profiles demonstrated that the MC internal structure was unchanged upon curcumin binding. The ζ-potential value of curcumin-doped MC indicated that curcumin did not modify the global charge of MC particles. Acid gelation studied by oscillation rheology and static multiple light scattering at 20 and 35 °C led to a similar behavior for native and curcumin-doped MC suspensions. For the first time, it was demonstrated that the colloidal and functional properties of MC were unchanged when doped with curcumin during acidification. PMID:26419313

  15. Preparation and reactivity of carboxylic acid-terminated boron-doped diamond electrodes

    Niedziolka-Joensson, Joanna [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France); Boland, Susan; Leech, Donal [School of Chemistry, National University of Irland, Galway (Ireland); Boukherroub, Rabah [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France); Szunerits, Sabine, E-mail: sabine.szunerits@iri.univ-lille1.f [Institut de Recherche Interdisciplinaire (IRI, USR 3078), Parc de la Haute Borne, 50 Avenue de Halley, BP 70478, 59658 Villeneuve d' Ascq (France); Institut d' Electronique, de Microelectronique et de Nanotechnologie (IEMN, UMR 8520), Cite Scientifique, Avenue Poincare, BP 60069, 59652 Villeneuve d' Ascq (France)

    2010-01-01

    The paper reports on the formation of carboxy-terminated boron-doped diamond (BDD) electrodes. The carboxylic acid termination was prepared in a controlled way by reacting photochemically oxidized BDD with succinic anhydride. The resulting interface was readily employed for the linking of an amine-terminated ligand such as an osmium complex bearing an amine terminal group. The interfaces were characterized using X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). Contact angle measurements were used to follow the changes in surface wetting properties due to surface functionalization. The chemical reactivity of the carboxyl-terminated BDD was investigated by covalent coupling of the acid groups to an amine-terminated osmium complex.

  16. Photocatalytic decomposition of perfluorooctanoic acid by iron and niobium co-doped titanium dioxide

    The photocatalytic decomposition of perfluorooctanoic acid (PFOA) in aqueous solution using Fe and Nb co-doped TiO2 (Fe:Nb-TiO2) prepared by sol-gel method was investigated. The photocatalytic activity of Fe:Nb-TiO2 towards PFOA degradation was compared to that of pure TiO2 synthesized using the same method, and that of the commercially available TiO2 photocatalyst, Aeroxide TiO2 P25 (AO-TiO2 P25). The photocatalysts were characterized by XRD, DRS, BET-N2 adsorption isotherm, and SEM-EDX techniques and the data were correlated to the photocatalytic activity. Fe:Nb-TiO2 showed the highest activity compared to the undoped TiO2 and the commercially available TiO2. Such activity was attributable to the effects of co-doping both on the physico-chemical properties and surface interfacial charge transfer mechanisms. Perfluorocarboxylic acids (PFCAs) with shorter carbon chain length and fluoride ions were identified as photocatalytic reaction intermediates and products.

  17. Photocatalytic decomposition of perfluorooctanoic acid by iron and niobium co-doped titanium dioxide

    Renan Estrellan, Carl, E-mail: estrellan.c.ac@m.titech.ac.jp [Department of International Development Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Salim, Chris; Hinode, Hirofumi [Department of International Development Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan)

    2010-07-15

    The photocatalytic decomposition of perfluorooctanoic acid (PFOA) in aqueous solution using Fe and Nb co-doped TiO{sub 2} (Fe:Nb-TiO{sub 2}) prepared by sol-gel method was investigated. The photocatalytic activity of Fe:Nb-TiO{sub 2} towards PFOA degradation was compared to that of pure TiO{sub 2} synthesized using the same method, and that of the commercially available TiO{sub 2} photocatalyst, Aeroxide TiO{sub 2} P25 (AO-TiO{sub 2} P25). The photocatalysts were characterized by XRD, DRS, BET-N{sub 2} adsorption isotherm, and SEM-EDX techniques and the data were correlated to the photocatalytic activity. Fe:Nb-TiO{sub 2} showed the highest activity compared to the undoped TiO{sub 2} and the commercially available TiO{sub 2}. Such activity was attributable to the effects of co-doping both on the physico-chemical properties and surface interfacial charge transfer mechanisms. Perfluorocarboxylic acids (PFCAs) with shorter carbon chain length and fluoride ions were identified as photocatalytic reaction intermediates and products.

  18. Continuous electrooxdiation of sulfuric acid on boron-doped diamond electrodes

    Highlights: • highly concentrated sulfuric acid was electrochemically oxidized to peroxosulfuric compounds • Diachem® boron-doped diamond electrodes were used both as anode and cathode to oxidize the sulfuric acid • a manufactured cation selective membrane was used in an unconventional electrolyte circuit • concentrations equivalent to a common SPM bath were reached • an alternative setup was applied using only one electrolyte circuit - ABSTRACT: This study reports on the electrochemical oxidation of highly concentrated sulfuric acid by Diachem® boron-doped diamond electrodes. The scope of this work was to evaluate a proposed continuous electrooxidation process in order to prepare a resist removal bath that contains equivalent amounts of peroxosulfuric compounds as a common SPM (sulfuric acid and hydrogen peroxide mixture) bath. The electrochemical processes at the electrode surface were investigated by cyclic voltammetry and by titration of the reaction products under real working conditions (> 80 wt% H2SO4). Furthermore, an alternative electrolysis test cell setup, exhibiting a thin and mechanically stable ion exchange membrane will be used. For this process only one electrolyte circuit is performed. The initial electrolysis product H2S2O8 immediately undergoes hydrolysis and forms H2SO5. The obtained concentration of H2SO5 was similar to a reference SPM bath (> 0.14 mol l−1 H2SO5 in 90 wt% H2SO4), even though the current efficiency was lower than for more diluted solutions. This can be attributed to a complex interplay of side and consumption reactions of peroxosulfuric compounds. This electrolysis bath has the potential to be a very promising alternative to standard SPM baths, as it operates as a continuous and sustainable process

  19. Synthesis and Characteristic Study on Complexes of Europium(Ⅲ) and Maleic Acid Doped with Non-Fluorescent Ions

    2007-01-01

    Complex of europium (Ⅲ) with maleic acid, and binuclear complexes of europium(Ⅲ)with maleic acid doped with non-fluorescent ions gadolinium, lanthanum and yttrium, were synthesized. The compositions and structures of complexes were characterized with elemental analysis, single crystal X-ray diffraction, IR and DSC-TG. Fluorescent properties were studied with fluorescence spectrum. The results indicated that the strongest fluorescent complexes were obtained when the ratio of europium and non-fluorescent ion was 8: 2. The order of Eu3+ fluorescence strengthened by three doped rare earths was Gd3+>La3+>Y3+.

  20. Inhibitive Effect of Hydrofluoric Acid Doped Poly Aniline (HFPANI on Corrosion of Iron in 1N Phosphoric Acid Solution

    G.Maheswari

    2015-03-01

    Full Text Available The inhibition effect of Hydrofluoric acid doped poly aniline HF-PANI on mild steel corrosion in 1N phosphoric acid has been studied by mass loss and polarization techniques and AC impedance measurements methods between 303 K and 333K.The inhibition efficiency increased with increase in concentration of HF PANI. The corrosion rate increased with increase in temperature and decreased with increase in concentration of inhibitor compared to blank. Potentiostatic polarization results revealed that HF-PANI act as mixed type inhibitor. The inhibitor of HF-PANI was chemically adsorbed and spontaneous adsorption on the mild steel surface .The values of activation energy (Ea, free energy of adsorption (ΔGads, heat of adsorption (Qads, enthalpy of adsorption (ΔH and entropy of adsorption (ΔS were calculated. The adsorption of inhibitor on mild steel surface has been found to obey Temkin’s adsorption isotherm. SEM analysis was agreed to establish the mechanism of corrosion inhibitor on mild steel corrosion in phosphoric acid medium.

  1. N, S co-doped carbon dots with orange luminescence synthesized through polymerization and carbonization reaction of amino acids

    Graphical abstract: N, S co-doped CDs with orange luminescence were synthesized through one-pot polymerization and carbonization reactions under hydrothermal conditions, using two different amino acids as raw materials. - Highlights: • N, S co-doped CDs were synthesized by one-pot carbonization reactions, using two different amino acids as raw materials. • The as-obtained N, S co-doped CDs showed unique orange fluorescence under excitation at room temperature. • The products could be applied in the imaging of peritoneal macrophages of mice without any functionalization. - Abstract: For practical application, it is highly desirable to obtain carbon dots (CDs) through environmentally benign synthetic route, using green raw materials. On the other hand, at present, most of CDs reported in the literature showed blue, green and yellow emission. Therefore it is still necessary to develop new strategy to obtain CDs with longer wavelength emission in order to expand their application range. Toward this end, in this study, N, S co-doped CDs were synthesized through one-pot condensation polymerization and carbonization reactions under hydrothermal conditions, using two different amino acids as raw materials. Taking the reaction of L-serine with L-cystine as an example, the as-obtained products were characterized by various techniques such as transmission electron microscopy, elemental analysis, Fourier-transform infrared spectrum, X-ray photoelectron spectra, and so on. Interestingly, N, S co-doped CDs displayed unique orange emission at room temperature. The possible photoluminescence mechanism of N, S co-doped CDs was proposed. Furthermore, the as-synthesized N, S co-doped CDs were directly applied in the imaging of peritoneal macrophages of mice

  2. N, S co-doped carbon dots with orange luminescence synthesized through polymerization and carbonization reaction of amino acids

    Zeng, Ya-Wen [Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027 (China); Ma, De-Kun, E-mail: dkma@wzu.edu.cn [Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027 (China); Wang, Wei; Chen, Jing-Jing; Zhou, Lin; Zheng, Yi-Zhou [Department of Hematology, The First Affiliated Hospital of Wenzhou Medical University, Wenzhou, Zhejiang 325027 (China); Yu, Kang, E-mail: yukang62@126.com [Department of Hematology, The First Affiliated Hospital of Wenzhou Medical University, Wenzhou, Zhejiang 325027 (China); Huang, Shao-Ming, E-mail: smhuang@wzu.edu.cn [Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027 (China)

    2015-07-01

    Graphical abstract: N, S co-doped CDs with orange luminescence were synthesized through one-pot polymerization and carbonization reactions under hydrothermal conditions, using two different amino acids as raw materials. - Highlights: • N, S co-doped CDs were synthesized by one-pot carbonization reactions, using two different amino acids as raw materials. • The as-obtained N, S co-doped CDs showed unique orange fluorescence under excitation at room temperature. • The products could be applied in the imaging of peritoneal macrophages of mice without any functionalization. - Abstract: For practical application, it is highly desirable to obtain carbon dots (CDs) through environmentally benign synthetic route, using green raw materials. On the other hand, at present, most of CDs reported in the literature showed blue, green and yellow emission. Therefore it is still necessary to develop new strategy to obtain CDs with longer wavelength emission in order to expand their application range. Toward this end, in this study, N, S co-doped CDs were synthesized through one-pot condensation polymerization and carbonization reactions under hydrothermal conditions, using two different amino acids as raw materials. Taking the reaction of L-serine with L-cystine as an example, the as-obtained products were characterized by various techniques such as transmission electron microscopy, elemental analysis, Fourier-transform infrared spectrum, X-ray photoelectron spectra, and so on. Interestingly, N, S co-doped CDs displayed unique orange emission at room temperature. The possible photoluminescence mechanism of N, S co-doped CDs was proposed. Furthermore, the as-synthesized N, S co-doped CDs were directly applied in the imaging of peritoneal macrophages of mice.

  3. Catalytic reduction of NO by methane using a Pt/C/polybenzimidazole/Pt/C fuel cell

    Petrushina, Irina; Cleemann, Lars Nilausen; Refshauge, Rasmus; Bjerrum, Niels; Bandur, Viktor

    2007-01-01

    The catalytic NO reduction by methane was studied using a (NO,CH4,Ar),Pt|polybenzimidazole(PBI)–H3PO4|Pt,(H2,Ar) fuel cell at 135 and 165°C. It has been found that, without any reducing agent (like CH4), NO can be electrochemically reduced in the (NO, Ar), Pt/C|PBI–H3PO4|Pt/C, (H2,Ar) fuel cell with participation of H+ or electrochemically produced hydrogen. When added, methane partially suppresses the electrochemical reduction of NO. Methane outlet concentration monitoring has shown the CH4 ...

  4. Experimental characterization and modeling of commercial polybenzimidazole-based MEA performance

    Korsgaard, Anders; Refshauge, R. H.; Nielsen, Mads Pagh; Bang, Mads; Kær, Søren Knudsen

    2006-01-01

    High temperature polymer fuel cells based on polybenzimidazole membranes (PBI) operated at 100-200 °C are currently receiving much attention in relation to fuel cell reforming systems due to two main reasons. At first they have proven to have excellent resistance to high CO concentrations, which...... decreases the number of system components in the fuel processing system. The preferential oxidation reactors can be left out and in addition a water condenser is not required. These system simplifications additionally decrease the parasitic losses associated with the components.  However, insufficient data...

  5. Radiation and storage-induced ageing of polypyrrole doped with dodecylbenzene sulfonic acid

    Kappen, P.; Brack, N.; Hale, P. S.; Prissanaroon, W.; Welter, E.; Pigram, P. J.

    2005-04-01

    The effects of storage and exposure to X-rays on the surface chemistry of electrochemically prepared polypyrrole (PPy) doped with dodecylbenzene sulfonic acid (DBSA) were investigated using X-ray photoelectron spectroscopy (XPS). For irradiation, different photon sources (lab source and synchrotron radiation) and energies (1.4-9 keV) were chosen. This covers an energy range of relevance for many X-ray based investigations (e.g. XPS or X-ray absorption spectroscopy) of PPy[DBSA], PPy-metal interfaces, and transition metals embedded into PPy. The DBSA doping level and the concentration ratio of sulfonate species are discussed as a function of storage and irradiation times, and links between both ageing parameters are given. New sulfur species are found to emerge upon repeated soft X-ray irradiation. Severe changes in the polaron/bipolaron structure of PPy[DBSA] during exposure to high energy (several keV) synchrotron radiation are observed, and the results are discussed in the light of photon absorption and photoelectron generation in the polymer surface.

  6. Radiation and storage-induced ageing of polypyrrole doped with dodecylbenzene sulfonic acid

    The effects of storage and exposure to X-rays on the surface chemistry of electrochemically prepared polypyrrole (PPy) doped with dodecylbenzene sulfonic acid (DBSA) were investigated using X-ray photoelectron spectroscopy (XPS). For irradiation, different photon sources (lab source and synchrotron radiation) and energies (1.4-9 keV) were chosen. This covers an energy range of relevance for many X-ray based investigations (e.g. XPS or X-ray absorption spectroscopy) of PPy[DBSA], PPy-metal interfaces, and transition metals embedded into PPy. The DBSA doping level and the concentration ratio of sulfonate species are discussed as a function of storage and irradiation times, and links between both ageing parameters are given. New sulfur species are found to emerge upon repeated soft X-ray irradiation. Severe changes in the polaron/bipolaron structure of PPy[DBSA] during exposure to high energy (several keV) synchrotron radiation are observed, and the results are discussed in the light of photon absorption and photoelectron generation in the polymer surface

  7. Radiation and storage-induced ageing of polypyrrole doped with dodecylbenzene sulfonic acid

    Kappen, P. [Centre for Materials and Surface Science, La Trobe University, Vic. 3086 (Australia)]. E-mail: p.kappen@latrobe.edu.au; Brack, N. [Centre for Materials and Surface Science, La Trobe University, Vic. 3086 (Australia); Hale, P.S. [Centre for Materials and Surface Science, La Trobe University, Vic. 3086 (Australia); Prissanaroon, W.; Welter, E. [Hamburg Synchrotron Radiation Laboratory (HASYLAB), Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, D-22607 Hamburg (Germany); Pigram, P.J. [Centre for Materials and Surface Science, La Trobe University, Vic. 3086 (Australia)

    2005-04-30

    The effects of storage and exposure to X-rays on the surface chemistry of electrochemically prepared polypyrrole (PPy) doped with dodecylbenzene sulfonic acid (DBSA) were investigated using X-ray photoelectron spectroscopy (XPS). For irradiation, different photon sources (lab source and synchrotron radiation) and energies (1.4-9 keV) were chosen. This covers an energy range of relevance for many X-ray based investigations (e.g. XPS or X-ray absorption spectroscopy) of PPy[DBSA], PPy-metal interfaces, and transition metals embedded into PPy. The DBSA doping level and the concentration ratio of sulfonate species are discussed as a function of storage and irradiation times, and links between both ageing parameters are given. New sulfur species are found to emerge upon repeated soft X-ray irradiation. Severe changes in the polaron/bipolaron structure of PPy[DBSA] during exposure to high energy (several keV) synchrotron radiation are observed, and the results are discussed in the light of photon absorption and photoelectron generation in the polymer surface.

  8. Polybenzimidazole Membranes Containing Benzimidazole Side Groups for High Temprature Polymer Electrolyte Membrane Fuel Cells

    Yang, Jingshuai; Li, Xueyuan; Xu, Yizin;

    2013-01-01

    temperatures without humidification. At an acid doping level of 13.1 mol H3PO4 per average molar repeat unit, the PBI membranes with a benzimidazole grafting degree of 10.6% demonstrated a conductivity of 0.15 S cm-1 and a H2-air fuel cell peak power density of 378 mW cm-2 at 180 oC at ambient pressure without...

  9. Flexible, all-organic ammonia sensor based on dodecylbenzene sulfonic acid-doped polyaniline films

    A stable chlorobenzene dispersion of conducting polyaniline (PANI) has been obtained by doping emeraldine base with dodecylbenzene sulfonic acid (DBSA) and studied by spectrophotometric measurements in the UV-vis-IR range. The electrical properties of PANI: DBSA films obtained from the above dispersion have been investigated under different temperature and relative humidity conditions. All-organic chemoresistive devices have been developed by spin-coating the PANI: DBSA dispersion on flexible substrates, and then by depositing electrodes on the top, from a carbon nanotube conducting ink. Sensing tests performed under exposition to calibrated amounts of ammonia reveal that these simple and inexpensive sensors are able to detect ammonia at room temperature in a reliable way, with a sensitivity linearly related to concentration in the range between 5 ppm and 70 ppm.

  10. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells

    Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

    2015-01-01

    The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells. PMID:26601132

  11. KDP crystal doped with L-arginine amino acid: growth, structure perfection, optical and strength characteristics

    Pritula, I. M.; Kostenyukova, E. I.; Bezkrovnaya, O. N.; Kolybaeva, M. I.; Sofronov, D. S.; Dolzhenkova, E. F.; Kanaev, A.; Tsurikov, V.

    2016-07-01

    Potassium Dihydrogen Phosphate (KDP) crystal doped with L-arginine (L-arg) amino acid with 1.4 wt% concentration in the solution was grown onto a point seed by the method of temperature reduction. For the first time an attempt was made to grow large-size (7 × 6 × 8 cm3) optically transparent crystals, which allowed to analyze the effect of L-arg additive on the physical properties of the different growth sectors ({100} and {101}) of KDP. The incorporation of L-arg into both growth sectors of the crystal was confirmed by the methods of optical and IR spectroscopy and found to be caused by the ability of the amino acid to form hydrogen bonds with the face {100} and electrostatically interact with the positively charged face {101} of KDP crystal. A slight variation in the unit cell parameters was reported, the elementary cell volume of KDP:L-arg crystal increased in comparison with the one of pure KDP by 2·10-2 and 2.07·10-2 Å3 in the sectors {100} and {101}, respectively. It was found that the doping of L-arg enhanced the SHG efficiency of KDP and depended on the crystal growth sectors. The SHG efficiency of KDP:L-arg was by a factor 2.53 and 3.95 higher in comparison with those of pure KDP for {101} and {100} growth sector, respectively. The doping was found to lead to softening of both faces by ∼3-10% and ∼14-17% in the sectors {101} and {100}, respectively. Investigation of the influence of L-arg molecules on the bulk laser damage threshold of the crystals showed that the bulk laser damage threshold of the samples of KDP:L-arg crystal was higher than the one of the pure crystal in the sector {101} and lower in the sector {100}. The correlation between microhardness and laser damage threshold were discussed. The study is helpful for further searching, designing and simulation of hybrid NLO materials.

  12. Dual responsive dysprosium-doped hydroxyapatite particles and toxicity reduction after functionalization with folic and glucuronic acids

    Sánchez Lafarga, Ana Karen; Pacheco Moisés, Fermín P. [Departamento de Química, Universidad de Guadalajara, Marcelino García Barragán 1421, C.P. 44430, Guadalajara, Jalisco (Mexico); Gurinov, Andrey [Research Resources Center for Magnetic Resonance, Saint Petersburg State University, Universitetskij pr. 26, 198504 St. Petersburg (Russian Federation); Ortiz, Genaro Gabriel [Laboratorio Desarrollo-Envejecimiento, Enfermedades Neurodegenerativas, Centro de Investigación Biomédica de Occidente (CIBO), Instituto Mexicano de Seguro Social (IMSS), Guadalajara, Jalisco (Mexico); Carbajal Arízaga, Gregorio Guadalupe, E-mail: gregoriocarbajal@yahoo.com.mx [Departamento de Química, Universidad de Guadalajara, Marcelino García Barragán 1421, C.P. 44430, Guadalajara, Jalisco (Mexico)

    2015-03-01

    The development of probes for biomedical applications demands materials with low toxicity levels besides fluorescence or magnetic properties to be detected by confocal microscopes or MRI resonators. Several drug delivery systems or other biomedical materials prepared with hydroxyapatite have been proposed, however, toxicity effects might arise when the size of particles is nanometric. In this study, hydroxyapatite functionalized with glucuronic or folic acids presented lower oxidative stress, measured from lipoperoxides and nitric oxide indicators in rats than pure hydroxyapatite. In separated experiments, hydroxyapatite was doped with dysprosium cations by coprecipitation producing a single crystal phase with fluorescent properties easily visualized by confocal microscopy when excited at 488 nm. These particles also presented the ability to modify the proton relaxation time in T1 maps collected by magnetic resonance imaging. These modified hydroxyapatite nanoparticles could be candidates to design bimodal probes with low toxicity. - Highlights: • Hydroxyapatite functionalized with glucuronic acid reduced oxidative stress in rats. • Functionalization with folic acid reduced oxidative stress in rats. • Dysprosium doping does not affect the crystalline structure of hydroxyapatite. • Dysprosium doped particles are visible in fluorescent microscope. • Dysprosium doped particles act as MRI contrast agents.

  13. Dual responsive dysprosium-doped hydroxyapatite particles and toxicity reduction after functionalization with folic and glucuronic acids

    The development of probes for biomedical applications demands materials with low toxicity levels besides fluorescence or magnetic properties to be detected by confocal microscopes or MRI resonators. Several drug delivery systems or other biomedical materials prepared with hydroxyapatite have been proposed, however, toxicity effects might arise when the size of particles is nanometric. In this study, hydroxyapatite functionalized with glucuronic or folic acids presented lower oxidative stress, measured from lipoperoxides and nitric oxide indicators in rats than pure hydroxyapatite. In separated experiments, hydroxyapatite was doped with dysprosium cations by coprecipitation producing a single crystal phase with fluorescent properties easily visualized by confocal microscopy when excited at 488 nm. These particles also presented the ability to modify the proton relaxation time in T1 maps collected by magnetic resonance imaging. These modified hydroxyapatite nanoparticles could be candidates to design bimodal probes with low toxicity. - Highlights: • Hydroxyapatite functionalized with glucuronic acid reduced oxidative stress in rats. • Functionalization with folic acid reduced oxidative stress in rats. • Dysprosium doping does not affect the crystalline structure of hydroxyapatite. • Dysprosium doped particles are visible in fluorescent microscope. • Dysprosium doped particles act as MRI contrast agents

  14. Effect of sorbic acid doping on flux pinning in bulk MgB2 with the percolation model

    In this paper, we study the doping effect of sorbic acid (C6H8O2), from 0 to 20 wt.% of the total MgB2, on critical temperature (Tc), critical current density (Jc), irreversibility field (Hirr) and crystalline structure. The XRD patterns of samples show a slightly decrease in a-axis lattice parameter for doped samples, due to the partial substitution of carbon at boron site. On the other hand, we investigate the influence of doping on the behavior of flux pinning and Jc(B) in the framework of percolation theory and it is found that the Jc(B) behavior could be well fitted in high field region. The two key parameters, anisotropy and percolation threshold, play very important roles. It is believed that the enhancement of Jc is due to the reduction of anisotropy in high field region.

  15. Electrochemical promotion of NO reduction by hydrogen on a platinum/polybenzimidazole catalyst

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm; Bjerrum, Niels; Sørensen, Rasmus Zink; Refshauge, R.H.; Li, Qingfeng

    2003-01-01

    The electrochemical promotion of catalytic NO reduction by hydrogen was studied using a (NO, H-2, Ar), Pt polybenzimidazole (PBI)-H3PO4\\Pt, (H-2, Ar) fuel cell at 135degreesC. A mixture of NO/H-2/Ar was used as the working mixture at one electrode and a mixture of H-2/Ar was used as reference and counter gas at the other electrode. Products of NO reduction (N-2 and H2O) were analyzed by an on-line mass spectrometer. At high NO+H-2+Ar flow rate (17 mL/min; 17 and 354 mL/min, respectively, at a...

