Science.gov

Sample records for enhanced electrochemical activity

  1. Enhanced photocatalytic activity of electrochemically synthesized aluminum oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Pathania, Deepak; Katwal, Rishu; Kaur, Harpreet

    2016-03-01

    In this study, aluminum oxide (Al2O3) nanoparticles (NPs) were synthesized via an electrochemical method. The effects of reaction parameters such as supporting electrolytes, solvent, current and electrolysis time on the shape and size of the resulting NPs were investigated. The Al2O3 NPs were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, thermogravimetric analysis/differential thermal analysis, energy-dispersive X-ray analysis, and ultraviolet-visible spectroscopy. Moreover, the Al2O3 NPs were explored for photocatalytic degradation of malachite green (MG) dye under sunlight irradiation via two processes: adsorption followed by photocatalysis; coupled adsorption and photocatalysis. The coupled process exhibited a higher photodegradation efficiency (45%) compared to adsorption followed by photocatalysis (32%). The obtained kinetic data was well fitted using a pseudo-first-order model for MG degradation.

  2. Cellulosic carbon fibers with branching carbon nanotubes for enhanced electrochemical activities for bioprocessing applications.

    PubMed

    Zhao, Xueyan; Lu, Xin; Tze, William Tai Yin; Kim, Jungbae; Wang, Ping

    2013-09-25

    Renewable biobased carbon fibers are promising materials for large-scale electrochemical applications including chemical processing, energy storage, and biofuel cells. Their performance is, however, often limited by low activity. Herein we report that branching carbon nanotubes can enhance the activity of carbonized cellulosic fibers, such that the oxidation potential of NAD(H) was reduced to 0.55 V from 0.9 V when applied for bioprocessing. Coordinating with enzyme catalysts, such hierarchical carbon materials effectively facilitated the biotransformation of glycerol, with the total turnover number of NAD(H) over 3500 within 5 h of reaction. PMID:24020801

  3. Carbon coated Cu2O nanowires for photo-electrochemical water splitting with enhanced activity

    NASA Astrophysics Data System (ADS)

    Shi, Weina; Zhang, Xiaofan; Li, Shaohui; Zhang, Bingyan; Wang, Mingkui; Shen, Yan

    2015-12-01

    Herein, we report on Cu2O nanowire photocathode covered with amorphous carbon thin layer by a simple and effective anodization method for photoelectrochemical (PEC) water splitting hydrogen production. The coating of carbon thin layer increases the photo-electrochemical performance of Cu2O nanowires, achieving a photocurrent density of up to 2.7 mA cm-2 at 0 V (vs. RHE) with a maximum photon to current conversion efficiency of 0.28% at 0.21 V (vs. RHE) under standard testing conditions. The nanocomposite electrode retains 61.3% of its photo-activity after 1000 s irradiation, which is higher than that of bare Cu2O (18.5%). The detailed investigation results reveal that the augmented photocurrent as well as the enhanced stability could be contributed to the acceleration of electrochemical charge transfer at the electrode/electrolyte interface and the reduced rate of photo-corrosion.

  4. CO2 Activated Carbon Aerogel with Enhanced Electrochemical Performance as a Supercapacitor Electrode Material.

    PubMed

    Lee, Eo Jin; Lee, Yoon Jae; Kim, Jeong Kwon; Hong, Ung Gi; Yi, Jongheop; Yoon, Jung Rag; Song, In Kyu

    2015-11-01

    Carbon aerogel (CA) was prepared by a sol-gel polymerization of resorcinol and formaldehyde in ambient conditions. A series of activated carbon aerogels (ACA-X, X = 1, 2, 3, 4, 5, and 6 h) were then prepared by CO2 activation of CA with a variation of activation time (X) for use as an electrode material for supercapacitor. Specific capacitances of CA and ACA-X electrodes were measured by cyclic voltammetry and galvanostatic charge/discharge methods in 6 M KOH electrolyte. Among the samples, ACA-5 h showed the highest BET surface area (2574 m2/g) and the highest specific capacitance (100 F/g). It was found that CO2 activation was a very efficient method for enhancing physicochemical property and supercapacitive electrochemical performance of activated carbon aerogel. PMID:26726618

  5. Enhancement of the photocatalytic activity and electrochemical property of graphene-SrWO4 nanocomposite

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoyan; Nie, Yu; Yang, Hongxun; Sun, Shengnan; Chen, Yingying; Yang, Tongyi; Lin, Shengling

    2016-05-01

    SrWO4 is a promising candidate as not only photocatalyst for the removal of organic pollutants from water, but also electrode material for energy storage devices. However, the drawbacks of its poor adsorptive performance, low electrical conductivity, and high recombination rate of photogenerated electron-hole pair impede its practical applications. In this work, we have developed a new graphene/SrWO4 nanocomposite synthesized via a facile chemical precipitation method. Characterizations show that SrWO4 nanoparticles with 80 nm or so deposited on the surface of graphene nanosheets. Graphene nanosheets in the graphene-SrWO4 hybrid could increase adsorptive property, improve the electrical conductivity of hybrid, and reduce the recombination of electron-hole pairs. As a kind of photocatalyst or electrode material for supercapacitor, the binary graphene-SrWO4 hybrid presents enhanced photocatalytic activity and electrochemical property compared to pure SrWO4.