  16. Polybenzimidazoles based on high temperature polymer electrolyte fuel cells

    Linares Leon, Jose Joaquin; Camargo, Ana Paula M.; Ashino, Natalia M.; Morgado, Daniella L.; Frollini, Elisabeth; Paganin, Valdecir A.; Gonzalez, Ernesto Rafael [Universidade de Sao Paulo (IQSC/USP), Sao Carlos, SP (Brazil); Bajo, Justo Lobato [University of Castilla-La Mancha, Ciudad Real (Spain). Dept. of Chemical Engineering

    2010-07-01

    This work presents an interesting approach in order to enhance the performance of Polymer Electrolyte Membrane Fuel Cells (PEMFC) by means of an increase in the operational temperature. For this, two polymeric materials, Poly(2,5-bibenzimidazole) (ABPBI) and Poly[2,2'-(m-phenyl en)-5,5' bib enzimidazol] (PBI), impregnated with phosphoric acid have been utilized. These have shown excellent properties, such as thermal stability above 500 deg C, reasonably high conductivity when impregnated with H{sub 3}PO{sub 4} and a low permeability to alcohols compared to Nafion. Preliminary fuel cells measurements on hydrogen based Polymer Electrolyte Membrane Fuel Cell (PEMFC) displayed an interestingly reasonable good fuel cell performance, a quite reduced loss when the hydrogen stream was polluted with carbon monoxide, and finally, when the system was tested with an ethanol/water (E/W) fuel, it displayed quite promising results that allows placing this system as an attractive option in order to increase the cell performance and deal with the typical limitations of low temperature Nafion-based PEMFC. (author)

  17. Assay of phospholipase A2 with E. coli membrane doped by 3H-arachidonic acid

    Objective: To develop a new radiochemistry method to assay the secretory phospholipase A2 (sPLA2) and cytosolic phospholipase A2 (cPLA2) with a same substrate. Methods: E.coli membrane doped by 3H-arachidonic acid was prepared and hydrolyzed by PLA2 in certain condition, and the enzyme activity was expressed with the hydrolyzing rate. Results: Intra-day coefficient of variation (CV) of cPLA2 was 5.2% and inter-day CV was 10.9%, and 4.9% and 7.8% for sPLA2 respectively. Results of a series proportional dilution assay showed a good linear relationship. Serum sPLA2 activities of patients with acute cholecystitis were significantly higher than that of normal control subjects. There was a significant difference of activities of sPLA2 and cPLA2 between the endotoxin induced leukemia cell K562 and control. Conclusions: This method is specific, stable and sensitive, it may be used in clinical and scientific research

  18. Simultaneous Chronoamperometric Sensing of Ascorbic Acid and Acetaminophen at a Boron-Doped Diamond Electrode

    Ciprian Radovan

    2008-06-01

    Full Text Available Cyclic voltammetry (CV and chronoamperometry (CA have been used to sense and determine simultaneously L-ascorbic acid (AA and acetaminophen (AC at a boron-doped diamond electrode (BDDE in a Britton-Robinson buffer solution. The calibration plots of anodic current peak versus concentration obtained from CV and CA data for both investigated compounds in single and di-component solutions over the concentration range 0.01 mM – 0.1 mM proved to be linear, with very good correlation parameters. Sensitivity values and RSD of 2-3% were obtained for various situations, involving both individual and simultaneous presence of AA and AC. The chronoamperometric technique associated with standard addition in sequential one step and/or two successive and continuous chronoamperograms at two characteristic potential levels represented a feasible option for the simultaneous determination of AA and AC in real sample systems such as pharmaceutical formulations. The average values indicated by the supplier were confirmed to a very close approximation from chronoamperomgrams by using several additions with the application of suitable current correction factors.

  19. Comparison of chondroitin sulfate and hyaluronic Acid doped conductive polypyrrole films for adipose stem cells.

    Björninen, Miina; Siljander, Aliisa; Pelto, Jani; Hyttinen, Jari; Kellomäki, Minna; Miettinen, Susanna; Seppänen, Riitta; Haimi, Suvi

    2014-09-01

    Polypyrrole (PPy) is a conductive polymer that has aroused interest due to its biocompatibility with several cell types and high tailorability as an electroconductive scaffold coating. This study compares the effect of hyaluronic acid (HA) and chondroitin sulfate (CS) doped PPy films on human adipose stem cells (hASCs) under electrical stimulation. The PPy films were synthetized electrochemically. The surface morphology of PPy-HA and PPy-CS was characterized by an atomic force microscope. A pulsed biphasic electric current (BEC) was applied via PPy films non-stimulated samples acting as controls. Viability, attachment, proliferation and osteogenic differentiation of hASCs were evaluated by live/dead staining, DNA content, Alkaline phosphatase activity and mineralization assays. Human ASCs grew as a homogenous cell sheet on PPy-CS surfaces, whereas on PPy-HA cells clustered into small spherical structures. PPy-CS supported hASC proliferation significantly better than PPy-HA at the 7 day time point. Both substrates equally triggered early osteogenic differentiation of hASCs, although mineralization was significantly induced on PPy-CS compared to PPy-HA under BEC. These differences may be due to different surface morphologies originating from the CS and HA dopants. Our results suggest that PPy-CS in particular is a potential osteogenic scaffold coating for bone tissue engineering. PMID:24823653

  20. Z-scan measurements of single walled carbon nanotube doped acetylenedicarboxylic acid polymer under CW laser

    Zidan, M. D.; Allaf, A. W.; Allahham, A.; AL-Zier, A.

    2016-06-01

    Z-scan measurements of single walled carbon nanotube (SWCNT) doped with acetylenedicarboxylic acid (ADC) polymer are performed using a CW diode laser at 635 nm wavelength with 17 mW power. The nonlinear absorption coefficient (β), nonlinear refractive index (n2), the real and imaginary parts of the third-order nonlinear optical susceptibility (Re χ3), (Im χ3) of the investigated samples are calculated. It was found that the β values decrease with increase in on-axis input intensity I0. Also, these values are found to be proportional with sample concentrations. The excited-state absorption cross sections were calculated to be at σex=5.08×10-14 cm2 for the (SWCNT) and at 15.1×10-14 cm2 for the ADC polymer. It was found that the σex is larger than ground-state absorption cross sections, indicating that the reverse saturable absorption mechanism (RSA) is the dominating mechanism for the observed absorption nonlinearities.

  1. Electrochemical oxidation of oxalic acid in the presence of halides at boron doped diamond electrode

    Martinez-Huitle, C.A. [University of Milan, Milan (Italy). Dept. of Analytical Chemistry]. E-mail: Carlos.Martinez@unimi.it; Ferro, S.; Battisti, A. de [University of Ferrara (Italy). Dept. of Chemistry. Lab. of Electrochemistry; Reyna, S.; Cerro-Lopez, M.; Quiroz, M.A. [Universidad de las Americas-Puebla, Puebla (Mexico). Dept. de Quimica y Biologia. Lab. de Electroquimica]. E-mail: marcoa.quiroz@udlap.mx

    2008-07-01

    Aim of this work is to discuss the electrochemical oxidation of oxalic acid (OA), analyzing the influence of NaCl and NaBr. Experiments were carried out at boron-doped diamond (BDD) electrodes, in alkaline media. BDD electrodes have a poor superficial adsorptivity so their great stability toward oxidation allows the reaction to take place with reactants and intermediates in a non-adsorbed state. The process is significantly accelerated by the presence of a halogen salt in solution; interestingly, the mediated process does not depend on applied current density. Based on the results, bromide was selected as a suitable mediator during OA oxidation at BDD. Br{sup -} primarily acts in the volume of the solution, with the formation of strong oxidants; while Cl{sup -} action has shown lower improvements in the OA oxidation rate at BDD respect to the results reported using Pt electrode. Finally, the parameters of removal efficiency and energy consumption for the electrochemical incineration of OA were calculated. (author)

  2. Photophysical characterization of cumarin-doped poly (lactic acid) microparticles and visualization of the biodistribution

    We prepared fluorescent coumarin dye-doped poly (acrylic acid) microparticles, which are well known as a biodegradable polyester, and the photophysical properties were characterized by scanning electron microscope, atomic force microscope and spectroscopic investigation. Spherical particles with diameters ranging from 0.5 to a few μm were obtained. Based on spectroscopic investigation, the internal environment was close to that of a polar solvent such as methanol, and the dyes were dispersed without aggregation inside the particles. The obtained particles were administered to a mouse through the tail vein, and the biodistribution was then observed after some organs were excited at 1-day and 1-week post-injection. The particles were accumulated in the organs, especially in the lung and spleen. After injection, the particles were trapped temporally in the lung, and then seemed to be transported to other organs by blood circulation. This tendency is similar to the biodistribution of TiO2 microparticles that we have reported previously.

  3. Photophysical characterization of cumarin-doped poly (lactic acid) microparticles and visualization of the biodistribution

    Abe, Shigeaki, E-mail: sabe@den.hokudai.ac.j [Department of Biomedical Materials and Engineering, Graduate School of Dental Medicine, Hokkaido University, Kita 13, Nishi 7, Sapporo 060-8586 (Japan); Kiba, Takayuki; Hosokawa, Kiyotada; Nitobe, Satoru; Hirota, Takashi; Kobayashi, Hirohisa [Division of Biotechnology and Macromolecular Chemistry, Graduate School of Hokkaido University, Sapporo 060-8628 (Japan); Akasaka, Tsukasa; Uo, Motohiro; Kuboki, Yoshinori [Department of Biomedical Materials and Engineering, Graduate School of Dental Medicine, Hokkaido University, Kita 13, Nishi 7, Sapporo 060-8586 (Japan); Sato, Shin-Ichiro [Division of Biotechnology and Macromolecular Chemistry, Graduate School of Hokkaido University, Sapporo 060-8628 (Japan); Watari, Fumio [Department of Biomedical Materials and Engineering, Graduate School of Dental Medicine, Hokkaido University, Kita 13, Nishi 7, Sapporo 060-8586 (Japan); Rosca, Iosif D. [Faculty of Engineering and Computer Science, Concordia University, 1455 de Maisonneuve Blvd. W, Montreal, QC H3G 1M8 (Canada)

    2010-08-15

    We prepared fluorescent coumarin dye-doped poly (acrylic acid) microparticles, which are well known as a biodegradable polyester, and the photophysical properties were characterized by scanning electron microscope, atomic force microscope and spectroscopic investigation. Spherical particles with diameters ranging from 0.5 to a few {mu}m were obtained. Based on spectroscopic investigation, the internal environment was close to that of a polar solvent such as methanol, and the dyes were dispersed without aggregation inside the particles. The obtained particles were administered to a mouse through the tail vein, and the biodistribution was then observed after some organs were excited at 1-day and 1-week post-injection. The particles were accumulated in the organs, especially in the lung and spleen. After injection, the particles were trapped temporally in the lung, and then seemed to be transported to other organs by blood circulation. This tendency is similar to the biodistribution of TiO{sub 2} microparticles that we have reported previously.

  4. Development of Polybenzimidazole-Based High-Temperature Membrane and Electrode Assemblies for Stationary and Automotive Applications

    Vogel, John A.

    2008-09-03

    The program began on August 1, 2003 and ended on July 31, 2007. The goal of the project was to optimize a high-temperature polybenzimidazole (PBI) membrane to meet the performance, durability, and cost targets required for stationary fuel cell applications. These targets were identified in the Fuel Cell section (3.4) of DOE’s Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year Research, Development and Demonstration Plan. A membrane that operates at high temperatures is important to the fuel cell industry because it is insensitive to carbon monoxide (a poison to low-temperature fuel cells), and does not require complex water management strategies. Together, these two benefits greatly simplify the fuel cell system. As a result, the high-temperature fuel cell system realizes a cost benefit as the number of components is reduced by nearly 30%. There is also an inherent reliability benefit as components such as humidifiers and pumps for water management are unnecessary. Furthermore, combined heat and power (CHP) systems may be the best solution for a commercial, grid-connected, stationary product that must offer a cost benefit to the end user. For a low-temperature system, the quality of the heat supplied is insufficient to meet consumer needs and comfort requirements, so peak heaters or supplemental boilers are required. The higher operating temperature of PBI technology allows the fuel cell to meet the heat and comfort demand without the additional equipment. Plug Power, working with the Rensselaer Polytechnic Institute (RPI) Polymer Science Laboratory, made significant advances in optimizing the PBI membrane material for operation at temperatures greater than 160oC with a lifetime of 40,000 hours. Supporting hardware such as flow field plates and a novel sealing concept were explored to yield the lower-cost stack assembly and corresponding manufacturing process. Additional work was conducted on acid loss, flow field design and cathode electrode

  5. Low thermal budget n-type doping into Ge(001) surface using ultraviolet laser irradiation in phosphoric acid solution

    Takahashi, Kouta, E-mail: ktakahas@alice.xtal.nagoya-u.ac.jp, E-mail: kurosawa@alice.xtal.nagoya-u.ac.jp; Sakashita, Mitsuo; Takeuchi, Wakana; Nakatsuka, Osamu [Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kurosawa, Masashi, E-mail: ktakahas@alice.xtal.nagoya-u.ac.jp, E-mail: kurosawa@alice.xtal.nagoya-u.ac.jp [Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Institute of Materials and Systems for Sustainability, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Institute for Advanced Research, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601 (Japan); Ikenoue, Hiroshi [Graduate School of Information Science and Electrical Engineering, Kyushu University, 744 Motooka, Fukuoka 819-0395 (Japan); Zaima, Shigeaki [Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Institute of Materials and Systems for Sustainability, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

    2016-02-01

    We have investigated phosphorus (P) doping into Ge(001) surfaces by using ultraviolet laser irradiation in phosphoric acid solution at room temperature. We demonstrated that the diffusion depth of P in Ge and the concentration of electrically activated P can be controlled by the number of laser shots. Indeed, a high concentration of electrically activated P of 2.4 × 10{sup 19} cm{sup −3} was realized by 1000-times laser shots at a laser energy of 1.0 J/cm{sup 2}, which is comparable or better than the counterparts of conventional n-type doping using a high thermal budget over 600 °C. The generation current is dominant in the reverse bias condition for the laser-doped pn-junction diodes independent on the number of laser shots, thus indicating low-damage during the pn-junction formation. These results open up the possibility for applicable low thermal budget doping process for Ge-based devices fabricated on flexible substrates as well as Si electronics.

  6. Low thermal budget n-type doping into Ge(001) surface using ultraviolet laser irradiation in phosphoric acid solution

    We have investigated phosphorus (P) doping into Ge(001) surfaces by using ultraviolet laser irradiation in phosphoric acid solution at room temperature. We demonstrated that the diffusion depth of P in Ge and the concentration of electrically activated P can be controlled by the number of laser shots. Indeed, a high concentration of electrically activated P of 2.4 × 1019 cm−3 was realized by 1000-times laser shots at a laser energy of 1.0 J/cm2, which is comparable or better than the counterparts of conventional n-type doping using a high thermal budget over 600 °C. The generation current is dominant in the reverse bias condition for the laser-doped pn-junction diodes independent on the number of laser shots, thus indicating low-damage during the pn-junction formation. These results open up the possibility for applicable low thermal budget doping process for Ge-based devices fabricated on flexible substrates as well as Si electronics

  7. Low thermal budget n-type doping into Ge(001) surface using ultraviolet laser irradiation in phosphoric acid solution

    Takahashi, Kouta; Kurosawa, Masashi; Ikenoue, Hiroshi; Sakashita, Mitsuo; Takeuchi, Wakana; Nakatsuka, Osamu; Zaima, Shigeaki

    2016-02-01

    We have investigated phosphorus (P) doping into Ge(001) surfaces by using ultraviolet laser irradiation in phosphoric acid solution at room temperature. We demonstrated that the diffusion depth of P in Ge and the concentration of electrically activated P can be controlled by the number of laser shots. Indeed, a high concentration of electrically activated P of 2.4 × 1019 cm-3 was realized by 1000-times laser shots at a laser energy of 1.0 J/cm2, which is comparable or better than the counterparts of conventional n-type doping using a high thermal budget over 600 °C. The generation current is dominant in the reverse bias condition for the laser-doped pn-junction diodes independent on the number of laser shots, thus indicating low-damage during the pn-junction formation. These results open up the possibility for applicable low thermal budget doping process for Ge-based devices fabricated on flexible substrates as well as Si electronics.

  8. High temperature proton exchange membranes based on polybenzimidazoles for fuel cells

    Li, Qingfeng; Jensen, Jens Oluf; Savinell, Robert F;

    2009-01-01

    havebeenmadeincluding spectroscopy,wateruptake and acid doping, thermal and oxidative stability, conductivity, electro-osmoticwater drag, methanol crossover, solubility and permeability of gases, and oxygen reduction kinetics. Related fuel cell technologies such as electrode and MEA fabrication have been developed...... with synthetically modified or N-substituted structures have been synthesized. Techniques for membrane casting from organic solutions and directly from acid solutions have been developed. Ionic and covalent cross-linking as well as inorganic–organic composites has been explored. Membrane characterizations......-term durability with a degradation rate of 5Vh−1 has been achieved under continuous operation with hydrogen and air at 150–160 ◦C. With load or thermal cycling, a performance loss of 300V per cycle or 40Vh−1 per operating hour was observed. Further improvement should be done by, e.g. optimizing the thermal...

  9. Oxygen reduction reaction over nitrogen-doped graphene oxide cathodes in acid and alkaline fuel cells at intermediate temperatures

    Highlights: • ORR for nitrogen-doped graphene in acid and alkaline fuel cells at intermediate temperatures. • Nitrogen-doped graphene had higher activity for the ORR than graphene. • The ORR activity was enhanced by an increase in the operating temperature. • The ORR activity was kept for long time in both acid and alkaline fuel cells. - Abstract: Graphene oxides with various nitrogen contents were prepared by annealing them in an NH3 flow between 350 and 850 °C, and their electrocatalytic properties toward the oxygen reduction reaction (ORR) in acid and alkaline fuel cells at intermediate temperatures were investigated. In both acid and alkaline fuel cells, graphene oxide treated with NH3 at 700 °C for 1 h was the most active cathode at operating temperatures between 75 and 200 °C, where the ORR activity was enhanced by an increase in the operating temperature. This cathode also exhibited high chemical and thermal stability toward the ORR. X-ray photoelectron and Raman spectroscopic measurements of the nitrogen-doped graphene oxides indicated that the pyridinic nitrogen introduced disordered edge planes into the graphene structure. BET analysis also revealed that the surface area of graphene oxide was increased by the exposure of such edge planes. These observations lead to the assumption that the defects introduced by pyridinic nitrogen act as active sites for the ORR. Considering the similarity in ORR activity between the acid and alkaline fuel cells, dissociative adsorption of O2 at the active site is a rate-determining step

  10. N-Co-O Triply Doped Highly Crystalline Porous Carbon: An Acid-Proof Nonprecious Metal Oxygen Evolution Catalyst.

    Yang, Shiliu; Zhan, Yi; Li, Jingfa; Lee, Jim Yang

    2016-02-10

    In comparison with nonaqueous Li-air batteries, aqueous Li-air batteries are kinetically more facile and there is more variety of non-noble metal catalysts available for oxygen electrocatalysis, especially in alkaline solution. The alkaline battery environment is however vulnerable to electrolyte carbonation by atmospheric CO2 resulting in capacity loss over time. The acid aqueous solution is immune to carbonation but is limited by the lack of effective non-noble metal catalysts for the oxygen evolution reaction (OER). This is contrary to the oxygen reduction reaction (ORR) in acid solution where a few good candidates exist. We report here the development of a N-Co-O triply doped carbon catalyst with substantial OER activity in acid solution by the thermal codecomposition of polyaniline, cobalt salt and cyanamide in nitrogen. Cyanamide and the type of cobalt precursor salt were found to determine the structure, crystallinity, surface area, extent of Co doping and consequently the OER activity of the final carbon catalyst in acid solution. We have also put forward some hypotheses about the active sites that may be useful for guiding further work. PMID:26795393

  11. Nitrogen-doped carbon nanofoam derived from amino acid chelate complex for supercapacitor applications

    Ramakrishnan, Prakash; Shanmugam, Sangaraju

    2016-06-01

    We report a novel strategy to fabricate the nitrogen-doped mesoporous carbon nanofoam structures (N-MCNF), derived from magnesium amino acid chelate complex (Mg-acc-complex) for its application towards high performance supercapacitor (SCs) system. A series of N-MCNF with well-connected carbon nanofoam structure have been developed by varying the synthesis temperature. The fabricated N-MCNF material possesses a high surface area (1564 m2 g-1) and pore volume (1.767 cm3 g-1) with nitrogen content of 3.42 wt%. A prototypical coin cell type symmetric N-MCNF SC device has been assembled with 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIMBF4] ionic liquid electrolyte, and evaluated for SCs studies. The N-MCNF with high textural properties delivers unprecedented SC performance, such as high specific capacitance (204 Fg-1 at 0.25 Ag-1, 25 °C), high energy density (63.4 Wh kg-1), high power density (35.9 kW kg-1) and long-term cycle life (32,500 cycles). Significantly, N-MCNF materials exhibited high power rate performance, at 500 mV-1 (115 Fg-1) and 25 Ag-1 (166 Fg-1) owing to the uniform mesopore size distribution (∼4 nm). The N-MCNF SC device delivered maximum energy densities of 83.4 and 93.3 Wh kg-1 at 60 °C and 90 °C, respectively. Such outstanding N-MCNF SC device is successfully demonstrated in solar energy harvester applications.

  12. Raman scattering investigations of the interaction of a COV with pure and acid doped ice particles

    Facq, S.; Oancea, A.; Focsa, C.; Chazallon, B.

    2009-04-01

    Ice present in polar stratosphere is as well a common component of the troposphere, particularly in cirrus clouds widespread in tropopause and upper troposphere region. With water droplets, ice constitutes the condensed matter that can interact with atmospheric trace gases via many different trapping processes (co-deposition i.e; incorporation during growing ice conditions, adsorption, freezing etc). The incorporation of trace gases in ice surface/volume can both affect the atmospheric chemistry and the ice structure and reactivity. This can therefore modify the nature and composition of the incorporated species in ice, or in the gas phase. Recently, field measurements have demonstrated the presence of nitric acid in ice particles from cirrus clouds(1,2) (concentration between 0.63 wt% and 2.5 wt %). Moreover, laboratory experiments have shown that the uptake of atmospheric trace gases can be enhanced up to 1 or 2 orders of magnitude in these doped ice particles. Among trace gases capable to interact with atmospheric condensed matter figure volatile organic compounds such as aldehydes, ketones and alcohols (ex: ethanol and methanol). They play an important role in the upper troposphere (3,4) and snowpack chemistry (5) as they can be easily photolysed, producing free radicals and so influence the oxidizing capacity and the ozone-budget of the atmosphere (3,4). The temperature range at which these physico-chemical processes occur extents between ~ 190 K and 273K. Interaction between ice and trace gases are therefore largely dependent on the ice surface properties as well as on the phase formation dynamic (crystalline or not). This study aims to examine and characterize the incorporation of a COV (ex: ethanol), at the surface or in the volume of ice formed by different growth mechanisms (vapour deposition or droplets freezing). Vibrational spectra of water OH and ethanol CH-spectral regions are analysed using confocal micro-Raman spectroscopy at different temperatures

  13. Development of Sensitive Analytical Approach for the Quantification of α-Lipoic Acid Using Boron Doped Diamond Electrode.

    Stankovic, Dalibor M; Mehmeti, Eda; Kalcher, Kurt

    2016-01-01

    A boron doped diamond (BDD) electrode was investigated for use as an electrochemical sensor for α-lipoic acid (LA) using amperometric and differential pulse voltammetric detection. LA displays a well expressed oxidation peak at +0.9 V vs. Ag/AgCl in solutions with a pH value of 3. It was found that signals obtained are linearly related to the concentration range from 0.3 to 105 μM with detection limit of 0.088 μM. Interferences by common compounds such as ascorbic acid, uric acid and dopamine were tested and the method was successfully applied to the determination of LA in human body fluids where it gave recoveries in the range from 95 to 97%. PMID:27506710

  14. Study of pure and L-tartaric acid doped ammonium dihydrogen phosphate single crystals: A novel nonlinear optical non-centrosymmetric crystal

    Hasmuddin, Mohd, E-mail: mhasmu@gmail.com [Crystal Growth Laboratory, Dept. of Physics, Jamia Millia Islamia, New Delhi 110 025 (India); Singh, Preeti [Crystal Growth Laboratory, Dept. of Physics, Jamia Millia Islamia, New Delhi 110 025 (India); Shkir, Mohd [Crystal Growth Laboratory, Dept. of Physics, Jamia Millia Islamia, New Delhi 110 025 (India); Department of Physics, School of Science, King Khalid University, P.O. Box. 9004, Abha 61413 (Saudi Arabia); Abdullah, M.M. [Crystal Growth Laboratory, Dept. of Physics, Jamia Millia Islamia, New Delhi 110 025 (India); Promising Centre for Sensors and Electronic Devices (PCSED), Department of Physics, College of Science and Arts, Najran University, P.O. Box 1988, Najran 11001 (Saudi Arabia); Vijayan, N. [CSIR – National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi 110 012 (India); Ganesh, V. [Department of Physics, Kakatiya University, Warangal, Andhra Pradesh 506009 (India); Wahab, M.A., E-mail: mwahab@jmi.ac.in [Crystal Growth Laboratory, Dept. of Physics, Jamia Millia Islamia, New Delhi 110 025 (India)

    2014-04-01

    Single crystals of pure and L-tartaric acid (LTA) C{sub 4}H{sub 6}O{sub 6} doped ammonium dihydrogen phosphate (ADP) (NH{sub 4}) H{sub 2}PO{sub 4} were grown by slow evaporation solution technique (SEST) at ambient conditions. Powder X-ray diffraction (PXRD) analysis was carried out to confirm the crystal structure and no additional phase was observed due to doping except a systematic variation in peak intensities. Fourier transform infrared spectral analysis was done to examine the presence of various functional groups in the grown crystals. UV–VIS–NIR spectroscopic analysis was carried out to see the change in optical transparency of pure ADP and crystals due to LTA with different doping concentrations. Second harmonic generation (SHG) efficiency measurement was done to examine the enhancement in the nonlinear optical characteristics of the grown crystals. The effect of LTA dopant on crystal morphology, thermal and mechanical properties of ADP have also been presented in this paper. The above studies reveal the effect of incorporation of LTA into the lattice of ADP crystals. - Highlights: • LTA doped ADP crystals were grown for the first time. • Optical transmission was found to be higher at 1 mol% LTA doping. • SHG was found to be enhanced nonlinearly due to doping. • Thermal stability was found to higher at 1 mol% LTA doping. • Hardness was found to be increases with doping.

  15. Tartaric acid-assisted co-precipitation synthesis of Er3+-doped Lu2O3 nanopowders

    Neng Li Wang; Xi Yan Zhang; Peng He Wang

    2012-01-01

    Erbium-doped lutetia nanopowders were synthesized by a novel co-precipitation method using tartaric acid as precipitant.The properties of the samples were investigated by Fourier transform infrared spectroscopy (FTIR),X-ray diffraction (XRD),TG-DSC,field emission scanning electron microscopy (FE-SEM),and upeonversion luminescence analysis.Pure cubic Lu2O3 nanopowders were directly obtained when the precursor was calcined at 800 ℃ for 2 h,the samples showed strong upconversion luminescence under excitation of 980 nm laser diode.

  16. Polybenzimidazole and sulfonated polyhedral oligosilsesquioxane composite membranes for high temperature polymer electrolyte membrane fuel cells

    Aili, David; Allward, Todd; Alfaro, Silvia Martinez;

    2014-01-01

    Composite membranes based on poly(2,2′(m-phenylene)-5,5́bibenzimidazole) (PBI) and sulfonated polyhedral oligosilsesquioxane (S-POSS) with S-POSS contents of 5 and 10wt.% were prepared by solution casting as base materials for high temperature polymer electrolyte membrane fuel cells. With membranes...... based on pure PBI as a reference point, the composite membranes were characterized with respect to spectroscopic and physicochemical properties. After doping with phosphoric acid, the composite membranes showed considerably improved ex situ proton conductivity under anhydrous as well as under fully...... humidified conditions in the 120-180°C temperature range. The conductivity improvements were also confirmed by in situ fuel cell tests at 160°C and further supported by the electrochemical impedance spectroscopy data based on the operating membrane electrode assemblies, demonstrating the technical...

  17. Polybenzimidazole and sulfonated polyhedral oligosilsesquioxane composite membranes for high temperature polymer electrolyte membrane fuel cells

    Composite membranes based on poly(2,2′(m-phenylene)-5,5′bibenzimidazole) (PBI) and sulfonated polyhedral oligosilsesquioxane (S-POSS) with S-POSS contents of 5 and 10 wt.% were prepared by solution casting as base materials for high temperature polymer electrolyte membrane fuel cells. With membranes based on pure PBI as a reference point, the composite membranes were characterized with respect to spectroscopic and physicochemical properties. After doping with phosphoric acid, the composite membranes showed considerably improved ex situ proton conductivity under anhydrous as well as under fully humidified conditions in the 120-180 °C temperature range. The conductivity improvements were also confirmed by in situ fuel cell tests at 160 °C and further supported by the electrochemical impedance spectroscopy data based on the operating membrane electrode assemblies, demonstrating the technical feasibility of the novel electrolyte materials

  18. Parametric investigations on proton conducting membrane by radiation induced grafting of 4-vinylpyridine onto poly(vinylidene fluoride) and phosphoric acid doping

    Proton conducting membrane composed of grafted basic moiety doped with phosphoric acid (PA) was studied. The membrane denoted as PVDF-g-4-VP/PA was prepared by radiation induced grafting of 4-vinylpyridine (4-VP) onto poly(vinylidene fluoride) (PVDF) films followed by doping with PA. The effect of grafting conditions on the degree of grafting (G%) was investigated. The acid doping conditions (G%, time and PA concentration) were also investigated with respect to doping level. The grafted precursors and the acid doped membranes were characterized by means of Fourier transform infrared (FTIR), X-ray diffractometry (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and field emission scanning electron microscopy (FESEM). The membranes showed a thermal stability up to a temperature of ∝ 160 C, above which they undergo a multi-step degradation pattern due to decomposition of the protonated functions, poly(4VP) grafts and PVDF matrix, respectively. The proton conductivities of the membranes were found to increase with the increase in G% (doping level) and the temperature with a maximum proton conductivity of 62 mS cm-1 achieved at 100 C without any humidification. The results of the present study show that the prepared membrane has a potential to be proposed for operating polymer electrolyte membrane fuel cell above 80 C. (orig.)

  19. Parametric investigations on proton conducting membrane by radiation induced grafting of 4-vinylpyridine onto poly(vinylidene fluoride) and phosphoric acid doping

    Shamsaei, E.; Saidi, H. [Universiti Teknologi Malaysia, Kuala Lumpur (Malaysia). Inst. of Hydrogen Economy (IHE); Nasef, M.M. [Universiti Teknologi Malaysia, Kuala Lumpur (Malaysia). Inst. of Hydrogen Economy (IHE); Malaysia Japan International Institute of Technology (MJIIT), Kuala Lumpur (Malaysia); Yahaya, A.H. [Malaya Univ., Kuala Lumpur (Malaysia). Chemistry Dept.

    2014-07-01

    Proton conducting membrane composed of grafted basic moiety doped with phosphoric acid (PA) was studied. The membrane denoted as PVDF-g-4-VP/PA was prepared by radiation induced grafting of 4-vinylpyridine (4-VP) onto poly(vinylidene fluoride) (PVDF) films followed by doping with PA. The effect of grafting conditions on the degree of grafting (G%) was investigated. The acid doping conditions (G%, time and PA concentration) were also investigated with respect to doping level. The grafted precursors and the acid doped membranes were characterized by means of Fourier transform infrared (FTIR), X-ray diffractometry (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and field emission scanning electron microscopy (FESEM). The membranes showed a thermal stability up to a temperature of ∝ 160 C, above which they undergo a multi-step degradation pattern due to decomposition of the protonated functions, poly(4VP) grafts and PVDF matrix, respectively. The proton conductivities of the membranes were found to increase with the increase in G% (doping level) and the temperature with a maximum proton conductivity of 62 mS cm{sup -1} achieved at 100 C without any humidification. The results of the present study show that the prepared membrane has a potential to be proposed for operating polymer electrolyte membrane fuel cell above 80 C. (orig.)

  20. Transient Fluorescence Spectroscopy and laser induced fluorescence lifetimes of terbium doped dipicolinic acid

    Makoui, Anali

    We have investigated the use of deep UV laser induced fluorescence for the sensitive detection and spectroscopic lifetime studies of terbium doped dipicolinic acid (DPA-Tb) and used this to study the optical characteristics of DPA which is a chemical surrounding most bacterial spores. Background absorption spectra, fluorescence spectra, and Excitation Emission Matrix (EEM) spectra were made of the DPA-Tb complex, using both fixed 266 nm wavelength and tunable (220 nm--280 nm) UV laser excitations. Of importance, the fluorescence lifetimes of the four main fluorescence peaks (488 nm, 543 nm, 581 nm, and 618 nm) of the DPA-Tb complex have been measured for the first time to our knowledge. The lifetimes of all the fluorescing lines have been measured as a function of DPA-Tb concentration, solvent pH, and solvent composition, including that for the weakest fluorescing line of DPA-Tb at 618 nm. In addition, a new spectroscopic lifetime measurement technique, which we call "Transient Fluorescence Spectroscopy", was developed. In this technique, a weak, quasi-CW, amplitude modulated UV laser (8.5 kHz) was used to measure the lifetimes of the fluorescence lines, and yields insight into energy transfer and excitation lifetimes within the system. This technique is especially useful when a high power laser is not either available or not suitable. In the latter case, this would be when a high power pulsed deep-UV laser could produce bleaching or destruction of the biological specimen. In addition, this technique simulated the excitation and fluorescence emission of the DPA-Tb using a 4-level energy model, and solved the dynamic transient rate equations to predict the temporal behavior of the DPA-Tb emitted fluorescence. Excellent agreement between the experiments and the simulation were found. This technique has the potential to provide a more accurate value for the fluorescence lifetime values. In addition, with the use of asymmetric excitation waveforms, the dynamic

  1. Exceptional durability enhancement of PA/PBI based polymer electrolyte membrane fuel cells for high temperature operation at 200°C

    Aili, David; Zhang, Jin; Jakobsen, Mark Tonny Dalsgaard; Zhu, Haijin; Yang, Tianyu; Liu, Jian; Forsyth, Maria; Pan, Chao; Jensen, Jens Oluf; Cleemann, Lars Nilausen; Jiang, San Ping; Li, Qingfeng

    2016-01-01

    The incorporation of phosphotungstic acid functionalized mesoporous silica in phosphoric acid doped polybenzimidazole (PA/PBI) substantially enhances the durability of PA/PBI based polymer electrolyte membrane fuel cells for high temperature operation at 200°C.......The incorporation of phosphotungstic acid functionalized mesoporous silica in phosphoric acid doped polybenzimidazole (PA/PBI) substantially enhances the durability of PA/PBI based polymer electrolyte membrane fuel cells for high temperature operation at 200°C....

  2. Enhanced forward osmosis from chemically modified polybenzimidazole (PBI) nanofiltration hollow fiber membranes with a thin wall

    Wang, Kai Yu

    2009-04-01

    To develop high-flux and high-rejection forward osmosis (FO) membranes for water reuses and seawater desalination, we have fabricated polybenzimidazole (PBI) nanofiltration (NF) hollow fiber membranes with a thin wall and a desired pore size via non-solvent induced phase inversion and chemically cross-linking modification. The cross-linking by p-xylylene dichloride can finely tune the mean pore size and enhance the salt selectivity. High water permeation flux and improved salt selectivity for water reuses were achieved by using the 2-h modified PBI NF membrane which has a narrow pore size distribution. Cross-linking at a longer time produces even a lower salt permeation flux potentially suitable for desalination but at the expense of permeation flux due to tightened pore sizes. It is found that draw solution concentration and membrane orientations are main factors determining the water permeation flux. In addition, effects of membrane morphology and operation conditions on water and salt transport through membrane have been investigated. © 2008 Elsevier Ltd. All rights reserved.

  3. Highly efficient electrochemical degradation of perfluorooctanoic acid (PFOA) by F-doped Ti/SnO2 electrode.

    Yang, Bo; Jiang, Chaojin; Yu, Gang; Zhuo, Qiongfang; Deng, Shubo; Wu, Jinhua; Zhang, Hong

    2015-12-15

    The novel F-doped Ti/SnO2 electrode prepared by SnF4 as the single-source precursor was used for electrochemical degradation of aqueous perfluorooctanoic acid (PFOA). Higher oxidation reactivity and significantly longer service life were achieved for Ti/SnO2-F electrode than Ti/SnO2-X (X=Cl, Br, I, or Sb) electrode, which could decomposed over 99% of PFOA (50 mL of 100 mg L(-1)) within 30-min electrolysis. The property of Ti/SnO2-F electrode and its electrooxidation mechanism were investigated by XRD, SEM-EDX, EIS, LSV, and interfacial resistance measurements. We propose that the similar ionic radii of F and O as well as strong electronegativity of F caused its electrochemical stability with high oxygen evolution potential (OEP) and smooth surface to generate weakly adsorbed OH. The preparation conditions of electrode were also optimized including F doping amount, calcination temperature, and dip coating times, which revealed the formation process of electrode. Additionally, the major mineralization product, F(-), and low concentration of shorter chain perfluorocarboxylic acids (PFCAs) were detected in solution. So the reaction pathway of PFOA electrooxidation was proposed by intermediate analysis. These results demonstrate that Ti/SnO2-F electrode is promising for highly efficient treatment of PFOA in wastewater. PMID:26183235

  4. A Study on Tannic Acid-doped Polypyrrole Films on Gold Electrodes for Selective Electrochemical Detection of Dopamine

    Shouzhuo Yao

    2005-04-01

    Full Text Available Tannic acid-doped polypyrrole (PPY/TA films have been grown on goldelectrodes for selective electrochemical detection of dopamine (DA. Electrochemicalquartz crystal microbalance (EQCM studies revealed that, in vivid contrast toperchlorate-doped polypyrrole films (PPY/ClO4-, the redox switching of PPY/TA filmsin aqueous solutions involved only cation transport if the solution pH was greater than3~4. The PPY/TA Au electrodes also exhibited attractive permselectivity forelectroactive cations, namely, effectively blocking the electrochemical reactions ofanionic ferricyanide and ascorbic acid (AA while well retaining the electrochemicalactivities of hexaammineruthenium (III and dopamine as cationic species. A 500 HzPPY/TA film could effectively block the redox current of up to 5.0 mM AA. Thecoexistence of ascorbic acid in the measurement solution notably enhanced the currentsignal for dopamine oxidation, due probably to the chemical regeneration of dopaminethrough an ascorbic acid-catalyzed reduction of the electro-oxidation product ofdopamine (EC’ mechanism, and the greatest amplification was found at an ascorbic acidconcentration of 1.0 mM. The differential pulse voltammetry peak current for DAoxidation was linear with DA concentration in the range of 0 to 10 μM, with sensitivityof 0.125 and 0.268 μA/μM, as well as lower detection limit of 2.0 and 0.3 μM in a PBSsolution without AA and with 1.0 mM coexisting AA, respectively.

  5. Mechanochemically assisted solid-state and citric acid complex syntheses of Cu-doped sodium cobaltite ceramics

    Pršić, S., E-mail: sanjaprsic@imsi.bg.ac.rs [Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade (Serbia); Savić, S.M., E-mail: slavicas@imsi.bg.ac.rs [Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade (Serbia); Branković, Z., E-mail: zorica.brankovic@imsi.bg.ac.rs [Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade (Serbia); Vrtnik, S., E-mail: stane.vrtnik@ijs.si [Institute Jožef Stefan, Condensed Matter Physics, Jamova cesta 39, 1000 Ljubljana (Slovenia); Dapčević, A., E-mail: hadzi-tonic@tmf.bg.ac.rs [Department of General and Inorganic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Branković, G., E-mail: goran.brankovic@imsi.bg.ac.rs [Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade (Serbia)

    2015-08-15

    Highlights: • Sodium cobaltite was synthesized by mechanochemically assisted solid-state reaction and citric acid complex (CAC) method. • We investigated effect of Cu-doping in NaCo{sub 2−x}Cu{sub x}O{sub 4} (x = 0, 0.01, 0.03, 0.05). • ICP analysis showed that the controlling of the samples composition is easier by the CAC method. • The Seebeck coefficient in Cu-doped samples was higher compared to the undoped one. • The highest figure of merit was observed in the sample with the lowest Cu concentration. - Abstract: In the last decade, the sodium cobaltite ceramic became a promising candidate for potential thermoelectric applications, because of its large thermopower and low resistivity. In this work, polycrystalline samples of NaCo{sub 2−x}Cu{sub x}O{sub 4} (x = 0, 0.01, 0.03, 0.05) were prepared using mechanochemically assisted solid-state reaction method (MASSR) and the citric acid complex method (CAC). Bulk samples were prepared by pressing into disc-shaped pellets and subsequently subjected to a thermal treatment at 880 °C in inert argon atmosphere. Changes in structural and microstructural characteristics of the samples, caused by the substitution of Cu for Co, were characterized using X-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM), respectively. The results of inductively coupled plasma (ICP) analysis showed that the compositions of the final products correspond to γ-NaCo{sub 2}O{sub 4} and confirmed that desired compound was obtained in both syntheses procedures. The advantages and disadvantages of these two syntheses procedures have been observed and discussed: the CAC method enabled obtaining samples with higher density and fine microstructure compared to the MASSR method, thus better thermoelectric properties. The Cu{sup 2+} substitution led to the increase in Seebeck coefficient in both synthesis routes. The highest figure of merit of 0.022 at 300 K was observed for the sample doped with 1 mol% Cu, obtained by

  6. Photo-catalytic decolourisation of toxic dye with N-doped titania: A case study with Acid Blue 25

    Dhruba Chakrabortty; Susmita Sen Gupta

    2013-01-01

    Dyes are one of the hazardous water pollutants.Toxic Acid Blue 25,an anthraquinonic dye,has been decolourised by photo-catalysing it with nitrogen doped titania in aqueous medium.The photo catalyst was prepared from 15% TiCl3 and 25% aqueous NH3 solution as precursor.XRD and TEM revealed the formation of well crystalline anatase phase having particle size in the nano-range.BET surface area of the sample was higher than that of pure anatase TiO2.DRS showed higher absorption of radiation in visible range compared to pure anatase TiO2.XPS revealed the presence of nitrogen in N-Ti-O environment.The experimental parameters,namely,photocatalyst dose,initial dye concentration as well as solution pH influence the decolourisation process.At pH 3.0,the N-TiO2 could decolourise almost 100% Acid Blue 25 within one hour.The influence of N-TiO2 dose,initial concentration of Acid Blue 25 and solution pH on adsorption-desorption equilibrium is also studied.The adsorption process follows Lagergren first order kinetics while the modified Langmuir-Hinselwood model is suitably fitted for photocatalytic decolourisation of Acid Blue 25.

  7. Au/ZnO hybrid nanocatalysts impregnated in N-doped graphene for simultaneous determination of ascorbic acid, acetaminophen and dopamine.

    Chen, Xianlan; Zhang, Guowei; Shi, Ling; Pan, Shanqing; Liu, Wei; Pan, Hiabo

    2016-08-01

    The formation of nitrogen-doped (N-doped) graphene uses hydrothermal method with urea as reducing agent and nitrogen source. The surface elemental composition of the catalyst was analyzed through XPS, which showed a high content of a total N species (7.12at.%), indicative of the effective N-doping, present in the form of pyridinic N, pyrrolic N and graphitic N groups. Moreover, Au nanoparticles deposited on ZnO nanocrystals surface, forming Au/ZnO hybrid nanocatalysts, undergo a super-hydrophobic to super-hydrophilic conversion. Herein, we present Au/ZnO hybrid nanocatalysts impregnated in N-doped graphene sheets through sonication technique of the Au/ZnO/N-doped graphene hybrid nanostructures. The as-prepared Au/ZnO/N-doped graphene hybrid nanostructure modified glassy carbon electrode (Au/ZnO/N-doped graphene/GCE) was first employed for the simultaneous determination of ascorbic acid (AA), dopamine (DA) and acetaminophen (AC). The oxidation over-potentials of AA, DA and AC decreased dramatically, and their oxidation peak currents increased significantly at Au/ZnO/N-doped graphene/GCE compared to those obtained at the N-doped graphene/GCE and bare CCE. The peak separations between AA and DA, DA and AC, and AC and AA are large up to 195, 198 and 393mV, respectively. The calibration curves for AA, DA and AC were obtained in the range of 30.00-13.00×10(3), 2.00-0.18×10(3) and 5.00-3.10×10(3)μM, respectively. The detection limits (S/N=3) were 5.00, 0.40 and 0.80μM for AA, DA and AC, respectively. PMID:27157730

  8. Thin film thermocouples for in situ membrane electrode assembly temperature measurements in a polybenzimidazole-based high temperature proton exchange membrane unit cell

    Ali, Syed Talat; Lebæk, Jesper; Nielsen, Lars Pleth;

    2010-01-01

    This paper presents Type-T thin film thermocouples (TFTCs) fabricated on Kapton (polyimide) substrate for measuring the internal temperature of PBI(polybenzimidazole)-based high temperature proton exchange membrane fuel cell (HT-PEMFC). Magnetron sputtering technique was employed to deposit a 2 mu...

  9. Shear bond strength of orthodontic brackets after acid-etched and erbium-doped yttrium aluminum garnet laser-etched

    Shiva Alavi

    2014-01-01

    Full Text Available Background: Laser ablation has been suggested as an alternative method to acid etching; however, previous studies have obtained contrasting results. The purpose of this study was to compare the shear bond strength (SBS and fracture mode of orthodontic brackets that are bonded to enamel etched with acid and erbium-doped yttrium aluminum garnet (Er:YAG laser. Materials and Methods: In this experimental in vitro study, buccal surfaces of 15 non-carious human premolars were divided into mesial and distal regions. Randomly, one of the regions was etched with 37% phosphoric acid for 15 s and another region irradiated with Er:YAG laser at 100 mJ energy and 20 Hz frequency for 20 s. Stainless steel brackets were then bonded using Transbond XT, following which all the samples were stored in distilled water for 24 h and then subjected to 500 thermal cycles. SBS was tested by a chisel edge, mounted on the crosshead of universal testing machine. After debonding, the teeth were examined under Χ10 magnification and adhesive remnant index (ARI score determined. SBS and ARI scores of the two groups were then compared using t-test and Mann-Whitney U test. Significant level was set at P < 0.05. Results: The mean SBS of the laser group (16.61 ± 7.7 MPa was not significantly different from that of the acid-etched group (18.86 ± 6.09 MPa (P = 0.41. There was no significant difference in the ARI scores between two groups (P = 0.08. However, in the laser group, more adhesive remained on the brackets, which is not suitable for orthodontic purposes. Conclusion: Laser etching at 100 mJ energy produced bond strength similar to acid etching. Therefore, Er:YAG laser may be an alternative method for conventional acid-etching.

  10. Shear bond strength of orthodontic brackets after acid-etched and erbium-doped yttrium aluminum garnet laser-etched

    Alavi, Shiva; Birang, Reza; Hajizadeh, Fatemeh

    2014-01-01

    Background: Laser ablation has been suggested as an alternative method to acid etching; however, previous studies have obtained contrasting results. The purpose of this study was to compare the shear bond strength (SBS) and fracture mode of orthodontic brackets that are bonded to enamel etched with acid and erbium-doped yttrium aluminum garnet (Er:YAG) laser. Materials and Methods: In this experimental in vitro study, buccal surfaces of 15 non-carious human premolars were divided into mesial and distal regions. Randomly, one of the regions was etched with 37% phosphoric acid for 15 s and another region irradiated with Er:YAG laser at 100 mJ energy and 20 Hz frequency for 20 s. Stainless steel brackets were then bonded using Transbond XT, following which all the samples were stored in distilled water for 24 h and then subjected to 500 thermal cycles. SBS was tested by a chisel edge, mounted on the crosshead of universal testing machine. After debonding, the teeth were examined under ×10 magnification and adhesive remnant index (ARI) score determined. SBS and ARI scores of the two groups were then compared using t-test and Mann-Whitney U test. Significant level was set at P < 0.05. Results: The mean SBS of the laser group (16.61 ± 7.7 MPa) was not significantly different from that of the acid-etched group (18.86 ± 6.09 MPa) (P = 0.41). There was no significant difference in the ARI scores between two groups (P = 0.08). However, in the laser group, more adhesive remained on the brackets, which is not suitable for orthodontic purposes. Conclusion: Laser etching at 100 mJ energy produced bond strength similar to acid etching. Therefore, Er:YAG laser may be an alternative method for conventional acid-etching. PMID:25097641

  11. Preparation and characterization of mesoporous N-doped and sulfuric acid treated anatase TiO2 catalysts and their photocatalytic activity under UV and Vis illumination

    Nitrogen-doped TiO2 catalysts were prepared by a precipitation method. The samples were calcined at 400 deg. C for 4 h in air. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), low temperature N2-adsorption was used for structural characterization and UV-diffuse reflectance (UV-DR) was applied to investigate the optical properties of the as-prepared samples. It was found that microporous N-doped catalysts have solely anatase crystalline structure. Acidic treatment of the calcined samples was performed using sulfuric acid agitation. The crystalline structure remained unchanged due to surface treatment, while the porosity and the surface areas (aBETS) were decreased dramatically. Optical characterization of the doped catalysts showed that they could be excited by visible light photons in the 400-500 nm wavelength range (λg,1=∼390 nm, λg,2=∼510 nm). It was also established that surface treatment enhances the Vis-light absorption of the N-TiO2 powders. Finally the catalysts were tested in the photocatalytic degradation of phenol in aqueous suspensions. Two different light sources were used; one of them was a UV-rich high pressure Hg-lamp, while the other was a tubular visible light source. We found that using visible light illumination N-doped, acid treated TiO2 samples were more catalytically active than non-doped TiO2 catalysts. - Graphical abstract: The effect of the acid treatment on the visible-light-driven photocatalytic activity of the N-doped, anatase TiO2 catalysts.

  12. Conversion of pristine and p-doped sulfuric-acid-treated single-walled carbon nanotubes to n-type materials by a facile hydrazine vapor exposure process

    Wang, Pen-Cheng, E-mail: wangpc@ess.nthu.edu.tw [Department of Engineering and System Science, National Tsing Hua University, 101 Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan (China); Liao, Yu-Chun [Department of Engineering and System Science, National Tsing Hua University, 101 Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan (China); National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Lai, Yu-Ling; Lin, Ying-Chang [National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Su, Ching-Yuan; Tsai, Chuen-Horng [Department of Engineering and System Science, National Tsing Hua University, 101 Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan (China); Hsu, Yao-Jane, E-mail: yjhsu@nsrrc.org.tw [National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China)

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer Discovery of a facile method to n-dope carbon nanotubes by vapor-phase hydrazine. Black-Right-Pointing-Pointer Confirming covalently bound sulfonic groups on CNTs treated with sulfuric acid. Black-Right-Pointing-Pointer Spectroscopic investigation of CNTs' bonding structures after hydrazine treatment. Black-Right-Pointing-Pointer Proposing a cycloaddition reaction between graphenic domains of CNTs and reactive nitrogen-containing radicals thermally decomposed from hydrazine. Black-Right-Pointing-Pointer Establishing aziridine as a probable n-doping chemical entity on hydrazine-treated CNTs. - Abstract: It was found in this study that a facile vapor-phase hydrazine (N{sub 2}H{sub 4}) treatment could effectively convert pristine and even p-doped sulfuric-acid-treated single-walled cabon nanotubes (SWCNTs) to n-type materials. The Raman spectroscopy results show that the facile vapor-phase hydrazine treatment could suppress the intensity of SWCNTs' radial breathing modes and alter SWCNTs' D-band vs. G-band intensity ratio. The sheet resistance measurement results show that the n-doping effect exerted by the vapor-phase hydrazine treatment could overwhelmingly counteract sulfuric acid's p-doping effect and subdue the SWCNTs' acquired p-type characteristics rendered by the sulfuric acid treatment. The ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy results suggest that certain reactive nitrogen-containing radicals thermally decomposed from hydrazine, such as nitrene and amidogen, could covalently functionalize CNTs and then n-dope the functionalzed CNTs.

  13. Cyclic voltammetry and impedance studies of electrodeposited polypyrrole nanoparticles doped with 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt

    Ebrahim, Sh. M., E-mail: shebrahim@igsr.alex.edu.e [Department of Materials Science, Institute of Graduate Studies and Research, Alexandria University, Postal Code 21526, Alexandria (Egypt); Latif, M.M. Abd-El [Mubarak City for Scientific Research and Technology Applications, Institute of Advanced Technology and New Materials, Borg El-Arab City, Alexandria (Egypt); Gad, A.M.; Soliman, M.M. [Department of Materials Science, Institute of Graduate Studies and Research, Alexandria University, Postal Code 21526, Alexandria (Egypt)

    2010-05-31

    Electrochemical synthesis of polypyrrole (PPY), doped with 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPSNa), was carried out using chronoamperometric technique. Cyclic voltammetry measurements showed that the electroactivity of PPY films, doped with AMPSNa, increases with the film thickness. Scanning electron microscopy photographs revealed that the PPY particles are in the nano-scale range and that their size depends on the potential at which the PPY has formed. Electrochemical impedance spectroscopy (EIS), in the potential range of + 1.0 and - 1.0 V, revealed in the PPY film charge transfer domination with a semicircle at high frequencies, and anion diffusion dominance at low frequencies. EIS also showed that the charge transfer resistance of PPY film at - 1.0 V is lower than what is expected and that on increasing the thickness of the PPY films, the overall impedance decreases. The proposed equivalent circuit model, based on the double layer capacity and the Warburg impedance, was replaced by two constant-phase elements to fit the experimental work of this study. The values of the fractional exponent of the first constant phase element at approximately 0.5 indicate that the processes have a diffusion-limited nature.

  14. Chlorine-doped reduced graphene oxide nanosheets as an efficient and stable electrode for supercapacitor in acidic medium.

    Kakaei, Karim; Hamidi, Milad; Husseindoost, Somayeh

    2016-10-01

    We demonstrate the efficient doping of reduced graphene oxide (RGO) by Chlorine and its capacitive performance was calculated by cyclic voltammetry and charge-discharge cycling in 1M H2SO4 solution. In this regard, we are prepared RGO nanosheets through a simple, eco-friendly and efficient electrochemical method, with selectively functionalized edges by chlorine which involves added the RGO to the halogen-containing acid solution and dispersed by ultrasonic. After synthesis, Cl-RGO is characterized using X-ray diffraction, Raman spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, Energy-dispersive X-ray (EDX) spectroscopy and tunneling electron microscopy. FTIR spectra show the chlorine-containing functional groups. Energy-dispersive X-ray spectroscopy analysis confirmed the presence of doped chlorine in RGO. Raman spectroscopy shows a high density of defects in the RGO layer. Electrochemical characteristics of Cl-RGO are characterized by cyclic voltammetery, galvanostatic charge/discharge and electrochemical impedance spectroscopy. According to the galvanostatic charge/discharge analysis, Cl-RGO represents specific capacitance (Cs) of 178.4Fg(-1) at current density of 1Ag(-1), which is higher than that of RGO (100.5Fg(-1)) in H2SO4 solution. PMID:27388125

  15. Synthesis, characterization and binding interactions of amino acids coupled perylene diimides with colloidal doped and undoped TiO2

    Kavery, E.; Nagarajan, N.; Paramaguru, G.; Renganathan, R.

    2015-07-01

    Two sensitizers based on amino acids coupled with perylene moiety having absorption in the visible region have been designed and their interaction with doped and undoped TiO2 for the application of dye sensitized solar cells (DSSCs) has been studied. The synthesized compounds PDI-PA and PDI-AA were characterized using 1H and 13C NMR, Mass and FT-IR spectroscopic techniques. The optical properties and lifetime measurements of the sensitizers were analyzed using various solvents with different polarity. The solvatochromism effect was studied using Lippert-Mataga plot. The electrochemical studies of both dyes were investigated in DMF with various scan rate ranging from 200 to 1000 mV s-1. Colloidal doped and undoped TiO2 was prepared and characterized by using absorption measurements. Binding ability of the sensitizers with the nanoparticles was studied through absorption, fluorescence quenching, cyclic voltammetry and FT-IR measurements. Results obtained from all the above analysis suggest the mode of quenching may be static. The binding constant values were calculated using Kamat-Fox equation indicates the binding behavior of the sensitizers with the nanoparticles. The fluorescence quenching was mainly attributed to electron transfer from the excited state of PDI's to the conduction band of colloidal semiconductors. The electron transfer mechanism was explained based on the Rehm-Weller equation as well as the energy level diagram.

  16. Nitrogen-doped carbon-TiO2 composite as support of Pd electrocatalyst for formic acid oxidation

    Qin, Yuan-Hang; Li, Yunfeng; Lam, Thomas; Xing, Yangchuan

    2015-06-01

    We report Pd nanoparticles supported on a composite consisting of oxide TiO2 and nitrogen-doped carbon for formic acid oxidation (FAO). The nitrogen-doped carbon-TiO2 (NCx-TiO2) composite support was prepared by a simple polymerization-pyrolysis process using commercial TiO2 nanoparticles (P25). Surface analysis showed that elements of Ti, C, O, and N were present on the composite surface, on which nitrogen existed in both pyridinic and quaternary forms. Pd nanoparticles with a mean size of ca. 4 nm were uniformly deposited on the composite via a polyol process. Electrochemical characterizations showed that the NCx-TiO2-supported Pd particles (Pd/NCx-TiO2) exhibited an electrocatalytic activity towards FAO that almost doubled that of the carbon black-supported Pd particles (Pd/C) with much enhanced electrocatalytic stability. The better performance of the composite supported Pd was attributed to a possible electronic structure modification in the metallic Pd particles and bifunctional effect produced by the NCx-TiO2 composite.

  17. Cyclic voltammetry and impedance studies of electrodeposited polypyrrole nanoparticles doped with 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt

    Electrochemical synthesis of polypyrrole (PPY), doped with 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPSNa), was carried out using chronoamperometric technique. Cyclic voltammetry measurements showed that the electroactivity of PPY films, doped with AMPSNa, increases with the film thickness. Scanning electron microscopy photographs revealed that the PPY particles are in the nano-scale range and that their size depends on the potential at which the PPY has formed. Electrochemical impedance spectroscopy (EIS), in the potential range of + 1.0 and - 1.0 V, revealed in the PPY film charge transfer domination with a semicircle at high frequencies, and anion diffusion dominance at low frequencies. EIS also showed that the charge transfer resistance of PPY film at - 1.0 V is lower than what is expected and that on increasing the thickness of the PPY films, the overall impedance decreases. The proposed equivalent circuit model, based on the double layer capacity and the Warburg impedance, was replaced by two constant-phase elements to fit the experimental work of this study. The values of the fractional exponent of the first constant phase element at approximately 0.5 indicate that the processes have a diffusion-limited nature.

  18. Electrochemical Oxidation of Methanol and Formic Acid in Fuel Cell Processes

    Seland, Frode

    2005-01-01

    The main objectives of the thesis work were: (1), to study the oxidation of methanol and formic acid on platinum electrodes by employing conventional and advanced electrochemical methods, and (2), to develop membrane electrode assemblies based on polybenzimidazole membranes that can be used in fuel cells up to 200 °C.D.c. voltammetry and a.c. voltammetry studies of methanol and formic acid on polycrystalline platinum in sulphuric acid electrolyte were performed to determine the mechanism and ...

  19. Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl Cellulose Doped with Oleic Acid and Plasticized with Glycerol

    Chai, M. N.; Isa, M. I. N.

    2016-06-01

    The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10‑4 S cm‑1 for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor.

  20. Novel Proton Conducting Solid Bio-polymer Electrolytes Based on Carboxymethyl Cellulose Doped with Oleic Acid and Plasticized with Glycerol

    Chai, M. N.; Isa, M. I. N.

    2016-01-01

    The plasticized solid bio-polymer electrolytes (SBEs) system has been formed by introducing glycerol (Gly) as the plasticizer into the carboxymethyl cellulose (CMC) doped with oleic acid (OA) via solution casting techniques. The ionic conductivity of the plasticized SBEs has been studied using Electrical Impedance Spectroscopy. The highest conductivity achieved is 1.64 × 10−4 S cm−1 for system containing 40 wt. % of glycerol. FTIR deconvolution technique had shown that the conductivity of CMC-OA-Gly SBEs is primarily influenced by the number density of mobile ions. Transference number measurement has shown that the cation diffusion coefficient and ionic mobility is higher than anion which proved the plasticized polymer system is a proton conductor. PMID:27265642

  1. Photoluminescence and thermoluminescence study of KCaSO4Cl doped with Dy and Ce synthesized by acid distillation method

    Photoluminescence and thermoluminescence properties of KCaSO4Cl doped with dysprosium and cerium have been studied. Dy/Ce doped KCaSO4Cl phosphors were synthesized by the acid distillation method. The samples were characterized by XRD, SEM, PL and TL for structural, morphological and luminescence studies. The SEM image analysis of KCaSO4Cl phosphor shows nearly spherical particles with diameter varying between 3–10 μm. In the present host Dy3+ emission at 482 and 573 nm is observed due to 4F9/2→6H15/2 and 4F9/2→6H13/2 transition, respectively, whereas the PL emission spectra of KCaSO4Cl:Ce phosphor shows two luminescence bands at 307 nm and 326 nm and are attributed to the allowed inter configurational transitions from the 5d-level to the 2F5/2 and 2F7/2 levels of Ce3+ ion. Effect of annealing on the structure of the glow curve is investigated for KCaSO4Cl:Dy phosphors. Thermoluminescence linearity has been studied for 0.1–9000 Gy dose of gamma rays. Linear behavior over a large dose range between 0.1 Gy and 170 Gy was found. In addition to this trap parameters of KCaSO4Cl:Dy were studied using computerized glow curve deconvolution. -- Highlights: • The novel phosphor is first time prepared by acid distillation method. • This study reports the thermoluminescence properties of KCaSO4Cl irradiated with gamma rays. • The trapping analysis was done by GCD function and Chen's peak shape method. • Its good photoluminescence property can be utilized in display devices as well. • The phosphor can be used as a good dosimeter for measuring the high doses of γ-rays

  2. Synthesis, characterization and visible light photocatalytic activity of Cr 3+ , Ce 3+ and N co-doped TiO 2 for the degradation of humic acid

    Rashid, S. G.

    2015-01-01

    The synthesis, characterization and photocatalytic activity of Cr3+ and Ce3+ co-doped TiON (N-doped TiO2) for the degradation of humic acid with exposure to visible light is reported. The synthesized bimetal (Cr3+ + Ce3+) modified TiON (Cr-Ce/TiON), with an evaluated bandgap of 2.1 eV, exhibited an enhanced spectral response in the visible region as compared to pure and Ce3+ doped TiON (Ce/TiON). The XRD analysis revealed the insertion of Cr3+ and Ce3+ in the crystal lattice along with Ti4+ and N that resulted in the formation of a strained TiON anatase structure with an average crystallite size of ∼10 nm. Raman analysis also supported the formation of stressed rigid structures after bimetal doping. HRTEM confirmed the homogeneous distribution of both the doped metallic components in the crystal lattice of TiON without the formation of surface oxides of either Cr3+ or Ce3+. Electron energy loss spectroscopy (EELS) analysis revealed no change in the oxidation of either Cr or Ce during the synthesis. The synthesized Cr-Ce/TiON catalyst exhibited appreciable photocatalytic activity for the degradation of humic acid on exposure to visible light. Additionally, a noticeable mineralization of carbon rich humic acid was also witnessed. The photocatalytic activity of the synthesized catalyst was compared with pristine and Ce3+ doped TiON. © The Royal Society of Chemistry 2015.

  3. Periodic DFT study of acidic trace atmospheric gas molecule adsorption on Ca and Fe doped MgO (001) surface basic sites

    Baltrusaitis, Jonas; Hatch, Courtney; Orlando, Roberto

    2012-01-01

    The electronic properties of undoped and Ca or Fe doped MgO (001) surfaces, as well as their propensity towards atmospheric acidic gas (CO2, SO2 and NO2) uptake was investigated with an emphasis on gas adsorption on the basic MgO oxygen surface sites, Osurf, using periodic Density Functional Theory (DFT) calculations. Adsorption energy calculations show that MgO doping will provide stronger interactions of the adsorbate with the Osurf sites than the undoped MgO for a given adsorbate molecule....

  4. Nitrogen-doped, FeNi alloy nanoparticle-decorated graphene as an efficient and stable electrode for electrochemical supercapacitors in acid medium

    El-Deen, Ahmed G.; El-Newehy, Mohamed; Kim, Cheol Sang; Barakat, Nasser AM

    2015-03-01

    Nitrogen-doped graphene decorated by iron-nickel alloy is introduced as a promising electrode material for supercapacitors. Compared to pristine and Ni-decorated graphene, in acid media, the introduced electrode revealed excellent specific capacitance as the corresponding specific capacitance was multiplied around ten times with capacity retention maintained at 94.9% for 1,000 cycles. Briefly, iron acetate, nickel acetate, urea, and graphene oxide were ultrasonicated and subjected to MW heating and then sintered with melanin in Ar. The introduced N-doped FeNi@Gr exhibits remarkable electrochemical behavior with long-term stability.

  5. Mineralization of salicylic acid in acidic aqueous medium by electrochemical advanced oxidation processes using platinum and boron-doped diamond as anode and cathodically generated hydrogen peroxide.

    Guinea, Elena; Arias, Conchita; Cabot, Pere Lluís; Garrido, José Antonio; Rodríguez, Rosa María; Centellas, Francesc; Brillas, Enric

    2008-01-01

    Solutions containing 164 mg L(-1) salicylic acid of pH 3.0 have been degraded by electrochemical advanced oxidation processes such as anodic oxidation, anodic oxidation with electrogenerated H(2)O(2), electro-Fenton, photoelectro-Fenton and solar photoelectro-Fenton at constant current density. Their oxidation power has been comparatively studied in a one-compartment cell with a Pt or boron-doped diamond (BDD) anode and a graphite or O(2)-diffusion cathode. In the three latter procedures, 0.5mM Fe(2+) is added to the solution to form hydroxyl radical (()OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the O(2)-diffusion cathode. Total mineralization is attained for all methods with BDD and for photoelectro-Fenton and solar photoelectro-Fenton with Pt. The poor decontamination achieved in anodic oxidation and electro-Fenton with Pt is explained by the slow removal of most pollutants by ()OH formed from water oxidation at the Pt anode in comparison to their quick destruction with ()OH produced at BDD. ()OH generated from Fenton's reaction oxidizes rapidly all aromatic pollutants, but it cannot destroy final Fe(III)-oxalate complexes. Solar photoelectro-Fenton treatments always yield quicker degradation rate due to the very fast photodecarboxylation of these complexes by UVA irradiation supplied by solar light. The effect of current density on the degradation rate, efficiency and energy cost of all methods is examined. The salicylic acid decay always follows a pseudo-first-order kinetics. 2,3-Dihydroxybenzoic, 2,5-dihydroxybenzoic, 2,6-dihydroxybenzoic, alpha-ketoglutaric, glycolic, glyoxylic, maleic, fumaric, malic, tartronic and oxalic acids are detected as oxidation products. A general reaction sequence for salicylic acid mineralization considering all these intermediates is proposed. PMID:17692891

  6. Thermal stability and surface acidity of mesoporous silica doubly doped by incorporation of sulfate and zirconium ions

    A sulfated Si-Zr-MCM-41 solid with highly ordered mesostructure was synthesized through a templated synthesis route where the CTAB surfactant was used as template. During the synthesis procedure, various amounts of (NH4)2SO4 were added into the mixed solution of Zr and Si precursors to in situ sulfate the MCM-41 solids, aiming to enhance the acidity and thermal stability. The resultant materials showed a long-range ordered hexagonal arrangement with high surface area larger than 797 m2/g and an average pore size distributed at approximate 2.5-2.8 nm. The high-resolution TEM observations confirmed that the order of the mesostructure gained when the molar ratio of SO42-/(ZrO2 + SiO2) increased from 0.1 to 0.3 but decreased as it reached 0.5, which is consistent with the results of 29Si MAS-NMR and XRD analysis. Compared to Si-MCM-41, the (Q2 + Q3)/Q4 ratio derived from the NMR spectra of the Zr-doped sample was higher, indicating that zirconium atoms were incorporated into the silica framework. Unexpectedly, in situ sulfation does not enhance the surface Broensted acidity, most likely due to the sulfur retained within the bulk of the materials; however, it indeed improved the thermal stability of the solid and long-range order of the structure

  7. Adsorption of Acid Yellow-73 and Direct Violet-51 Dyes from Textile Wastewater by Using Iron Doped Corncob Charcoal

    The presence of synthetic dyes in textile industry wastewater lead to deterioration of precious fresh water resources, making the need to remove dyes crucial for environmental protection. Recently, different techniques have been employed to remove these dyes from water resources. Among them, biosorption has gained tremendous popularity due to its eco-friendly nature and inexpensive method. In this study, the removal potential of two acid dyes, i.e. yellow-73 and direct violet-51, was assessed from textile effluent samples using iron modified corncob charcoal. The adsorption efficiency ranged between 93.93 97.96 % and 92.2 - 95.4 % for acid yellow-73 and direct violet-51, respectively. Furthermore, study highlights optimum parameters for successful adsorption of these dyes, such as stirring time (numbers), pH (numbers), temperature (numbers), and adsorbent dosage (numbers). Keeping in consideration these findings, we recommend the use of Iron Doped Corncob Charcoal (IDCC) as a low-cost, efficient alternative for wastewater treatment, primarily minimizing the detrimental effects of hazardous dyes. (author)

  8. Voltammetric behaviour of levodopa and its quantification in pharmaceuticals using a -cyclodextrine doped poly (2,5-diaminobenzenesulfonic acid) modified electrode

    Mehmet Aslanoglu; Aysegul Kutluay; Sultan Goktas; Serpil Karabulut

    2009-03-01

    A cyclic voltammetric method based on a -cyclodextrine doped poly(2,5-diaminobenzenesulfonic acid) modified glassy carbon electrode (GCE) was developed for the determination of levodopa. Compared with bare GCE and poly(2,5-diaminobenzenesulfonic acid)/GCE, the poly(2,5-diaminobenzenesulfonic acid)--cyclodextrine/GCE exhibits a remarkable shift of the oxidation potentials of levodopa in the cathodic direction and a drastic enhancement of the anodic current response. The incorporation of -cyclodextrine into the polymer film exhibited that the electrode provides more stable and sensitive current responses for levodopa. Levodopa exhibited a single broad peak at about 0.6 V at bare GCE. However, at the -cyclodextrine doped poly(2,5-diaminobenzenesulfonic acid)/GCE, a well-defined redox wave of levodopa was obtained, with the oxidation and the reduction peak potential at 0.193 and 0.164 V, respectively. The separation of peak potentials was 29 mV. The linear current response was obtained in the range of 1.0 × 10-6 ∼ 2.0 ∼ 10-4 M with a detection limit of 4.18 ∼ 10-7 M for levodopa, The poly(2,5-diaminobenzenesulfonic acid)--cyclodextrine/GCE was also effective to simultaneously detect levodopa and ascorbic acid. The modified electrode has been successfully applied for the determination of levodopa in pharmaceuticals. The poly(2,5-diaminobenzenesulfonic acid)--cyclodextrine/GCE showed excellent stability and reproducibility.

  9. Water-free Alkaline Polymer-inorganic Acid Complexes with High Conductivity at Ambient Temperature

    O.V.Chervakov; M.V.Andriianova; V.V.Riabenko; A.V.Markevich; E.M.Shembel; D.Meshri

    2007-01-01

    1 Results Recently increased interest is shown to proton conducting materials based on the alkaline polymer-inorganic acid complexes that is caused by a possibility of their application as the high-temperature electrolyte systems for various electrochemical devices (fuel cells,sensors,lithium power sources etc.).Complexes of inorganic acids with the alkaline polymers (polybenzimidazoles[1],polyvinylpyridines[2]) are characterized by high ionic conductivity at ambient temperatures (up to 10-2 Ω-1·cm-1) a...

  10. Graphitic carbon nitride nanosheets doped graphene oxide for electrochemical simultaneous determination of ascorbic acid, dopamine and uric acid

    Graphical abstract: Schematic drawing of electrochemical oxidize AA, DA and UA on graphitic carbon nitride nanosheets-graphene oxide composite modified electrode. - Highlights: • Synthesize g-C3N4, GO and CNNS-GO composite. • CNNS-GO composite was the first time for simultaneous determination of AA, DA and UA. • CNNS-GO/GCE displays fantastic selectivity and sensitivity for AA, DA and UA. • CNNS-GO/GCE was applied to detect real sample with satisfactory results. - Abstract: Graphitic carbon nitride nanosheets with a graphite-like structure have strong covalent bonds between carbon and nitride atoms, and nitrogen atoms in the carbon architecture can accelerate the electron transfer and enhance electrical properties effectually. The graphitic carbon nitride nanosheets-graphene oxide composite was synthesized. And the electrochemical performance of the composite was investigated by cyclic voltammetry and differential pulse voltammetry ulteriorly. Due to the synergistic effects of layer-by-layer structures by π-π stacking or charge-transfer interactions, graphitic carbon nitride nanosheets-graphene oxide composite can improved conductivity, electro-catalytic and selective oxidation performance. The proposed graphitic carbon nitride nanosheets-graphene oxide composite modified electrode was employed for simultaneous determination of ascorbic acid, dopamine and uric acid in their mixture solution, it exhibited distinguished sensitivity, wide linear range and low detection limit. Moreover, the modified electrode was applied to detect urine and dopamine injection sample, and then the samples were spiked with certain concentration of three substances with satisfactory recovery results

  11. High fluorescence S, N co-doped carbon dots as an ultra-sensitive fluorescent probe for the determination of uric acid.

    Wang, Haiyan; Lu, Qiujun; Hou, Yuxin; Liu, Yalan; Zhang, Youyu

    2016-08-01

    Sulfur, nitrogen co-doped carbon dots (S, N co-doped C-dots) as highly selective fluorescent probe for uric acid (UA) detection were designed. The S, N co-doped C-dots with high quantum yield of 73.1% were prepared by hydrothermal method. It was found that the fluorescence of S, N co-doped C-dots was quenched apparently by hydroxyl radicals from Fenton reaction between H2O2 and Fe(2+). The production of H2O2 originated from the oxidization of UA by uricase. Therefore, an optical biosensor was developed for the detection of UA based on Fenton reaction and enzymatic reaction. Under the optimized conditions, two linear relationships between the ratio of fluorescence quenching of the C-dots and UA concentration were found in the range of 0.08-10µM and 10-50µM, respectively. The detection limit was down to 0.07µM. Moreover, the proposed biosensor was successfully applied to the detection of uric acid in human serum samples. PMID:27216657

  12. Phosphoric acid doped polysulfone membranes with aminopyridine pendant groups and imidazole cross-links

    Hink, Steffen; Elsøe, Katrine; Cleemann, Lars Nilausen;

    2015-01-01

    Udel polysulfone based membranes with 4-aminopyridine pendant groups and cross-linking imidazole units are synthesized in a simple two step reaction. The ratio of 4-aminopyridine and imidazole is varied and the materials are extensively characterized. The average phosphoric acid uptake (in 85 wt...... tests at 130 °C. The relationships between PA uptake, chemical composition and mechanical stability are reported. Proton conductivity and mechanical properties only depend on the phosphoric acid content, which, however is a function of the chemical composition....

  13. The use of polybenzimidazole membranes in vanadium redox flow batteries leading to increased coulombic efficiency and cycling performance

    An issue with conventional vanadium redox flow batteries (VRFB) with Nafion membranes is the crossover of vanadium ions, resulting in low coulombic efficiency and rapid decay in capacity. In this work, a VRFB with a polybenzimidazole (PBI) membrane is tested and compared with the Nafion system. Results show that the PBI-based VRFB exhibits a substantially higher coulombic efficiency of up to 99% at current densities ranging from 20 mA cm−2 to 80 mA cm−2. More importantly, it is demonstrated that the PBI-based VRFB has a capacity decay rate of as low as 0.3% per cycle, which is four times lower than that of the Nafion system (1.3% per cycle). The improved coulombic efficiency and cycling performance are attributed to the low crossover of vanadium ions through the PBI membrane

  14. Metal-polybenzimidazole complexes as a nonviral gene carrier: effects of the DNA affinity on gene delivery.

    Huang, Xueying; Dong, Xiongwei; Li, Xue; Meng, Xianggao; Zhang, Dan; Liu, Changlin

    2013-12-01

    The metal complex-based carriers are emerging likely as a new type of gene-delivery systems prone to systematic structural alteration and chemical tailoring. In our work, the DNA affinity of metal complexes with polybenzimidazoles was found to be one of the determinants that can regulate expression of the transgenes. Here, the correlations between the DNA affinity and transfection efficacy were explored by characterizing gene-delivering properties of a series of Co(2+)- and Ca(2+)-polybenzimidazole complexes. The binding equilibrium constants (Kobs) of the divalent metal complexes to DNA, which is considered as a measure of the DNA affinity of metal complexes, were evaluated by isothermal titration calorimetry (ITC) and UV-visible absorption titration. The properties of DNA condensates formed with the metal complexes including sizes, ζ potential and morphology were observed to be altered with Kobs values. The monodispersed spherical condensates were found only for the Ca(2+) complexes whose DNA affinity is weaker than that of the Co(2+) complexes. However, the cell internalization examination indicated that cell uptake of the DNA condensates is independent of homogeneity in their sizes and morphology. The comparison of transgene expression showed that that the Ca(2+) complex-mediated transfection has higher efficiency than the Co(2+) complexes under the conditions tested, and the transfection efficacy cannot be correlated with the cell uptake of DNA condensates. Moreover, the Ca(2+) complexes and their DNA condensates had lower cytotoxicity than the Co(2+) complexes. Thus, the DNA affinity should be one of the factors to be capable of regulating the gene-delivering property of metal complexes. PMID:24099694

  15. Selective interfacial synthesis of metal-organic frameworks on a polybenzimidazole hollow fiber membrane for gas separation

    Biswal, Bishnu P.; Bhaskar, Anand; Banerjee, Rahul; Kharul, Ulhas K.

    2015-04-01

    Metal-organic frameworks (MOFs) have gained immense attention as new age materials due to their tuneable properties and diverse applicability. However, efforts on developing promising materials for membrane based gas separation, and control over the crystal growth positions on polymeric hollow fiber membranes still remain key challenges. In this investigation, a new, convenient and scalable room temperature interfacial method for growing MOFs (ZIF-8 and CuBTC) on either the outer or inner side of a polybenzimidazole based hollow fiber (PBI-BuI-HF) membrane surface has been achieved in a controlled manner. This was made possible by the appropriate selection of an immiscible solvent pair and the synthetic conditions. The growth of MOFs on the PBI-BuI-HF membrane by the interfacial method was continuous and showed an appreciable gas separation performance, conveying promise for their applicability.Metal-organic frameworks (MOFs) have gained immense attention as new age materials due to their tuneable properties and diverse applicability. However, efforts on developing promising materials for membrane based gas separation, and control over the crystal growth positions on polymeric hollow fiber membranes still remain key challenges. In this investigation, a new, convenient and scalable room temperature interfacial method for growing MOFs (ZIF-8 and CuBTC) on either the outer or inner side of a polybenzimidazole based hollow fiber (PBI-BuI-HF) membrane surface has been achieved in a controlled manner. This was made possible by the appropriate selection of an immiscible solvent pair and the synthetic conditions. The growth of MOFs on the PBI-BuI-HF membrane by the interfacial method was continuous and showed an appreciable gas separation performance, conveying promise for their applicability. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00299k

  16. Studies of doped negative valve-regulated lead-acid battery electrodes

    Micka, Karel; Calábek, M.; Bača, P.; Křivák, P.; Lábus, R.; Bilko, R.

    2009-01-01

    Roč. 191, č. 1 (2009), s. 154-158. ISSN 0378-7753 Institutional research plan: CEZ:AV0Z40400503 Keywords : lead-acid * negative electrode * sulfation suppression Subject RIV: CG - Electrochemistry Impact factor: 3.792, year: 2009

  17. A Doped Polyaniline Modified Electrode Amperometric Biosensor for Gluconic Acid Determination in Grapes

    Donatella Albanese

    2014-06-01

    Full Text Available In winemaking gluconic acid is an important marker for quantitative evaluation of grape infection by Botrytis cinerea. A screen-printed amperometric bienzymatic sensor for the determination of gluconic acid based on gluconate kinase (GK and 6-phospho-D-gluconate dehydrogenase (6PGDH coimmobilized onto polyaniline/poly (2-acrylamido-2-methyl-1-propanesulfonic acid; PANI-PAAMPSA is reported in this study. The conductive polymer electrodeposed on the working electrode surface allowed the detection of NADH at low potential (0.1 V with a linear range from 4 × 10−3 to 1 mM (R2 = 0.99 and a sensitivity of 419.44 nA∙mM−1. The bienzymatic sensor has been optimized with regard to GK/6PGDH enzymatic unit ratio and ATP/NADP+ molar ratio which resulted equal to 0.33 and 1.2, respectively. Under these conditions a sensitivity of 255.2 nA∙mM−1, a limit of detection of 5 μM and a Relative Standard Deviation (RSD of 4.2% (n = 5 have been observed. Finally, the biosensor has been applied for gluconic acid measurements in must grape samples and the matrix effect has been taken into consideration. The results have been compared with those obtained on the same samples with a commercial kit based on a spectrophotometric enzyme assay and were in good agreement, showing the capability of the bienzymatic PANI-PAAMPSA biosensor for gluconic acid measurements and thus for the evaluation of Botrytis cinerea infection in grapes.

  18. Synthesis and luminescence properties of polymeric complexes of Cu(II), Zn(II) and Al(III) with functionalized polybenzimidazole containing 8-hydroxyquinoline side group

    Zhong, Chaofan; Wu, Qian; Guo, Rongfang; Zhang, Hailiang

    2008-02-01

    The polymeric ligand PBI-8Q ( 2) (functionalized polybenzimidazole containing 8-hydroxyquinoline side group) was successfully synthesized by the reaction of polybenzimidazole (PBI) ( 1) with 5-chloro-8-hydroxyquinoline (5-Cl-8Q) in DMSO solvent by using NaH as deprotonation reagent. Its corresponding metal complexes of Cu(II), Zn(II) and Al(III) were prepared and characterized through FT-IR, 1H NMR, molar conductance measurements and thermal analysis. The luminescence properties of all compounds were also studied by UV-vis and fluorescence spectra at ambient temperature. When excited from 338 to 415 nm, these compounds emit blue light of about 415 nm in solution and blue/green light from 483 to 552 nm in solid state, respectively. Thermal properties measurement and analysis show that they have good thermal stabilities.

  19. Nitrogen-doped, FeNi alloy nanoparticle-decorated graphene as an efficient and stable electrode for electrochemical supercapacitors in acid medium

    El-Deen, Ahmed G; El-Newehy, Mohamed; Kim, Cheol Sang; Barakat, Nasser AM

    2015-01-01

    Nitrogen-doped graphene decorated by iron-nickel alloy is introduced as a promising electrode material for supercapacitors. Compared to pristine and Ni-decorated graphene, in acid media, the introduced electrode revealed excellent specific capacitance as the corresponding specific capacitance was multiplied around ten times with capacity retention maintained at 94.9% for 1,000 cycles. Briefly, iron acetate, nickel acetate, urea, and graphene oxide were ultrasonicated and subjected to MW heati...

  20. Graphenated tantalum(IV) oxide and poly(4-styrene sulphonic acid)-doped polyaniline nanocomposite as cathode material in an electrochemical capacitor

    Nanostructured poly(4-styrene sulphonic acid) and tantalum (IV) oxide-doped polyaniline nanocomposite were synthesised and their electro-conductive properties were determined. The oxide was synthesized using a modified sol-gel method and then dispersed in acidic media through sonication and entrapped in-situ into the polymeric matrix during the oxidative chemical polymerization of aniline doped with poly(4-styrene sulphonic acid). The oxides and novel polymeric nanocomposite were characterised with TEM, SEM, EDX, XRD, FTIR, UV-visible to ascertain elemental and phase composition, successful polymerization, doping, morphology and entrapment of the metal oxide nanoparticles. The electro-conductivity of the nanomaterial was interrogated using scanning electrochemical microscopy (SECM) and cyclic voltammetry (CV). The material was then anchored on activated graphitic carbon and used in the design of an asymmetric supercapacitor cell using 6 M KOH aqueous electrolyte. Characteristically high specific capacitance values of 318.4 F/g with a corresponding energy and power densities of 1.57 kWh/kg and 0.435 kW/kg, respectively, were demonstrated. The cell also showed high coulombic efficiency of 94.9% with a long cycle life and good cycle stability making the nanomaterial suitable for constructing supercapacitor cell electrodes

  1. Fabrication of Nitrogen-Doped Mesoporous-Carbon-Coated Palladium Nanoparticles: An Intriguing Electrocatalyst for Methanol and Formic Acid Oxidation.

    Ray, Chaiti; Dutta, Soumen; Sahoo, Ramkrishna; Roy, Anindita; Negishi, Yuichi; Pal, Tarasankar

    2016-05-20

    Inspired by the attractive catalytic properties of palladium and the inert nature of carbon supports in catalysis, a concise and simple methodology for in situ nitrogen-doped mesoporous-carbon-supported palladium nanoparticles (Pd/N-C) has been developed by carbonizing a palladium dimethylglyoximate complex. The as-synthesized Pd/N-C has been exfoliated as a fuel cell catalyst by studying the electro-oxidation of methanol and formic acid. The material synthesized at 400 °C,namely, Pd/N-C-400,exhibitssuperior mass activity and stability among catalysts synthesized under different carbonization temperaturesbetween300 and 500 °C. The unique 1D porous structure in Pd/N-C-400 helps better electron transport at the electrode surface, which eventually leads to about five times better catalytic activity and about two times higher stability than that of commercial Pd/C. Thus, our designed sacrificial metal-organic templatedirected pathway becomes a promising technique for Pd/N-C synthesis with superior catalytic performances. PMID:27016895

  2. Targeting and Photodynamic Killing of Cancer Cell by Nitrogen-Doped Titanium Dioxide Coupled with Folic Acid

    Jin Xie

    2016-06-01

    Full Text Available Titanium dioxide (TiO2 has attracted wide attention as a potential photosensitizer (PS in photodynamic therapy (PDT. However, bare TiO2 can only be excited by ultraviolet illumination, and it lacks specific targeting ligands, which largely impede its application. In our study, we produced nitrogen-doped TiO2 and linked it with an effective cancer cell targeting agent, folic acid (FA, to obtain N-TiO2-FA nanoconjugates. Characterization of N-TiO2-FA included Zeta potential, absorption spectra and thermogravimetric analysis. The results showed that N-TiO2-FA was successfully produced and it possessed better dispersibility in aqueous solution than unmodified TiO2. The N-TiO2-FA was incubated with human nasopharyngeal carcinoma (KB and human pulmonary adenocarcinoma (A549 cells. The KB cells that overexpress folate receptors (FR on cell membranes were used as FR-positive cancer cells, while A549 cells were used as FR-negative cells. Laser scanning confocal microscopy results showed that KB cells had a higher uptake efficiency of N-TiO2-FA, which was about twice that of A549 cells. Finally, N-TiO2-FA is of no cytotoxicity, and has a better photokilling effect on KB cells under visible light irradiation. In conclusion, N-TiO2-FA can be as high-value as a PS in cancer targeting PDT.

  3. Photoinduced proton transfer coupled with energy transfer: Mechanism of sensitized luminescence of terbium ion by salicylic acid doped in polymer.

    Misra, Vinita; Mishra, Hirdyesh

    2008-06-28

    In the present work, excited state intramolecular proton transfer (ESIPT) in salicylic acid (SA) monoanion and subsequent sensitization of Tb(3+) ion in polyvinyl alcohol (PVA) have been studied. The study has been carried out both by steady state and time domain fluorescence measurement techniques at room temperature. It is found that the SA completely ionizes and exists as monoanion in PVA. It exhibits a large Stokes shifted blue emission (10 000 cm(-1)) due to ESIPT and shows a decay time of 6.85 ns. On the other hand, Tb(3+) ion shows a very weak green emission and a decay time of approximately 641 mus in PVA film. Upon incorporating Tb(3+) ion in SA doped PVA film, both intensity and decay time of SA decrease and sensitized emission from Tb(+3) ion along with 3.8 mus rise time is observed. Energy transfer is found to take place both from excited singlet as well as triplet states. A brief description of the properties of the present system from the viewpoint of luminescent solar collector material is addressed. PMID:18601359

  4. Amperometric ascorbic acid sensor based on doped ferrites nanoparticles modified glassy carbon paste electrode.

    Dimitrijević, Teodora; Vulić, Predrag; Manojlović, Dragan; Nikolić, Aleksandar S; Stanković, Dalibor M

    2016-07-01

    In this study, a novel electrochemical sensor for quantification of ascorbic acid with amperometric detection in physiological conditions was constructed. For this purpose, cobalt and nickel ferrites were synthesized using microwave and ultrasound assistance, characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and X-ray powder diffraction (XRPD), and used for modification of glassy carbon paste electrode (GCPE). It was shown that introducing these nanoparticles to the structure of GCPE led to increasing analytical performance. Co ferrite modified GCPE (CoFeGCPE) showed better characteristics toward ascorbic acid sensing. The limit of detection (LOD) obtained by sensor was calculated to be 0.0270 mg/L, with linear range from 0.1758 to 2.6010 mg/L. This sensor was successfully applied for practical analysis, and the obtained results demonstrated that the proposed procedure could be a promising replacement for the conventional electrode materials and time-consuming and expensive separation methods. PMID:27059753

  5. Growth of boric acid crystallites on the surface of boron-doped silicon carbide samples

    White crystallites were visually observed on fractured or polished surfaces of SiC samples (grain sizes below ∼500 nm) during exposure to air at room temperature for several days. Characterization of the crystallites by scanning electron microscopy, secondary ion mass spectroscopy, and X-ray diffraction identified B(OH)3 crystals with a strong (002) texture. The rate of boric acid formation was determined by a gravimetric experiment. The rate of weight gain increased significantly after an incubation period of 1 week. Nucleation is initially the rate-limiting process. Subsequently small B(OH)3 crystals form on the surface, whose growth rate is determined by grain boundary diffusion of boron to the SiC surface. An estimated grain boundary boron to the SiC surface. An estimated grain boundary diffusion coefficient of boron in SiC was many orders of magnitude higher than extrapolated literature values

  6. Investigations on the growth, optical, thermal, dielectric, and laser damage threshold properties of crystal violet dye-doped potassium acid phthalate single crystal

    Rao, G. Babu; Rajesh, P.; Ramasamy, P.

    2016-03-01

    Influence of crystal violet dye with different concentration on potassium acid phthalate single crystal grown by conventional method has been studied. No change has been observed in the structure, whereas changes have been observed in the external morphology of the crystal when the dyes are incorporated in the crystal lattice. Thermogravimetric and differential thermal analyses show the onset decomposition temperatures to be at 302, 285, 284, and 285 °C for pure, 0.1, 0.3, and 0.5 mol% crystal violet-doped potassium acid phthalate crystals, respectively. The dielectric measurement was carried out on the grown crystals as a function of frequency at various temperatures. In addition, strong luminescent emission bands at 638, 648, and 640 nm were observed in which the relative intensity was found to be reversed as a result of doping concentration. The laser damage threshold value significantly increased for dye-doped crystal in comparison with pure crystal which may make it suitable for the solid-state dye laser applications.

  7. Mechanical Stability of H3PO4-Doped PBI/Hydrophilic-Pretreated PTFE Membranes for High Temperature PEMFCs

    Graphical abstract: - Highlights: • PBI/PTFE membrane was prepared by porous PTFE with hydrophilic surface pretreatment. • The durability of the prepared PBI/PTFE membrane was compared with pure PBI, PBI with untreated PTFE, and PBI-Nafion with untreated PTFE membranes. • Accelerated durability tests and SEM showed improved durability based the PBI/PTFE membrane with pretreated PTFE. - Abstract: A novel polybenzimidazole (PBI)/poly(tetrafluoroethylene) (PTFE) composite membrane doped with phosphoric acid was fabricated for high temperature operation in a polymer electrolyte membrane (PEM) fuel cell. A hydrophilic surface pretreatment was applied to the porous PTFE matrix film to improve its interfacial adhesion to the PBI polymer, thereby avoiding the introduction of Nafion ionomer which is traditionally used as a coupling agent. The pretreated PTFE film was embedded within the composite membrane during solution-casting using 5wt% PBI/DMAc solution. The mechanical stability and durability of three types of MEAs assembled with PBI only, PBI with pretreated PTFE, and PBI-Nafion with untreated PTFE membranes were evaluated under an accelerated degradation testing protocol employing extreme temperature cycling. Degradation was characterized by recording polarization curves, hydrogen crossover, and proton resistance. Cross-sections of the membranes were examined before and after thermal cycling by scanning electron microscope. Energy-dispersive X-ray spectroscopy verified that the PBI is dispersed homogeneously in the porous PTFE matrix. Results show that the PBI composite membrane with pretreated PTFE has a lower degradation rate than the Nafion/PBI membrane with untreated PTFE. Thus, the hydrophilic pretreatment employed here greatly improved the mechanical stability of the composite membrane, which resulted in improved durability under an extreme thermal cycling regime

  8. Effective role of trifluoroacetic acid (TFA) to enhance the photocatalytic activity of F-doped TiO2 prepared by modified sol-gel method

    Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd; Juan, Joon Ching; Basirun, Wan Jefrey; Kandjani, Ahmad Esmaielzadeh; Bhargava, Suresh K.

    2016-03-01

    Highly photoactive mesoporous F-doped TiO2 with improved physico-chemical characteristics is achieved using modified sol-gel method. The usage of trifluoroacetic as fluorine precursor significantly modifies the morphology, size, pore shape, crystal phase, crystal structure, surface chemical state and to a lesser extent, {1 0 1} and {0 0 1} facets. The accessibility of fluoride ions on Tisbnd Osbnd Ti polymer chains during crystal growth during the sol-gel process remarkably influences the properties of catalyst. To the best of our knowledge, preparation of F-doped TiO2 using modified sol-gel and trifluoroacetic acid are limited, and still not enough. Thus this work provides additional insight by using an approach which is less hazardous, less costly and practical for large scale agile development in the photocatalysis industry.

  9. Improved Durability of Electrocatalyst Based on Coating of Carbon Black with Polybenzimidazole and their Application in Polymer Electrolyte Fuel Cells.

    Fujigaya, Tsuyohiko; Hirata, Shinsuke; Berber, Mohamed R; Nakashima, Naotoshi

    2016-06-15

    Improvement of durability of the electrocatalyst has been the key issue to be solved for the practical application of polymer electrolyte membrane fuel cells. One of the promising strategies to improve the durability is to enhance the oxidation stability of the carbon-supporting materials. In this report, we describe in detail the mechanism of the stability improvement of carbon blacks (CBs; Vulcan and Ketjen) by coating with polybenzimidazole (PBI). Nitrogen adsorption experiments reveal that the PBI coating of CBs results in the capping of the gates of the CB-micropores by the PBI. Since the surface of the micropores inside the CBs are inherently highly oxidized, the capping of such pores effectively prevents the penetration of the electrolyte into the pore and works to avoid the further oxidation of interior of the micropore, which is proved by cyclic voltammogram measurements. Above mechanism agrees very well with the dramatic enhancement of the durability of the membrane electrode assembly fabricated using Pt on the PBI-coated CBs as an electrocatalyst compared to the conventional Pt/CB (PBI-non coated) catalyst. PMID:27227977

  10. Gypsum (CaSO42H2O) scaling on polybenzimidazole and cellulose acetate hollow fiber membranes under forward osmosis

    Chen, Si Cong

    2013-11-08

    We have examined the gypsum (CaSO42H2O) scaling phenomena on membranes with different physicochemical properties in forward osmosis (FO) processes. Three hollow fiber membranes made of (1) cellulose acetate (CA), (2) polybenzimidazole (PBI)/polyethersulfone (PES) and (3) PBI-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) were studied. For the first time in FO processes, we have found that surface ionic interactions dominate gypsum scaling on the membrane surface. A 70% flux reduction was observed on negatively charged CA and PBI membrane surfaces, due to strong attractive forces. The PBI membrane surface also showed a slightly positive charge at a low pH value of 3 and exhibited a 30% flux reduction. The atomic force microscopy (AFM) force measurements confirmed a strong repulsive force between gypsum and PBI at a pH value of 3. The newly developed PBI-POSS/PAN membrane had ridge morphology and a contact angle of 51.42 14.85 after the addition of hydrophilic POSS nanoparticles and 3 min thermal treatment at 95 C. Minimal scaling and an only 1.3% flux reduction were observed at a pH value of 3. Such a ridge structure may reduce scaling by not providing a locally flat surface to the crystallite at a pH value of 3; thus, gypsum would be easily washed away from the surface. 2013 by the authors; licensee MDPI, Basel, Switzerland.

  11. Fouling behaviors of polybenzimidazole (PBI)-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) hollow fiber membranes for engineering osmosis processes

    Chen, Sicong

    2014-02-01

    This paper investigated the individual effects of reverse salt flux and permeate flux on fouling behaviors of as-spun and annealed polybenzimidazole (PBI)-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) hollow fiber membranes under forward osmosis (FO) and pressure retarded osmosis (PRO) processes. Two types of membrane fouling had been studied; namely, inorganic fouling (CaSO4·2H2O gypsum scaling) during FO operations and organic fouling (sodium alginate fouling) during PRO operations. It is found that gypsum scaling on the membrane surface may be inhibited and even eliminated with an increase in reverse MgCl2 flux due to competitive formations of MgSO4° and CaSO4·2H2O. In contrast, the increase of reverse NaCl flux exhibits a slight enhancement on alginate fouling in both FO and PRO processes. Comparing to the reverse salt flux, the permeate flux always plays a dominant role in fouling. Therefore, lesser fouling has been observed on the membrane surface under the pressurized PRO process than FO process because the reduced initial flux mitigates the fouling phenomena more significantly than the enhancement caused by an increase in reverse NaCl flux. © 2013 Elsevier B.V.

  12. Effects of the sintering temperature on the flux-pinning mechanism and the activation energy of malic-acid doped MgB2

    J Peleckis

    2012-12-01

    Full Text Available   The flux-pinning mechanism and activation energy of 10 wt % malic acid-doped MgB2 were investigated by measuring of the critical current density and resistivity as a function of magnetic field and temperature. A crossover field, Bsb, was observed from the single vortex to the small vortex bundle pinning regime. For the sintered sample, the temperature dependence of Bsb(T at low temperature is in good agreement with the δℓ pinning mechanism, i.e., pinning associated with charge-carrier mean free path fluctuation. The activation energy was decreased by increasing the magnetic field and increased by increasing sintering temperature.

  13. Complete doping in solid-state by silica-supported perchloric acid as dopant solid acid: Synthesis and characterization of the novel chiral composite of poly [(±)-2-(sec-butyl) aniline

    Farrokhzadeh, Abdolkarim; Modarresi-Alam, Ali Reza

    2016-05-01

    Poly [(±)-2-(sec-butyl) aniline]/silica-supported perchloric acid composites were synthesized by combination of poly[(±)-2-sec-butylaniline] base (PSBA) and the silica-supported perchloric acid (SSPA) as dopant solid acid in solid-state. The X-ray photoelectron spectroscopy (XPS) and CHNS results confirm nigraniline oxidation state and complete doping for composites (about 75%) and non-complete for the PSBA·HCl salt (about 49%). The conductivity of samples was (≈0.07 S/cm) in agreement with the percent of doping obtained of the XPS analysis. Also, contact resistance was determined by circular-TLM measurement. The morphology of samples by the scanning electron microscopy (SEM) and their coating were investigated by XPS, SEM-map and energy-dispersive X-ray spectroscopy (EDX). The key benefits of this work are the preparation of conductive chiral composite with the delocalized polaron structure under green chemistry and solid-state condition, the improvement of the processability by inclusion of the 2-sec-butyl group and the use of dopant solid acid (SSPA) as dopant.

  14. POLYMER ELECTROLYTE MEMBRANE FUEL CELLS

    2001-01-01

    A method for preparing polybenzimidazole or polybenzimidazole blend membranes and fabricating gas diffusion electrodes and membrane-electrode assemblies is provided for a high temperature polymer electrolyte membrane fuel cell. Blend polymer electrolyte membranes based on PBI and various...... thermoplastic polymers for high temperature polymer electrolyte fuel cells have also been developed. Miscible blends are used for solution casting of polymer membranes (solid electrolytes). High conductivity and enhanced mechanical strength were obtained for the blend polymer solid electrolytes. With the...... thermally resistant polymer, e.g., polybenzimidazole or a mixture of polybenzimidazole and other thermoplastics as binder, the carbon-supported noble metal catalyst is tape-cast onto a hydrophobic supporting substrate. When doped with an acid mixture, electrodes are assembled with an acid doped solid...

  15. A rapid microwave synthesis of nitrogen-sulfur co-doped carbon nanodots as highly sensitive and selective fluorescence probes for ascorbic acid.

    Duan, Junxia; Yu, Jie; Feng, Suling; Su, Li

    2016-06-01

    A ultrafast one-step microwave-assisted method was developed for the synthesis of nitrogen-sulfur co-doped carbon nanodots (N,S-CDs) by using ethylenediamine as the carbon source and sulfamic acid as the surface passivation reagent. The morphology and the properties of N,S-CDs were explored by a series of techniques, such as high-resolution transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, UV-vis absorption and fluorescence spectroscopy. The prepared N,S-CDs exhibit bright blue photoluminescence with a high fluorescence quantum yield (FLQY) up to 28%, and high stability and excellent water solubility. A N,S-CDs-based fluorescent probe was developed for sensitive detection ascorbic acid (AA) in the presence of Cu(2+), based on the mechanism that AA reduces Cu(2+) to Cu(+), then Cu(+) quenches the fluorescence of N,S-CDs through electron or energy transfer due to the interaction between Cu(+) and thiol ligand on the N,S-CDs surface. The observed linear response concentration range was from 0.057 to 4.0μM to AA with a detection limit as low as 18nM. The probe exhibited a highly selective response toward AA even in the presence of possible interfering substances, such as uric acid and citric acid. Moreover, these promising features made the sensing system used for the analysis of human serum and urine samples. PMID:27130124

  16. Investigation of catalytic activity towards oxygen reduction reaction of Pt dispersed on boron doped graphene in acid medium.

    Pullamsetty, Ashok; Sundara, Ramaprabhu

    2016-10-01

    Boron doped graphene was prepared by a facile method and platinum (Pt) decoration over boron doped graphene was done in various chemical reduction methods such as sodium borohydride (NaBH4), polyol and modified polyol. X-ray diffraction analysis indicates that the synthesized catalyst particles are present in a nanocrystalline structure and transmission and scanning electron microscopy were employed to investigate the morphology and particle distribution. The electrochemical properties were investigated with the help of the rotating disk electrode (RDE) technique and cyclic voltammetry. The results show that the oxygen reduction reaction (ORR) takes place by a four-electron process. The kinetics of the ORR was evaluated using K-L and Tafel plots. The electrocatalyst obtained in modified polyol reduction method has shown the better catalytic activity compared to other two electrocatalysts. PMID:27393888

  17. A Quaternary Polybenzimidazole Membrane for Intermediate Temperature Polymer Electrolyte Membrane Fuel Cells

    Xu, C.; Scott, K.; Li, Qingfeng;

    2013-01-01

    at 150 °C with the PA acid loading level of 3.5 PRU (amount of H3PO4 per repeat unit of polymer QPBI). The QPBI membrane was characterized in terms of composition, structure and morphology by NMR, FTIR, SEM, and EDX. The fuel cell performance with the membrane gave peak power densities of 440 and 240...

  18. White light emission from Mn2+ doped ZnS nanocrystals through the surface chelating of 8-hydroxyquinoline-5-sulfonic acid

    White light emitting semiconductor nanocrystals (NCs) have been successfully synthesized from 8-hydroxyquinoline-5-sulfonic acid (HQS) decorated manganese doped ZnS NCs through fine tuning the surface-coordination emission and dopant emission of the NC host. The HQS functionalized manganese doped ZnS NCs (QS-ZnS:Mn), with a cubic crystal structure, have the same diameter of about 4.0 nm as ZnS:Mn NCs without HQS. The intensity of the surface-coordination emission peak increased with increasing HQS content or augmenting excited wavelength. The emission of white light was achieved by carefully controlling the dosage of HQS in NCs and appropriately tuning the excited wavelength. The color coordinates (0.35, 0.34) for the efficient white light emitting NCs were very close to the ideal Commission Internationale de l'Eclairage (CIE) chromaticity coordinates for pure white light (0.33, 0.33). The photoluminescence (PL) decay study revealed that the white light emitting NCs exhibited maximum lifetime values at different emission peaks for different NC samples. The study results also indicated that the HQS molecules were attached to the surface of ZnS:Mn NCs in a single coordination fashion due to the steric hindrance effect of the special spherical surface of NCs, which made the QS-ZnS:Mn NCs possess stable and high fluorescent properties in different organic solvents as compared with the conventional small molecule complexes.

  19. Nanocrystalline semiconductor doped rare earth oxide for the photocatalytic degradation studies on Acid Blue 113: A di-azo compound under UV slurry photoreactor.

    Suganya Josephine, G A; Mary Nisha, U; Meenakshi, G; Sivasamy, A

    2015-11-01

    Preventive measures for the control of environmental pollution and its remediation has received much interest in recent years due to the world-wide increase in the contamination of water bodies. Contributions of these harmful effluents are caused by the leather processing, pharmaceutical, cosmetic, textile, agricultural and other chemical industries. Nowadays, advanced oxidation processes considered to be better option for the complete destruction of organic contaminants in water and wastewater. Acid Blue 113 is a most widely used di-azo compound in leather, textile, dying and food industry as a color rending compound. In the present study, we have reported the photo catalytic degradation of Acid Blue 113 using a nanocrystalline semiconductor doped rare earth oxide as a photo catalyst under UV light irradiation. The photocatalyst was prepared by a simple precipitation technique and were characterized by XRD, FT-IR, UV-DRS and FE-SEM analysis. The experimental results proved that the prepared photo catalyst was nanocrystalline and highly active in the UV region. The UV-DRS results showed the band gap energy was 3.15eV for the prepared photo catalyst. The photodegradation efficiency was analyzed by various experimental parameters such as pH, catalyst dosage, variation of substrate concentration and effect of electrolyte addition. The photo degradation process followed a pseudo first order kinetics and was continuously monitored by UV-visible spectrophotometer. The experimental results proved the efficacy of the nanocrystalline zinc oxide doped dysprosium oxide which are highly active under UV light irradiations. It is also suggested that the prepared material would find wider applications in environmental remediation technologies to remove the carcinogenic and toxic moieties present in the industrial effluents. PMID:26025644

  20. Effects of the Doping ZnO on the property of Magnetic Solid Acid SO/sub 4/sup 2-/ZrO/sub 2-/Fe/sub 3/O/sub 4/

    Two kinds of magnetic solid acid catalysts are prepared via a simple chemical co-precipitation approach. The obtained materials are characterized by X-ray Diffraction, FT-IR Spectrometer, Different Scanning Calorimetry, Vibrating Sample Magnetometer, Transmission Electron Microscopy, High-resolution Transmission Electron Microscopy and Hammett indicator. The results indicate that the doping of ZnO restrains the phase transformation from tetragonal zirconia to monoclinic zirconia. Furthermore, the samples show a magnetic behavior. Saturation magnetization of the sample SO/sub 4//sup 2-/ /ZrO/sub 2/-Fe/sub 3/O/sub 4/ is smaller than SO/sub 4/sup 2/-/ZrO/sub 2/-Fe/sub 3/O/sub 4/-ZnO; Transmission Electron Microscopy results indicate that the increasing ZnO makes the grains size considerably smaller, and the High-resolution Transmission Electron Microscopy shows that the doping of ZnO maintains the desired tetragonal zirconia phase, and the interplanar spacing is d(101)=0.29 nm. Hammett indicator results show that the acid strength becomes stronger because of the doping of ZnO. The synthesis of methyl laurate as the probe reactions of magnetic solid acids is studied, and the result indicates that the doping of ZnO delays the deactivation rate of catalysts. (author)

  1. Synthesis and development of low cost, high temperature N-arylene polybenzimidazole foam material

    Harrison, E. S.

    1975-01-01

    Polymer (and foam) studies followed two basic routes: (1) formation of high molecular weight uncyclized polyamide followed by subsequent fusion and cyclodehydration to yield NABI (foam) and (2) polymer and foam formation by reaction of diphenyl esters (or anhydrides) with the tetramine. The latter route was found much more attractive since considerable versatility in both basic polymer structure and crosslinkability is achievable. Preliminary studies on BAB, phthalic anhydride (PA), and 3, 3 (prime), 4, 4(prime) benzo pheno netetracarboxylic acid dianhydride (BTDA) as crosslinked polymer precursors were conducted. Nonmelting rigid char forming foams with densities as low as 2.7 lb/cubic ft. were achieved. The program was successful in the preparation of a potentially low cost, low density, high char yield, high temperature foam material.

  2. Boronic acid functionalized N-doped carbon quantum dots as fluorescent probe for selective and sensitive glucose determination

    Jiang, Guohua; Jiang, Tengteng; Li, Xia; Wei, Zheng; Du, Xiangxiang; Wang, Xiaohong

    2014-04-01

    Nitrogen doped carbon quantum dots (NCQDs) of about 10 nm in diameter have been obtained by hydrothermal reaction from collagen. Because of the superiority of water dispersion, low toxicity and ease of functionlization, the NCQDs were designed as a glucose sensor after covalent grafting by 3-aminophenylboronic (APBA) (APBA-NCQDs). The as-prepared APBA-NCQDs were imparted with glucose sensitivity and selectivity from other saccharides via fluorescence (FL) quenching effect at physiological pH and at room temperature, which show high sensitivity and specificity for glucose determination with a wide range from 1 mM to 14 mM. FL quenching mechanism of APBA-NCQDs was also investigated by adding an external quencher. The APBA-NCQDs-based platform is an environmentally friendly way to substitute inorganic quantum dots containing heavy metals which offer a facile and low cost detection method.

  3. Palladium Nanoparticles Supported on Nitrogen and Sulfur Dual-Doped Graphene as Highly Active Electrocatalysts for Formic Acid and Methanol Oxidation.

    Zhang, Xin; Zhu, Jixin; Tiwary, Chandra Sekhar; Ma, Zhongyuan; Huang, Huajie; Zhang, Jianfeng; Lu, Zhiyong; Huang, Wei; Wu, Yuping

    2016-05-01

    Optimized designing of highly active electrocatalysts has been regarded as a critical point to the development of portable fuel cell systems with high power density. Here we report a facile and cost-effective strategy to synthesis of ultrafine Pd nanoparticles (NPs) supported on N and S dual-doped graphene (NS-G) nanosheets as multifunctional electrocatalysts for both direct formic acid fuel cell and direct methanol fuel cell. The incorporation of N and S atoms into graphene frameworks is achieved by a thermal treatment process, followed by the controlled growth of Pd NPs via a solvothermal approach. Owning to the unique structural features as well as the strong synergistic effects, the resulting Pd/NS-G hybrid exhibits outstanding electrocatalytic performance toward both formic acid and methanol electro-oxidation, such as higher anodic peak current densities and more exceptional catalytic stability than those of Pd/Vulcan XC-72R and Pd/undoped graphene catalysts. These findings open up new possibility in the construction of advanced Pd-based catalysts, which is conducive to solving the current bottlenecks of fuel cell technologies. PMID:27082661

  4. Enhancement of periodate-hydrogen peroxide chemiluminescence by nitrogen doped carbon dots and its application for the determination of pyrogallol and gallic acid.

    Shah, Syed Niaz Ali; Li, Haifang; Lin, Jin-Ming

    2016-06-01

    A new sensitized chemiluminescence (CL) was developed to broaden the analytical application of KIO4-H2O2 system. The nitrogen doped carbon dots (N-CDs) dramatically boosted the CL intensity of KIO4-H2O2 system which was further enriched by basic medium. In light of EPR analysis, free radical scavenging studies and CL spectra the detail mechanism for the enhancement was conferred in the presence of N-CDs and NaOH. The results suggested that CL of KIO4-H2O2 system in the presence and absence of N-CDs and NaOH proceeds via radical pathway. The enhanced CL was used for the determination of pyrogallol and gallic acid in range of 1.0×10(-4)-1.0×10(-7)M with 4.6×10(-8) and 6.1×10(-8)M limit of detection respectively. The relative standard deviation (RSD) at a concentration of 10(-5) for gallic acid and pyrogallol was 1.4% and 2.3% respectively (n=11). The attained results unveil that the present method is sensitive, faster, simpler and less costly compared to other methods and could be applied to determine polyphenols in real samples. PMID:27130085

  5. Humidity sensing with doped polyaniline

    Jain, Shilpa; Chakane, Sanjay D. S.; Bhoraskar, S. V.; Samui, A. B.; Krishnamurthy, V. N.

    2001-03-01

    Polyaniline (PANI) was doped with different dopants like camphosulphoric acid (CSA), diphenyl phosphate (DPPH), Sulphonic acid (S) and Maleic acid (MAC) by chemical method. The samples were prepared in the form of pellets as well as films. Polyaniline doped with Maleic acid was found to be mechanically and chemically stable as compared to other dopants and therefore the effect of humidity on conductivity was further investigated. Films prepared out of styrene buryl acrylate copolymer with different concentrations of PANI Maleic acid were used for sensing humidity ranging between 20% to 90% relative humidity. A maximum change in the conductivity of three to four orders of magnitude was obtained for the Maleic acid doped polyaniline pellet while two orders of magnitude change was obtained for the film samples over the range of humidity measured.

  6. A glassy carbon electrode modified with a polyaniline doped with silicotungstic acid and carbon nanotubes for the sensitive amperometric determination of ascorbic acid

    We report on an electrochemical sensor for the sensitive amperometric determination of ascorbic acid (AA). Aniline containing suspended silicotungstic acid and carbon nanotubes was electropolymerized on the surface of a glassy carbon electrode in a single step which provides a simple and controllable method and greatly improves the electrocatalytic oxidation of AA. The effects of scan rate, solution pH and working potential were studied. A linear relationship exists between the current measured and the concentration of AA in the range from 1 μM to 10 μM and 0.01 mM to 9 mM, with a limit of detection as low as 0.51 μM (S/N = 3). The sensor is selective, stable and satisfyingly reliable in real sample experiments. In our eyes, it has a large potential for practical applications. (author)

  7. An investigation of proton conductivity of binary matrices sulfonated polysulfone/polyvinyltriazole after doping with inorganic acids

    Serkan Sevinç; Sevim Ünügür Çelik; Ayhan Bozkurt

    2015-04-01

    As anhydrous proton conductive membranes, sulfonated polysulfone (SPSU) and polyvinyl triazole were studied as binary matrices. The sulfonation of polysulfone was performed with trimethylsilylchlorosulfonate and high degree of sulfonation (140%) was obtained. Ion exchange capacity of SPSU was determined as 3.05 mmol−1/g. The polymer electrolyte membranes were prepared by blending of sulfonated polysulfone with polyvinyl triazole and phosphoric acid. Fourier transform infrared spectroscopy confirmed the sulfonation of the polysulfone and the ionic interaction between sulfonic acid and triazole units. Thermogravimetric analysis showed that the polymer electrolyte membranes are thermally stable up to at least 150° C. Scanning electron microscopy analysis indicated the homogeneity of the ternary composites. The maximum proton conductivity has been measured as 3.63 × 10−4S cm−1 at 150° C.

  8. Multifunctional electroactive electrospun nanofiber structures from water solution blends of PVA/ODA–MMT and poly(maleic acid-alt-acrylic acid): effects of Ag, organoclay, structural rearrangement and NaOH doping factors

    Şimşek, Murat; Rzayev, Zakir M. O.; Bunyatova, Ulviya

    2016-06-01

    Novel multifunctional colloidal polymer nanofiber electrolytes were fabricated by green reactive electrospinning nanotechnology from various water solution/dispersed blends of poly (vinyl alcohol-co-vinyl acetate) (PVA)/octadecyl amine-montmorillonite (ODA–MMT) as matrix polymer nanocomposite and poly(maleic acid-alt-acrylic acid) (poly(MAc-alt-AA) and/or its Ag-carrying complex as partner copolymers. Polymer nanofiber electrolytes were characterized using FTIR, XRD, thermal (DSC, TGA–DTG), SEM, and electrical analysis methods. Effects of partner copolymers, organoclay, in situ generated silver nanoparticles (AgNPs), and annealing procedure on physical and chemical properties of polymer composite nanofibers were investigated. The electrical properties (resistance, conductivity, activation energy) of nanofibers with/without NaOH doping agent were also evaluated. This work presented a structural rearrangement of nanofiber mats by annealing via decarboxylation of anhydride units with the formation of new conjugated double bond sites onto partner copolymer main chains. It was also found that the semiconductor behaviors of nanofiber structures were essentially improved with increasing temperature and fraction of partner copolymers as well as presence of organoclay and AgNPs in nanofiber composite.

  9. High-Performance Flexible Solid-State Carbon Cloth Supercapacitors Based on Highly Processible N-Graphene Doped Polyacrylic Acid/Polyaniline Composites.

    Wang, Yongguang; Tang, Shaochun; Vongehr, Sascha; Ali Syed, Junaid; Wang, Xiangyu; Meng, Xiangkang

    2016-01-01

    Improving the solubility of conductive polymers to facilitate processing usually decreases their conductivity, and they suffer from poor cycling stability due to swelling-shrinking during charging cycles. We circumvent these problems with a novel preparation method for nitrogen-doped graphene (NG) enhanced polyacrylic acid/polyaniline (NG-PAA/PANI) composites, ensuring excellent processibility for scalable production. The content of PANI is maximized under the constraint of still allowing defect-free coatings on filaments of carbon cloth (CC). The NG content is then adjusted to optimize specific capacitance. The optimal CC electrodes have 32 wt.% PANI and 1.3 wt.% NG, thus achieving a high capacitance of 521 F/g at 0.5 F/g. A symmetric supercapacitor made from 20 wt.% PANI CC electrodes has more than four times the capacitance (68 F/g at 1 A/g) of previously reported flexible capacitors based on PANI-carbon nanotube composites, and it retains the full capacitance under large bending angles. The capacitor exhibits high energy and power densities (5.8 Wh/kg at 1.1 kW/kg), a superior rate capability (still 81% of the 1 A/g capacitance at 10 A/g), and long-term electrochemical stability (83.2% retention after 2000 cycles). PMID:26883179

  10. Fluorine doped zinc oxide thin films deposited by chemical spray, starting from zinc pentanedionate and hydrofluoric acid: Effect of the aging time of the solution

    Fluorine doped zinc oxide thin films, ZnO:F, were deposited on sodocalcic glass substrates, starting from zinc pentanedionate and hydrofluoric acid, by the chemical spray technique. The effect of the aging time of the starting solution on the electrical, structural, morphological and optical characteristics of the ZnO thin films was studied. Uniform, adherent, and mirror-like films were deposited at different days. A high electrical resistivity, was found in the films deposited the first day. However, a decrease in the resistivity, until a minimum, in the order of 3 x 10-2 Ω cm was reached for films deposited after the starting solution was aged for twelve days. The films fit well with the hexagonal, wurtzite-type ZnO structure, with a (0 0 2) preferential growth. Variation in the grain size was observed as a consequence of the aging of the solution. An average crystallite size varied between 17.3 and 22.8 nm due to aging effect, and some variations in surface morphology were encountered. All the films are highly transparent in the near UV-vis range, with an average transmittance oscillating between 83% and 90%.

  11. High-Performance Flexible Solid-State Carbon Cloth Supercapacitors Based on Highly Processible N-Graphene Doped Polyacrylic Acid/Polyaniline Composites

    Wang, Yongguang; Tang, Shaochun; Vongehr, Sascha; Ali Syed, Junaid; Wang, Xiangyu; Meng, Xiangkang

    2016-02-01

    Improving the solubility of conductive polymers to facilitate processing usually decreases their conductivity, and they suffer from poor cycling stability due to swelling-shrinking during charging cycles. We circumvent these problems with a novel preparation method for nitrogen-doped graphene (NG) enhanced polyacrylic acid/polyaniline (NG-PAA/PANI) composites, ensuring excellent processibility for scalable production. The content of PANI is maximized under the constraint of still allowing defect-free coatings on filaments of carbon cloth (CC). The NG content is then adjusted to optimize specific capacitance. The optimal CC electrodes have 32 wt.% PANI and 1.3 wt.% NG, thus achieving a high capacitance of 521 F/g at 0.5 F/g. A symmetric supercapacitor made from 20 wt.% PANI CC electrodes has more than four times the capacitance (68 F/g at 1 A/g) of previously reported flexible capacitors based on PANI-carbon nanotube composites, and it retains the full capacitance under large bending angles. The capacitor exhibits high energy and power densities (5.8 Wh/kg at 1.1 kW/kg), a superior rate capability (still 81% of the 1 A/g capacitance at 10 A/g), and long-term electrochemical stability (83.2% retention after 2000 cycles).

  12. Aptameric Recognition-Modulated Electroactivity of Poly(4-Styrenesolfonic Acid-Doped Polyaniline Films for Single-Shot Detection of Tetrodotoxin

    Gertrude Fomo

    2015-09-01

    Full Text Available The work being reported is the first electrochemical sensor for tetrodotoxin (TTX. It was developed on a glassy carbon electrodes (C that was modified with poly(4-styrenesolfonic acid-doped polyaniline film (PANI/PSSA. An amine-end functionalized TTX-binding aptamer, 5′-NH2-AAAAATTTCACACGGGTGCCTCGGCTGTCC-3′ (NH2-Apt, was grafted via covalent glutaraldehyde (glu cross-linking. The resulting aptasensor (C//PANI+/PSSA-glu-NH2-Apt was interrogated by cyclic voltammetry (CV and electrochemical impedance spectroscopy (EIS in sodium acetate buffer (NaOAc, pH 4.8 before and after 30 min incubation in standard TTX solutions. Both CV and EIS results confirmed that the binding of the analyte to the immobilized aptamer modulated the electrochemical properties of the sensor: particularly the charge transfer resistance (Rct of the PANI+/PSSA film, which served as a signal reporter. Based on the Rct calibration curve of the TTX aptasensor, the values of the dynamic linear range (DLR, sensitivity and limit of detection (LOD of the sensor were determined to be 0.23–1.07 ng·mL−1 TTX, 134.88 ± 11.42 Ω·ng·mL−1 and 0.199 ng·mL−1, respectively. Further studies are being planned to improve the DLR as well as to evaluate selectivity and matrix effects in real samples.

  13. Optical sensing of 3-phenoxybenzoic acid as a pyrethroid pesticides exposure marker by surface imprinting polymer capped on manganese-doped zinc sulfide quantum dots

    Vivek Pandey

    2015-09-01

    Full Text Available The present communication deals with the synthesis of luminescent Mn-doped ZnS quantum dots (QDs anchored to surface imprinted polymer for the optical sensing of 3-phenoxy benzoic acid (3-PBA in urine samples. The combination of sensing and surface functionalization not only improves the selectivity of the method, but also increases the optosensing ability of the material for non-phosphorescent substances. The developed material was utilized for the selective and sensitive detection of 3-PBA in urine samples. The proposed method shows good linearity with a regression coefficient (R2 of 0.98. The limit of detection was found to be 0.117 μM. The method has an acceptable precision and accuracy which are found to be less than 8% and 80–90% respectively at three different concentrations. The quenching constant of quantum dot-molecular imprinted polymer was found to be 3.4 times higher to that of the quantum dot-non imprinted polymer (QD-NIP as calculated by Stern–Volmer equation. The sensing method developed has shown immense utility to detect 3-PBA in complex biological samples like urine.

  14. An ultrasensitive electrochemical sensor for simultaneous determination of xanthine, hypoxanthine and uric acid based on Co doped CeO2 nanoparticles.

    Lavanya, N; Sekar, C; Murugan, R; Ravi, G

    2016-08-01

    A novel electrochemical sensor has been fabricated using Co doped CeO2 nanoparticles for selective and simultaneous determination of xanthine (XA), hypoxanthine (HXA) and uric acid (UA) in a phosphate buffer solution (PBS, pH5.0) for the first time. The Co-CeO2 NPs have been prepared by microwave irradiation method and characterized by Powder XRD, Raman spectroscopy, HRTEM and VSM measurements. The electrochemical behaviours of XA, HXA and UA at the Co-CeO2 NPs modified glassy carbon electrode (GCE) were studied by cyclic voltammetry and square wave voltammetry methods. The modified electrode exhibited remarkably well-separated anodic peaks corresponding to the oxidation of XA, HXA and UA over the concentration range of 0.1-1000, 1-600 and 1-2200μM with detection limits of 0.096, 0.36, and 0.12μM (S/N=3), respectively. For simultaneous detection by synchronous change of the concentrations of XA, HXA and UA, the linear responses were in the range of 1-400μM each with the detection limits of 0.47, 0.26, and 0.43μM (S/N=3), respectively. The fabricated sensor was further applied to the detection of XA, HXA and UA in human urine samples with good selectivity and high reproducibility. PMID:27157753

  15. Synthesis of nitrogen-doped and amino acid-functionalized graphene quantum dots from glycine, and their application to the fluorometric determination of ferric ion

    We report on a single-step thermolysis strategy to prepare highly luminescent nitrogen-doped and amino acid-functionalized graphene quantum dots (NA-GQDs) by using glycine as both carbon and nitrogen source. The NA-GQDs display an excitation wavelength-dependent fluorescence with maximum excitation and emission wavelengths of 380 and 450 nm, respectively, and a quantum yield of ∼16 %. Fluorescence is quenched by Fe(III) and Hg(II), and the effect was used to develop a method for the determination of Fe(III). Quenching by Fe(III) is attributed to its higher thermodynamic affinity (compared to other transition-metal ions) for the ligands on the GQDs in which nitrogen atoms mainly act as the chelating atoms. A linear relationship was observed between fluorescence intensity and the concentration of Fe(III) over the 0.5 μM to 0.5 mM range. The detection limit is 0.1 μM. (author)

  16. High-Performance Flexible Solid-State Carbon Cloth Supercapacitors Based on Highly Processible N-Graphene Doped Polyacrylic Acid/Polyaniline Composites

    Wang, Yongguang; Tang, Shaochun; Vongehr, Sascha; Ali Syed, Junaid; Wang, Xiangyu; Meng, Xiangkang

    2016-01-01

    Improving the solubility of conductive polymers to facilitate processing usually decreases their conductivity, and they suffer from poor cycling stability due to swelling-shrinking during charging cycles. We circumvent these problems with a novel preparation method for nitrogen-doped graphene (NG) enhanced polyacrylic acid/polyaniline (NG-PAA/PANI) composites, ensuring excellent processibility for scalable production. The content of PANI is maximized under the constraint of still allowing defect-free coatings on filaments of carbon cloth (CC). The NG content is then adjusted to optimize specific capacitance. The optimal CC electrodes have 32 wt.% PANI and 1.3 wt.% NG, thus achieving a high capacitance of 521 F/g at 0.5 F/g. A symmetric supercapacitor made from 20 wt.% PANI CC electrodes has more than four times the capacitance (68 F/g at 1 A/g) of previously reported flexible capacitors based on PANI-carbon nanotube composites, and it retains the full capacitance under large bending angles. The capacitor exhibits high energy and power densities (5.8 Wh/kg at 1.1 kW/kg), a superior rate capability (still 81% of the 1 A/g capacitance at 10 A/g), and long-term electrochemical stability (83.2% retention after 2000 cycles). PMID:26883179

  17. Kinetic study of formic acid degradation by Fe3+ doped TiO2 self-cleaning nanostructure surfaces prepared by cold spray

    Sayyar, Zahra; Akbar Babaluo, Ali; Shahrouzi, Javad Rahbar

    2015-04-01

    A self-cleaning solution was introduced in this paper based on sol-gel and was applied for preparing self-cleaning TiO2. Fe3+ ions have been doped into the TiO2 crystal lattice. XRD analysis indicated that the obtained TiO2 powder contains mainly the anatase phase and TiO2 powder has a crystallite size distribution of 10-12 nm. SEM micrographs have also confirmed nanometric distribution of the obtained powder. A series of uniform and transparent TiO2 and Fe/TiO2 films were prepared by cold spray technique which may result in high uniformity in the final coated surfaces. Photocatalytic activity of the thin films was investigated through degradation of aqueous formic acid under UV-visible light. The Langmuir-Hinshelwood kinetic model was used to interpret quantitatively the observed kinetic experimental result. Comparative study of the obtained coated surfaces with those of uncoated surfaces, demonstrated a remarkable performance. The Fe/TiO2 films and their calcination at 650 °C demonstrated the highest photocatalytic activity.

  18. EPR and optical absorption studies of Cu2+ doped L-histidinium dihydrogen phosphate–phosphoric acid single crystal

    The EPR spectra of Cu2+ in L-histidinium dihydrogen phosphate phosphoric acid at room temperature reveal the presence of two magnetically inequivalent Cu2+ sites in the lattice. The principal values of the g- and A-tensors indicate existence of rhombic symmetry around the Cu2+ ion. From the direction cosines of the principal values of the g- and A-tensors, the locations of Cu2+ in the lattice have been identified as substitutional sites. Optical absorption study shows four bands confirm the rhombic symmetry. Photoluminescence study also confirms the rhombic symmetry around the ions

  19. Effect of High Temperature on the Electrochemical and Optical Properties of Emeraldine Salt Doped with DBSA and Sulfuric Acid

    Salma Gul

    2015-01-01

    Full Text Available A comprehensive study of thermally treated polyaniline in its emeraldine salt form is presented here. It offers an understanding of the thermal stability of the polymer. Emeraldine salt was prepared by a novel emulsion polymerization pathway using dodecylbenzene sulfonic acid and sulfuric acid together as dopants. The effect of temperature and heating rate on the degradation of this emeraldine salt was studied via thermogravimetric analysis. The thermally analyzed sample was collected at various temperatures, that is, 250, 490, 500, and 1000°C. The gradual changes in the structure of the emeraldine salt were followed through cyclic voltammetry, Fourier transform infrared spectroscopy, and ultraviolet-visible spectroscopy. Results demonstrate that emeraldine salt shows high thermal stability up to 500°C. This is much higher working temperature for the use of emeraldine salt in higher temperature applications. Further heat treatment seems to induce deprotonation in emeraldine salt. Cyclic voltammetry and ultraviolet-visible spectroscopy revealed that complete deprotonation takes place at 1000°C where it loses its electrical conductivity. It is interesting to note that after the elimination of the dopants, the basic backbone of emeraldine salt was not destroyed. The results reveal that the dopants employed have a stability effect on the skeleton of emeraldine salt.

  20. Poly-glutamic acid modified carbon nanotube-doped carbon paste electrode for sensitive detection of L-tryptophan.

    Liu, Xiao; Luo, Liqiang; Ding, Yaping; Ye, Daixin

    2011-08-01

    A novel poly-glutamic acid (PGA) film modified carbon paste electrode (CPE) incorporating carbon nanotubes (CNTs) was first prepared for the determination of l-tryptophan (l-Trp). Scanning electron microscopy and Fourier transform infrared spectroscopy were applied for characterization of the surface morphology of the modified electrodes and cyclic voltammetry was used to investigate the electrochemical properties of the proposed electrode towards the oxidation of l-Trp. Optimization of the experimental parameters was performed with regard to pH, ratio of CNTs, concentration of glutamic acid, electro-polymerization cycles, accumulation time and concentration of sodium dodecylbenzene sulfonate. The linearity between the oxidation peak current and the l-Trp concentration was obtained in the range of 5.0×10(-8) to 1.0×10(-4)M with a detection limit of 1.0×10(-8)M (S/N=3) and the sensitivity was calculated to be 1143.79μA∙mM(-1)∙cm(-2). In addition, the PGA modified CPE incorporating CNTs displayed high selectivity, good stability and reproducibility, making it suitable for the routine analysis of l-Trp in clinical use. PMID:21640670

  1. Structural, electronic and photoluminescence properties of Eu3+-doped CaYAlO4 obtained by using citric acid complexes as precursors

    Perrella, R. V.; Júnior, C. S. Nascimento; Góes, M. S.; Pecoraro, E.; Schiavon, M. A.; Paiva-Santos, C. O.; Lima, H.; Couto dos Santos, M. A.; Ribeiro, S. J. L.; Ferrari, J. L.

    2016-07-01

    The search for new materials that meet the current technological demands for photonic applications, make the Rare Earth ions embedded in inorganic oxides as excellent candidates for several technological devices. This work presents the synthesis of Eu3+-doped CaYAlO4 using citric acid as ligand to form a complex precursor. The methodology used has big draw due to its easy handling and low cost of the materials. The thermal analysis of viscous solutions was evaluated and the obtained compounds show the formation of a polycrystalline tetragonal phase. Rietveld refinement was used to understand the structural and the cell parameters of the crystalline phase as a function of temperature of heat-treatment. Crystallite size and microstrain were determined and were shown to have a direct relationship with the temperature of the heat-treatment. The band-gap of the CaYAlO4 doped with 1 and 10 mol% of Eu3+ showed values close to 4.30 eV, resulting in their transparency in the visible region between 330 and 750 nm. Besides the intense photoluminescence from Eu3+, a study was conducted to evaluate the possible position of the Eu3+ in the CaYAlO4 as host lattice. Lifetime of the emission decay from Eu3+ excited state 5D0 show that CaYAlO4 is a good host to rare earth ions, once it can avoid clustering of these ions in concentration as high as 10 mol%. The predictions of the sublevels of the 7F1 crystal field level are discussed through the method of equivalent nearest neighbours (MENN). The intensity parameters (Ωλ, λ = 2 and 4) are reproduced with physically reasonable values of average polarizabilities. The set of charge factors used in both calculations are in good agreement with the charge of the europium ion described by the Batista-Longo improved model (BLIM). The quantum efficiencies of the materials were calculated based on Judd-Ofelt theory. Based on the results obtained in this work, the materials have potential use in photonic devices such as lasers and solid

  2. Study of polyaniline doped with trifluoromethane sulfonic acid in gas-diffusion electrodes for proton-exchange membrane fuel cells

    Gharibi, Hussein; Zhiani, Mohammad; Kheirmand, Mehdi; Kakaei, Karim [Department of Physical Chemistry, Faculty of Science, Tarbiat Modarres University, P.O. Box 14115-175, Tehran (Iran); Entezami, Ali Akbar [Faculty of Chemistry, Tabriz University, Tabriz (Iran); Mirzaie, Rasol Abdullah [Department of Chemistry, Faculty of Science, Shahid Rajaee University, Tehran (Iran)

    2006-04-21

    Polytetrafluoroethylene (PTFE)-bonded gas-diffusion electrodes (GDEs), modified with polyaniline as an electron and proton conductor in the catalyst layer, are prepared and evaluated for use in proton-exchange membrane fuel cells (PEMFCs). Polyaniline is coated on the GDE by electropolymerization of aniline and trifluoromethane sulfonic acid as the proton-conductive monomer. The electrodes are characterized by cyclic voltammetry, current-potential measurements, electrochemical impedance spectroscopy, and chronoamperometry. The polyaniline is found to be homogenously dispersed in the catalyst layer, making it a good candidate proton and electron conductor. Use of polyaniline instead of Nafion in the catalyst layer, increases the utility of the electrocatalyst by 18%. The results are consistent with the presence of polyaniline as a conductive polymer in the reaction layer reducing the polarization resistance of the electrode in comparison with that of a corresponding electrode containing Nafion. Thus, the present results indicate that PEMFCs using polyaniline-containing electrocatalysts should give superior performance to those using catalysts containing traditional ionomers. (author)

  3. Electrochemical Performance of a Carbon Nanotube/La-Doped TiO2 Nanocomposite and its Use for Preparation of an Electrochemical Nicotinic Acid Sensor

    Hanxing Liu

    2008-11-01

    Full Text Available A carbon nanotube/La-doped TiO2 (La-TiO2 nanocomposite (CLTN was prepared by a procedure similar to a complex/adsorption process. Scanning electron microscopy (SEM images show that the La-TiO2 distributes on the carbon nanotube walls. The CLTN was mixed with paraffin to form a CLTN paste for the CLTN paste electrode (CLTNPE. The electrochemical characteristics of CLTNPE were compared with that of conventional carbon electrodes such as the carbon paste electrode (CPE and glass carbon electrode (GC. The CLTNPE exhibits electrochemical activity and was used to investigate the electrochemistry of nicotinic acid (NA. The modified electrode has a strong electrocatalytic effect on the redox of NA. The cyclic voltammetry (CV redox potential of NA at the CLTNPE is 320 mV. The oxidation process of NA on the CLTNPE is pH dependent. A sensitive chronoamperometric response for NA was obtained covering a linear range from 1.0×10-6 mol·L-1 to 1.2×10-4 mol·L-1, with a detection limit of 2.7×10-7 mol·L-1. The NA sensor displays a remarkable sensitivity and stability. The mean recovery of NA in the human urine is 101.8%, with a mean variation coefficient (RSD of 2.6%.

  4. Gypsum (CaSO4·2H2O Scaling on Polybenzimidazole and Cellulose Acetate Hollow Fiber Membranes under Forward Osmosis

    Tai-Shung Chung

    2013-11-01

    Full Text Available We have examined the gypsum (CaSO4·2H2O scaling phenomena on membranes with different physicochemical properties in forward osmosis (FO processes. Three hollow fiber membranes made of (1 cellulose acetate (CA, (2 polybenzimidazole (PBI/polyethersulfone (PES and (3 PBI-polyhedral oligomeric silsesquioxane (POSS/polyacrylonitrile (PAN were studied. For the first time in FO processes, we have found that surface ionic interactions dominate gypsum scaling on the membrane surface. A 70% flux reduction was observed on negatively charged CA and PBI membrane surfaces, due to strong attractive forces. The PBI membrane surface also showed a slightly positive charge at a low pH value of 3 and exhibited a 30% flux reduction. The atomic force microscopy (AFM force measurements confirmed a strong repulsive force between gypsum and PBI at a pH value of 3. The newly developed PBI-POSS/PAN membrane had ridge morphology and a contact angle of 51.42° ± 14.85° after the addition of hydrophilic POSS nanoparticles and 3 min thermal treatment at 95 °C. Minimal scaling and an only 1.3% flux reduction were observed at a pH value of 3. Such a ridge structure may reduce scaling by not providing a locally flat surface to the crystallite at a pH value of 3; thus, gypsum would be easily washed away from the surface.

  5. Boron doping a semiconductor particle

    Stevens, Gary Don; Reynolds, Jeffrey Scott; Brown, Louanne Kay

    1998-06-09

    A method (10,30) of boron doping a semiconductor particle using boric acid to obtain a p-type doped particle. Either silicon spheres or silicon powder is mixed with a diluted solution of boric acid having a predetermined concentration. The spheres are dried (16), with the boron film then being driven (18) into the sphere. A melt procedure mixes the driven boron uniformly throughout the sphere. In the case of silicon powder, the powder is metered out (38) into piles and melted/fused (40) with an optical furnace. Both processes obtain a p-type doped silicon sphere with desired resistivity. Boric acid is not a restricted chemical, is inexpensive, and does not pose any special shipping, handling, or disposal requirements.

  6. Synthesis and characterization of Sn doped TiO2 photocatalysts: Effect of Sn concentration on the textural properties and on the photocatalytic degradation of 2,4-dichlorophenoxyacetic acid

    Abstract: TiO2 and Sn-doped TiO2 materials were prepared by sol–gel method using titanium and tin alkoxides at different Sn concentration (0.1 mol%, 0.5 mol%, 1 mol%, 3 mol% and 5 mol%). Samples were characterized by thermo gravimetric analyzer with differential scanning calorimeter (TGA–DSC), X-ray Rietveld refinement, N2 adsorption (BET), transmission electron microscopy (TEM), UV–vis spectroscopies technology and Raman spectroscopy. Only anatase phase was observed in pure TiO2, whereas anatase and brookite were obtained in Sn-doped TiO2 samples. Sn dopant acts as a promoter in phase transformation of TiO2. The Rietveld refinements method was used to determine the relative weight of anatase and brookite, and crystallite size as a function of Sn concentration after calcination of samples at 673 K. It was also demonstrated the incorporation of Sn4+ into the anatase TiO2 structure. Sn4+ inhibits the growth of TiO2 crystallite size, which leads to an increase of the specific surface area of TiO2. From XRD analysis, the solid solution limit of Sn4+ into TiO2 is 5 mol% Sn. The photocatalytic activity on Sn4+ doped TiO2 was determined for the 2,4-dichlorophenoxyacetic acid reaction. The maximum in activity was attributed to the coexistence of anatase and brookite phases in the appropriate ratio and crystallite size

  7. CO tolerance by the PEMFC operational at temperatures up to 200°C

    Li, Qingfeng; He, Ronghuan; Gao, Ji-An; Jensen, Jens Oluf; Bjerrum, Niels

    The CO poisoning effect on carbon-supported platinum catalysts in polymer electrolyte membrane fuel cells has been investigated in a temperature range from 125 to 200°C with the phosphoric acid-doped polybenzimidazole membranes as electrolyte. The effect is very temperature-dependent and can be...

  8. The CO poisoning effect in PEMFCs operational at temperatures up to 200 degrees C

    Li, Qingfeng; He, Ronghuan; Gao, Ji-An; Jensen, Jens Oluf; Bjerrum, Niels

    2003-01-01

    The CO poisoning effect on carbon-supported platinum catalysts (at a loading of 0.5 mg Pt/cm(2) per electrode! in polymer electrolyte membrane fuel cells (PEMFCs) has been investigated in a temperature range from 125 to 200 degreesC with the phosphoric acid-doped polybenzimidazole membranes as...

  9. Fe3C-based oxygen reduction catalysts: synthesis, hollow spherical structures and applications in fuel cells

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei; Fernandez, Santiago Martin; Chenitz, Regis; Pan, Chao; Xing, Wei; Bjerrum, Niels J.; Li, Qingfeng

    2015-01-01

    and stability. A new ORR active phase of Fe3C nanoparticles encapsulated by thin graphitic layers is proposed. The activity and durability of the catalysts are demonstrated in both Nafion-based low temperature and acid doped polybenzimidazole-based high temperature proton exchange membrane fuel cells....

  10. Method of operating a direct dme fuel cell system

    2011-01-01

    The present invention relates to a method of operating a fuel cell system comprising one or more fuel cells with a proton exchange membrane, wherein the membrane is composed of a polymeric material comprising acid-doped polybenzimidazole (PBI). The method comprises adjusting the operating...

  11. Comparison between FTIR and XPS characterization of amino acid glycine adsorption onto diamond-like carbon (DLC) and silicon doped DLC

    Diamond-like carbon (DLC) coatings are extremely useful for creating biocompatible surfaces on medical implants. DLC and silicon doped DLC synthesized on silicon wafer substrate by using plasma enhanced chemical vapour deposition (PECVD). The adsorption of glycine onto prepared samples has been investigated with a range of surface analysis techniques. The effects of surface morphology on the interaction of glycine with doped and undoped DLC films have been investigated. The chemical composition of the surface before and after adsorption was analyzed using X-ray photoelectron spectroscopy (XPS). For undoped DLC the spectra show peaks at 285 eV (C 1s), 532 eV (O 1s) and in the case of Si-doped DLC films a band at ∼100 eV (Si 2p) is observed. Following exposure to solutions containing (0.001 M) glycine, for undoped DLC the peaks at ∼285.0, ∼399 and ∼532 eV reduced in intensity and for Si-DLC samples, the peak at 100 eV was reduced. This gives an indication of the quantitative change in the amounts of C, N and O on the surfaces. From Fourier transform infrared (FTIR) spectrum, the peaks occur the following functional groups were assigned as COO-R, COO-bar , -NH3+, NH2, C-H and C-C-N. Both XPS and FTIR spectroscopy confirm that glycine was bound onto the surfaces of the DLC and Si-DLC films via interaction of ionized carboxyl groups and the amino group did not play a significant role in the adsorption of glycine. These results from SE show that an adsorbed layer of glycine is higher at low silicon doping whilst increased doping levels led to a reduced adsorption compared to undoped DLC. Therefore doping of DLC may provide an approach to controlling the protein adsorption.

  12. Sporda Doping

    İmamoğlu, Osman

    2014-01-01

    Doping yeni bir şey değildir. Dopingli sporculara teşhis konulduğunda gündeme gelip çok konuşulmakta ve zamanla unutulup gitmektedir.Doping, organizmaya yabancı bir ajanın, hangi yoldan olursa olsun veya fizyolojik maddelerin anormal miktarlarda, alınması ya da anormal bir yolla bir şahsa yarışma esnasındaki performansı artırmak amacıyla uygulanan bazı psikolojik prosedürlerdir.Bazı anabolizmaların antrenman devrelerinde kullanılmaları bile doping sayılmaktadır.

  13. CO-DOPED POLYPYRROLE COATINGS FOR STAINLESS STEEL PROTECTION

    W. PRISSANAROON; Brack, N.; Pigram, P. J.; J. LIESEGANG

    2006-01-01

    Polypyrrole (PPy) films have been successfully electrodeposited on stainless steel substrates in aqueous solution. In this work, three systems of electrolytes were studied: oxalic acid, dodecylbenzenesulfonic acid (DBSA) and a mixture of oxalic acid and DBSA. A combination of XPS and TOF–SIMS revealed the formation of an iron oxalate layer at the interface between the oxalic acid-doped PPy (PPy(Ox)) and stainless steel and a thin layer of DBSA was observed at the interface between DBSA-doped ...

  14. Effect of chloride impurities on the performance and durability of polybenzimidazole-based high temperature proton exchange membrane fuel cells

    Ali, Syed Talat; Li, Qingfeng; Pan, Chao;

    2011-01-01

    performance loss was recovered when switching from the HCl solution back to pure water in the air humidifier. Under an accelerated aging performance test conducted through potential cycling between 0.9 V and 1.2 V, the PBI-based fuel cell initially containing 0.5 NaCl mg cm−2 on the cathode catalyst layer...... the Pt/C catalysts. Linear sweep voltammetry was employed to study the redox behavior of platinum in 85% phosphoric acid containing chloride ions, showing increase in oxidation and decrease in reduction current densities during the potential scans at room temperature. The potential scans at high...... temperatures in 85% phosphoric acid containing chloride ions showed both increase in oxidation and reduction current densities. The fuel cell performance, i.e. the current density at a constant voltage of 0.4 V and 0.5 V was found to be degraded as soon as HCl was introduced in the air humidifier. The...

  15. Polybenzimidazole/strontium cerate nanocomposites with enhanced proton conductivity for proton exchange membrane fuel cells operating at high temperature

    In this work, perovskite-type SrCeO3 nanoparticles were used for improving the properties of high temperature polybenzimodazole (PBI) based proton exchange membranes. Novel proton conducting membrane nanocomposites were prepared using different amounts of SrCeO3 nanopowders dispersed into by solution casting method.The nanocomposite membranes were studied by using AC impedance spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray and thermo gravimetric analysis. The prepared nanocomposite membranes showed a higher acid uptake, proton conductivity and thermal stability compared with the pure PBI membranes. The highest acid uptake (190%) and proton conductivity (0.105 S/cm at 180 °C and 0% RH) were observed for phosphoric acide-dopped PBI nanocomposite membranes containing 8 wt% of SrCeO3 nanoparticles (PSC8). The PSC8 nanocomposite membranes were tested in a fuel cell and the polarization and power curves were obtained at different temperatures. The PSC8 showed 0.44 W/cm2 power density and 0.88 A/ cm2 current density in 0.5 V at 180 °C. The result obtained from our studies shows the enhanced potential of the PSC8 as proton exchange membranes for high temperature proton exchange membrane fuel cells

  16. Synthesis and characterization of Sn doped TiO{sub 2} photocatalysts: Effect of Sn concentration on the textural properties and on the photocatalytic degradation of 2,4-dichlorophenoxyacetic acid

    Rangel-Vázquez, I.; Del Angel, G.; Bertin, V. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael, Atlixco No 1865, México 09340 D.F. (Mexico); González, F. [Departamento de Ingeniería de Procesos e Hidráulica, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael, Atlixco No 1865, México 09340 D.F. (Mexico); Vázquez-Zavala, A.; Arrieta, A. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael, Atlixco No 1865, México 09340 D.F. (Mexico); Padilla, J.M. [Universidad Tecnológica del Centro de Veracruz, Área de Tecnología, Av. Universidad Carretera Federal Cuitláhuac-La Tinaja No. 350, Cuitláhuac, Veracruz 94910 (Mexico); Barrera, A. [Universidad de Guadalajara, Centro Universitario de la Ciénega, Av. Universidad, Número 1115, Col. Linda Vista, Apdo. Postal 106, Ocotlán Jal. (Mexico); Ramos-Ramirez, E. [Departamento de Química, División de Ciencias Naturales y Exactas, Campus Guanajuato de la Universidad de Guanajuato Noria Alta S/N, Col. Noria Alta, Guanajuato, Gto. C.P. 36050 (Mexico)

    2015-09-15

    Abstract: TiO{sub 2} and Sn-doped TiO{sub 2} materials were prepared by sol–gel method using titanium and tin alkoxides at different Sn concentration (0.1 mol%, 0.5 mol%, 1 mol%, 3 mol% and 5 mol%). Samples were characterized by thermo gravimetric analyzer with differential scanning calorimeter (TGA–DSC), X-ray Rietveld refinement, N{sub 2} adsorption (BET), transmission electron microscopy (TEM), UV–vis spectroscopies technology and Raman spectroscopy. Only anatase phase was observed in pure TiO{sub 2}, whereas anatase and brookite were obtained in Sn-doped TiO{sub 2} samples. Sn dopant acts as a promoter in phase transformation of TiO{sub 2}. The Rietveld refinements method was used to determine the relative weight of anatase and brookite, and crystallite size as a function of Sn concentration after calcination of samples at 673 K. It was also demonstrated the incorporation of Sn{sup 4+} into the anatase TiO{sub 2} structure. Sn{sup 4+} inhibits the growth of TiO{sub 2} crystallite size, which leads to an increase of the specific surface area of TiO{sub 2}. From XRD analysis, the solid solution limit of Sn{sup 4+} into TiO{sub 2} is 5 mol% Sn. The photocatalytic activity on Sn{sup 4+} doped TiO{sub 2} was determined for the 2,4-dichlorophenoxyacetic acid reaction. The maximum in activity was attributed to the coexistence of anatase and brookite phases in the appropriate ratio and crystallite size.

  17. Effects of Zn/citric acid mole fraction on the structure and luminescence properties of the un-doped and 1.5% Pb{sup 2+} doped ZnAl{sub 2}O{sub 4} powders synthesized by citrate sol–gel method

    Motloung, S.V., E-mail: motloungsv@qwa.ufs.ac.za [Department of Physics, University of the Free State (Qwaqwa Campus), Private Bag X13, Phuthaditjhaba 9866 (South Africa); Dejene, F.B. [Department of Physics, University of the Free State (Qwaqwa Campus), Private Bag X13, Phuthaditjhaba 9866 (South Africa); Swart, H.C.; Ntwaeaborwa, O.M. [Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein 9300 (South Africa)

    2015-07-15

    Un-doped and 1.5% Pb{sup 2+}doped zinc aluminate (ZnAl{sub 2}O{sub 4}) was successfully prepared at a relatively low temperature (~80 °C) using the sol–gel process. The Zn/citric acid (CA) mole fraction was varied from 0.083 to 1.3. The X-ray diffraction (XRD) data revealed that most of the annealed samples consist of the cubic ZnAl{sub 2}O{sub 4} structure with ZnO impurities. The surface morphology of the phosphors was influenced by the Zn/CA mole fractions. The increase in the CA content lead to the morphological evolution and transformation from small particles to rods-like-needles. The nanopowder samples exhibited violet luminescence that varied from 400 to 410 nm, which suggested that the CA content affected the bandgap energy of the host. The results suggest that the emission originated either from the host, Pb{sup 2+} or ZnO impurities. Emission at 400 nm is attributed to the oxygen vacancies (V{sub 0}{sup *}) in the host and emission peak at 410 nm is attributed to the intrinsic defects emission of ZnO, while the emission at 552 nm is attributed to the second order emission of the excitation wavelength. The emission intensity was influenced by the Zn/CA mole fractions. The CIE colour coordinates of all samples are close to each other in the blue region. Two distinct peaks were observed at around 160 and 385 °C in thermo luminescence (TL) glow curve, which indicates that there are two set of traps. - Highlights: • Un-doped and 1.5% Pb{sup 2+}doped zinc aluminate (ZnAl{sub 2}O{sub 4}) was successfully prepared at a relatively low temperature (~80 °C) using the sol–gel process. • The increase in the catalyst content lead to the morphological evolution from small particles to rods-like-needles. • The catalyst content affected the band gap energy of the host. • Results showed that the emission can only arise from the host and ZnO impurities. • CIE colour coordinates of all samples is situated in the blue region of the chart.

  18. Electrochemical Performance of a Carbon Nanotube/La-Doped TiO2 Nanocomposite and its Use for Preparation of an Electrochemical Nicotinic Acid Sensor

    Hanxing Liu; Zhidong Lin; Jing Wu

    2008-01-01

    A carbon nanotube/La-doped TiO2 (La-TiO2) nanocomposite (CLTN) was prepared by a procedure similar to a complex/adsorption process. Scanning electron microscopy (SEM) images show that the La-TiO2 distributes on the carbon nanotube walls. The CLTN was mixed with paraffin to form a CLTN paste for the CLTN paste electrode (CLTNPE). The electrochemical characteristics of CLTNPE were compared with that of conventional carbon electrodes such as the carbon paste electrode (CPE) and glass carbon elec...

  19. Mineralization of phthalic acid by solar photoelectro-Fenton with a stirred boron-doped diamond/air-diffusion tank reactor: Influence of Fe3+ and Cu2+ catalysts and identification of oxidation products

    Highlights: • Almost total mineralization of phthalic acid by solar photoelectro-Fenton with Fe3+, Cu2+ and Fe3+–Cu2+ mixtures. • Hydroxyl radical generation from photo-Fenton reaction under solar radiation. • Enhancement of the mineralization rate using Fe3+ and small amounts of Cu2+. • Detection of eleven aromatic intermediates and six short-linear carboxylic acids. • Oxidation of Cu(II)-carboxylate complexes with ·OH and photolysis of Fe(III)-carboxylate species. -- Abstract: Here, the substrate decay and mineralization rate for 100 cm3 of a 2.0 mM phthalic acid solution in 0.10 M Na2SO4 of pH 3.0 have been studied by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF). The electrochemical cell was a stirred tank reactor containing a 3 cm2 boron-doped diamond (BDD) anode and a 3 cm2 air-diffusion cathode that generates H2O2. Cu2+ and/or Fe3+ were added as catalysts with total concentration of 0.50 mM and a constant current density of 33.3 mA cm−2 was applied. In EF with Cu2+ or Fe3+ alone and SPEF with only Cu2+, phthalic acid decayed slowly and poor mineralization was reached because the main oxidant was ·OH produced at the BDD surface from water oxidation. In contrast, the substrate destruction was largely enhanced using SPEF with 0.50 mM Fe3+ since a high quantity of oxidant ·OH was produced in the bulk induced by photo-Fenton reaction. This treatment led to an almost total mineralization by the photolysis of generated Fe(III)-carboxylate complexes. In all cases, the decay of phthalic acid obeyed a pseudo-first-order reaction. The combination of Cu2+ and Fe3+ as catalysts accelerated the mineralization process in SPEF because Cu(II)-carboxylate complexes were also removed with ·OH formed from photo-Fenton reaction. The best SPEF process was found for 0.125 mM Cu2+ + 0.375 mM Fe3+, giving rise to 99% mineralization with 40% current efficiency and 0.294 kWh g−1 TOC energy consumption. Eleven aromatics and six short-linear carboxylic

  20. Mechanisms of doping graphene

    Pinto, H; Jones, R; Goss, J. P.; Briddon, P. R.

    2010-01-01

    We distinguish three mechanisms of doping graphene. Density functional theory is used to show that electronegative molecule like F4-TCNQ and electropositive metals like K dope graphene p- and n-type respectively. These dopants are expected to lead to a decrease in carrier mobility arising from Coulomb scattering but without any hysteresis effects. Secondly, a novel doping mechanism is exhibited by Au which dopes bilayer graphene but not single layer. Thirdly, electrochemical doping is effecte...

  1. Folic acid-conjugated chromium(III) doped nanoparticles consisting of mixed oxides of zinc, gallium and tin, and possessing near-infrared and long persistent phosphorescence for targeted imaging of cancer cells

    Folic acid-conjugated luminescent nanomaterials have long been widely used in targeted bioimaging, often simultaneously acting as vehicles for drug delivery. They often require, however, intense light sources for photoexcitation, and this often results in photo bleaching, strong luminescence background, and strong light scattering. This article describes the preparation of nanoparticles (NPs) of the type Zn1.1Ga1.8Sn0.1O4 doped with Cr(III) ions and surface-modified with folic acid. The functionalization of the NPs was monitored via measurement of zeta potentials, FTIR spectra and thermogravimetry. Cell viability and biocompatibility were tested using the MTT kit. The NPs have a size of 220 nm and were characterized by dynamic X-ray diffraction, light scattering, field emission scanning electron microscopy and high-resolution transmission electron microscopy. After annealing the NPs for 10 min at 300 °C and irradiating them with 254 nm light for 10 min, they display deep red emission that persists for up to 10 h. The NPs are easily dispersed, small-sized, and crystalline. In our perception, the new material with its long decay time offers quite novel features in terms of targeted optical imaging in providing high resolution, weak disturbance by background luminescence, and the absence of light scattering. They were successfully applied to image MCF-7 and A549 cells. (author)

  2. Electrochemical oxidation of acid black 210 dye on the boron-doped diamond electrode in the presence of phosphate ions: Effect of current density, pH, and chloride ions

    The electrochemical oxidation of acid black 210 dye (AB-210) on the boron-doped diamond (BDD) was investigated under different pH conditions. The best performance for the AB-210 oxidation occurred in alkaline phosphate solution. This is probably due to oxidizing agents such as phosphate radicals and peroxodiphosphate ions, which can be electrochemically produced with good yields on the BDD anode, mainly in alkaline solution. Under this condition, the COD (chemical oxygen demand) removal was higher than that obtained from the model proposed by Comninellis. Electrolyses performed in phosphate buffer and in the presence of chloride ions resulted in faster COD and color removals in acid and neutral solutions, but in alkaline phosphate solution, a better performance in terms of TOC removal was obtained in the absence of chloride. Moreover, organochloride compounds were detected in all electrolyses performed in the presence of chloride. The AB-210 electrooxidation on BDD using phosphate as supporting electrolyte proved to be interesting since oxidizing species generated from phosphate ions were able to completely degrade the dye without producing organochloride compounds.

  3. Study of hole mobility in poly(N-vinylcarbazole) films doped with CdSe/ZnS quantum dots encapsulated by 11-(N-carbazolyl) undecanoic acid (C11)

    Khetubol, Adis; Hassinen, Antti; Firdaus, Yuliar; Vanderlinden, Willem; Van Snick, Sven; Flamée, Stijn; Li, Bing; De Feyter, Steven; Hens, Zeger; Dehaen, Wim; Van der Auweraer, Mark

    2013-11-01

    We report the experimental study of hole transport in poly(vinylcarbazole) (PVK) films doped with colloidal CdSe/ZnS core-shell quantum dots (QDs) determined using the Time-of-Flight (TOF) method. The miscibility between PVK and the QDs is improved by capping the QDs with a novel 11-(N-carbazolyl) undecanoic acid (C11) ligand instead of commonly used organic ligands, such as oleic acid. The study of the hole mobility of the pristine and doped PVK films with a doping concentration of the C11 capped QDs ranging from 1.61 × 1017 to 7.10 × 1018 dots/cm3 was performed as a function of electric field and temperature in the range of 105-106 V/cm and 298-338 K, respectively. Upon increasing the QD concentration, a decrease of hole mobility was observed by up to nearly 2 orders in magnitude at a doping concentration of 3.87 × 1018 dots/cm3 at T = 298 K. This suggests that the QDs induce shallow hole traps. The field and temperature dependence of the hole mobility was characterized using the Bässler disorder model and showed an increase of the energetic disorder (σ) from 124 to 204 meV as well as of the spatial disorder (Σ) from 0.95 to 5 when the concentration of the QDs was increased to 3.87 × 1018 dots/cm3. At higher concentration of the QDs (7.10 × 1018 dots/cm3), an increase of the hole mobility was observed suggesting hopping of the holes through the QD clusters. In addition, we also found that for this high doping concentration, the field dependence of the hole mobility was no longer in agreement with the Bässler disorder model. One should consider that at this doping concentration, the volume occupied by the inorganic (CdSe + ZnS) and organic (C11) components of the QDs in the doped film was estimated to be 14.6 and 15.8 volume %, respectively. This implies that the volume fraction of the inorganic material is very close to the percolation threshold, which amounts to 17 volume % for small spherical particles embedded in a three dimensional matrix

  4. Remote gaseous acid sensing within a porphyrin-doped TiO2 sol-gel layer inside a structured optical fibre

    Huyang, George; Canning, John; Åslund, Mattias L.; Naqshbandi, Masood; Stocks, Danial; Crossley, Maxwell J.

    2010-09-01

    A porphyrin containing sol-gel layer has been deposited within the interior of the channels of a silica structured optical fibre. Gaseous HCl detection based on protonation of the porphyrin and observed as a change in the spectrum is demonstrated. This system is compared to previous work based on an acid sensor within a liquid-core fibre. The signal-to- noise of this type of fibre system shows a higher level of sensitivity than the liquid-core and has a forty-fold acid diffusion rate increase due to the different medium for acidification.

  5. Anomalous doping effects by nitric acid on the epitaxial graphene grown on Si-terminated 6H-SiC%Si面6H-SiC衬底外延石墨烯的异常硝酸掺杂效应

    郝昕; 王泽高; 刘竞博; 田洪军

    2013-01-01

    The nitric acid doping effects on the electrical properties of epitaxial graphene grown on Si-and Cterminated SiC,CVD graphene transferred onto SiO2/Si were investigated,respectively.The results show that the p-type doping and decrease in sheet resistance are originated from nitric acid doping with regard to the epitaxial graphene grown on C-terminated SiC and CVD graphene,which attribute to the charge transfer in the redox reaction between nitric acid and graphene.While as for the epitaxial graphene grown on Si-terminated SiC,the n-type doping and increase in sheet resistance are originated from nitric acid doping.The anomalous doping effects are due to the thermal energy generated by the redox reaction between nitric acid and graphene,which lead to oxygen desorption from the dangling bonds between the interface of buffer layer and SiC.Hence the coupling effect between the interface and substrate is effectively enhanced,which results in the increase in electron concentration and decrease in electron mobility.%比较研究了Si面、C面SiC外延石墨烯以及CVD石墨烯的硝酸掺杂效应.结果表明对C面SiC外延石墨烯和CVD石墨烯,硝酸掺杂显现出p型掺杂特性使其方阻降低,这是由于硝酸与石墨烯氧化还原反应过程中电荷转移所导致;而对于Si面SiC外延石墨烯,硝酸掺杂则显现出n型掺杂特性使其方阻增大,这种异常掺杂效应是由于硝酸与石墨烯发生氧化还原反应释放出的热量使悬挂键吸附的氧脱附,增强了石墨烯与衬底之间的耦合效应,从而使得电子浓度增大,电子的迁移率显著减小.

  6. Enhancement of CO2 Adsorption and Catalytic Properties by Fe-Doping of [Ga2(OH)2(L)] (H4L = Biphenyl-3,3′,5,5′-tetracarboxylic Acid), MFM-300(Ga2)

    2016-01-01

    Metal–organic frameworks (MOFs) are usually synthesized using a single type of metal ion, and MOFs containing mixtures of different metal ions are of great interest and represent a methodology to enhance and tune materials properties. We report the synthesis of [Ga2(OH)2(L)] (H4L = biphenyl-3,3′,5,5′-tetracarboxylic acid), designated as MFM-300(Ga2), (MFM = Manchester Framework Material replacing NOTT designation), by solvothermal reaction of Ga(NO3)3 and H4L in a mixture of DMF, THF, and water containing HCl for 3 days. MFM-300(Ga2) crystallizes in the tetragonal space group I4122, a = b = 15.0174(7) Å and c = 11.9111(11) Å and is isostructural with the Al(III) analogue MFM-300(Al2) with pores decorated with −OH groups bridging Ga(III) centers. The isostructural Fe-doped material [Ga1.87Fe0.13(OH)2(L)], MFM-300(Ga1.87Fe0.13), can be prepared under similar conditions to MFM-300(Ga2) via reaction of a homogeneous mixture of Fe(NO3)3 and Ga(NO3)3 with biphenyl-3,3′,5,5′-tetracarboxylic acid. An Fe(III)-based material [Fe3O1.5(OH)(HL)(L)0.5(H2O)3.5], MFM-310(Fe), was synthesized with Fe(NO3)3 and the same ligand via hydrothermal methods. [MFM-310(Fe)] crystallizes in the orthorhombic space group Pmn21 with a = 10.560(4) Å, b = 19.451(8) Å, and c = 11.773(5) Å and incorporates μ3-oxo-centered trinuclear iron cluster nodes connected by ligands to give a 3D nonporous framework that has a different structure to the MFM-300 series. Thus, Fe-doping can be used to monitor the effects of the heteroatom center within a parent Ga(III) framework without the requirement of synthesizing the isostructural Fe(III) analogue [Fe2(OH)2(L)], MFM-300(Fe2), which we have thus far been unable to prepare. Fe-doping of MFM-300(Ga2) affords positive effects on gas adsorption capacities, particularly for CO2 adsorption, whereby MFM-300(Ga1.87Fe0.13) shows a 49% enhancement of CO2 adsorption capacity in comparison to the homometallic parent material. We thus report herein the

  7. Proton conductive membranes based on doped sulfonated polytriazole

    Boaventura, M.; Brandao, L.; Mendes, A. [Laboratorio de Engenharia de Processos, Ambiente e Energia (LEPAE), Faculdade de Engenharia da Universidade do Porto, Rua Roberto Frias, 4200-465 Porto (Portugal); Ponce, M.L.; Nunes, S.P. [GKSS Research Centre Geesthacht GmbH, Max Planck Str. 1, D-21502, Geesthacht (Germany)

    2010-11-15

    This work reports the preparation and characterization of proton conducting sulfonated polytriazole membranes doped with three different agents: 1H-benzimidazole-2-sulfonic acid, benzimidazole and phosphoric acid. The modified membranes were characterized by scanning electron microscopy (SEM), infrared spectra, thermogravimetric analysis (TGA), dynamical mechanical thermal analysis (DMTA) and electrochemical impedance spectroscopy (EIS). The addition of doping agents resulted in a decrease of the glass transition temperature. For membranes doped with 85 wt.% phosphoric acid solution proton conductivity increased up to 2.10{sup -3} S cm{sup -1} at 120 C and at 5% relative humidity. The performance of the phosphoric acid doped membranes was evaluated in a fuel cell set-up at 120 C and 2.5% relative humidity. (author)

  8. Electrochemiluminescence sensor for melamine based on a Ru(bpy)₃²⁺-doped silica nanoparticles/carboxylic acid functionalized multi-walled carbon nanotubes/Nafion composite film modified electrode.

    Chen, Xiaomei; Lian, Sai; Ma, Ying; Peng, Aihong; Tian, Xiaotian; Huang, Zhiyong; Chen, Xi

    2016-01-01

    In this work, a sensitive electrochemiluminescence (ECL) sensor for the determination of melamine (MEL) was developed based on a Ru(bpy)3(2+)-doped silica nanoparticles (RUDS)/carboxylic acid functionalized multi-walled carbon nanotubes (CMWCNTs)/Nafion composite film modified electrode. The homogeneous spherical RUDS were synthesized by a reverse microemulsion method. As Ru(bpy)3(2+) were encapsulated in the RUDS, Ru(bpy)3(2+) dropping from the modified electrode can be greatly prevented, which is helpful for obtaining a stable ECL signal. Moreover, to improve the conductivity of the film and promote the electron transfer rate on electrode surface, CMWCNTs with excellent electrical conductivity and large surface area were applied in the construction of the sensing film. As CMWCNTs acted as electron bridges making more Ru(bpy)3(2+) participate in the reaction, the ECL intensity was greatly enhanced. Under the optimum conditions, the relative ECL signal (△IECL) was proportional to the logarithmic MEL concentration ranging from 5×10(-13) to 1×10(-7) mol L(-1) with a detection limit of 1×10(-13) mol L(-1). To verify the reliability, the thus-fabricated ECL sensor was applied to determine the concentration of MEL in milk. Based on these investigations, the proposed ECL sensor exhibited good feasibility and high sensitivity for the determination of MEL, promising the applicability of this sensor in practical analysis. PMID:26695338

  9. Electro-Fenton, UVA photoelectro-Fenton and solar photoelectro-Fenton degradation of the drug ibuprofen in acid aqueous medium using platinum and boron-doped diamond anodes

    Skoumal, Marcel; Rodriguez, Rosa Maria; Cabot, Pere Lluis; Centellas, Francesc; Garrido, Jose Antonio; Arias, Conchita [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Brillas, Enric [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)], E-mail: brillas@ub.edu

    2009-02-28

    The degradation of a 41 mg dm{sup -3} ibuprofen (2-(4-isobutylphenyl)propionic acid) solution of pH 3.0 has been comparatively studied by electrochemical advanced oxidation processes (EAOPs) like electro-Fenton, UVA photoelectro-Fenton and solar photoelectro-Fenton at constant current density. Experiments were performed in a one-compartment cell with a Pt or boron-doped diamond (BDD) anode and an O{sub 2}-diffusion cathode. Heterogeneous hydroxyl radical ({center_dot}OH) is generated at the anode surface from water oxidation, while homogeneous {center_dot}OH is formed from Fenton's reaction between Fe{sup 2+} and H{sub 2}O{sub 2} generated at the cathode, being its production strongly enhanced from photo-Fenton reaction induced by sunlight. Higher mineralization is attained in all methods using BDD instead Pt, because the former produces greater quantity of {center_dot}OH enhancing the oxidation of pollutants. The mineralization rate increases under UVA and solar irradiation by the rapid photodecomposition of complexes of Fe(III) with acidic intermediates. The most potent method is solar photoelectro-Fenton with BDD giving 92% mineralization due to the formation of a small proportion of highly persistent final by-products. The effect of Fe{sup 2+} content, pH and current density on photoelectro-Fenton degradation has been studied. The ibuprofen decay always follows a pseudo-first-order kinetics and its destruction rate is limited by current density and UV intensity. Aromatics such as 1-(1-hydroxyethyl)-4-isobutylbenzene, 4-isobutylacetophenone, 4-isobutylphenol and 4-ethylbenzaldehyde, and carboxylic acids such as pyruvic, acetic, formic and oxalic have been identified as oxidation by-products. Oxalic acid is the ultimate by-product and the fast photodecarboxylation of its complexes with Fe(III) under UVA or solar irradiation explains the higher oxidation power of photoelectro-Fenton methods in comparison to electro-Fenton procedures.

  10. EPR and optical absorption studies of Cu{sup 2+} doped L-histidinium dihydrogen phosphate–phosphoric acid single crystal

    Prabakaran, R.; Sheela, K. Juliet; Rosy, S. Margret [Department of Physics, Gandhigram Rural Institute—Deemed University, Gandhigram, Dindigul-624302, Tamilnadu (India); Radha Krishnan, S.; Shanmugam, V.M. [CSIR-Central Electrochemical Research Institute, Karaikudi-630006, Tamilnadu (India); Subramanian, P., E-mail: psmanian_gri@yahoo.com [Department of Physics, Gandhigram Rural Institute—Deemed University, Gandhigram, Dindigul-624302, Tamilnadu (India)

    2014-02-01

    The EPR spectra of Cu{sup 2+} in L-histidinium dihydrogen phosphate phosphoric acid at room temperature reveal the presence of two magnetically inequivalent Cu{sup 2+} sites in the lattice. The principal values of the g- and A-tensors indicate existence of rhombic symmetry around the Cu{sup 2+} ion. From the direction cosines of the principal values of the g- and A-tensors, the locations of Cu{sup 2+} in the lattice have been identified as substitutional sites. Optical absorption study shows four bands confirm the rhombic symmetry. Photoluminescence study also confirms the rhombic symmetry around the ions.