  6. On the origin of enhanced electrochemical behavior of oxidized activated carbon

    NASA Astrophysics Data System (ADS)

    Niu, Rui; Li, Haibo; Ma, Yulong

    2016-08-01

    The amount of ions stored within the electrochemical double layer is dominantly determined by the surface area of porous electrode. High surface area indicates high capacitance. However, this is not the case when the pore is extremely small, ∼less than 1 nm. To observe this phenomenon, we have carried out an experiment by comparatively investigating the electrochemical performance of activated carbon (AC) and sulfuric acid treated AC (SAC). The results show that the electrochemical performance of SAC involving the specific capacitance, rate capability and cycling stability is significantly increased as compared to pristine AC. These are attributed to the improved porosity by differentiating the respective contributions of electrochemical double layer capacity and pseudo-capacity from SAC and AC, respectively.

  7. Geobacter sp. SD-1 with enhanced electrochemical activity in high-salt concentration solutions.

    PubMed

    Sun, Dan; Call, Douglas; Wang, Aijie; Cheng, Shaoan; Logan, Bruce E

    2014-12-01

    An isolate, designated strain SD-1, was obtained from a biofilm dominated by Geobacter sulfurreducens in a microbial fuel cell. The electrochemical activity of strain SD-1 was compared with type strains, G. sulfurreducens PCA and Geobacter metallireducens GS-15, and a mixed culture in microbial electrolysis cells. SD-1 produced a maximum current density of 290 ± 29 A m−3 in a high-concentration phosphate buffer solution (PBS-H, 200 mM). This current density was significantly higher than that produced by the mixed culture (189 ± 44 A m−3) or the type strains (< 70 A m−3). In a highly saline water (SW; 50 mM PBS and 650 mM NaCl), current by SD-1 (158 ± 4 A m−3) was reduced by 28% compared with 50 mM PBS (220 ± 4 A m−3), but it was still higher than that of the mixed culture (147 ± 19 A m−3), and strains PCA and GS-15 did not produce any current. Electrochemical tests showed that the improved performance of SD-1 was due to its lower charge transfer resistance and more negative potentials produced at higher current densities. These results show that the electrochemical activity of SD-1 was significantly different than other Geobacter strains and mixed cultures in terms of its salt tolerance. PMID:25756125

  8. Surface-enhanced Raman scattering-active Au/TiO{sub 2} films prepared by electrochemical and photochemical methods

    SciTech Connect

    Yang, Kuang-Hsuan; Chang, Chia-Ming

    2013-02-15

    Graphical abstract: In the presence of TiO{sub 2} NPs before the ORCs the optimal wavelength of UV light resulting in the strongest SERS effect being 310 nm. Display Omitted Highlights: ► SERS-active Au/TiO{sub 2} prepared by electrochemical and photochemical methods. ► UV light of 310 nm is suitable for obtaining Au/TiO{sub 2} with strong SERS effect. ► Presence of TiO{sub 2} before ORCs is responsible for obtaining SERS-active Au/TiO{sub 2}. -- Abstract: In this work, we report a new strategy for the preparation of surface-enhanced Raman scattering (SERS)-active Au/TiO{sub 2}(P25) nanocomposites (NCs), using electrochemical and photochemical methods. First, Au substrates were subjected to electrochemical oxidation–reduction cycles (ORCs) in a deoxygenated aqueous solution containing 0.1 M HCl and 1 mM TiO{sub 2}. After the ORC treatment AuCl{sub 4}{sup −}-adsorbed TiO{sub 2} complexes were produced in the solution. These complex-containing substrates were then irradiated with UV light at 310 nm to synthesize Au/TiO{sub 2} NCs with strong SERS activities for probe molecules of rhodamine 6G (R6G) and conductive polymers of polypyrrole (PPy). Experimental results indicated that the wavelength of UV light and the presence of TiO{sub 2} before and after the ORC procedure during the preparation process both affected the resulting SERS activities.

  9. Enhanced Intrinsic Catalytic Activity of λ-MnO2 by Electrochemical Tuning and Oxygen Vacancy Generation.

    PubMed

    Lee, Sanghan; Nam, Gyutae; Sun, Jie; Lee, Jang-Soo; Lee, Hyun-Wook; Chen, Wei; Cho, Jaephil; Cui, Yi

    2016-07-18

    Chemically prepared λ-MnO2 has not been intensively studied as a material for metal-air batteries, fuel cells, or supercapacitors because of their relatively poor electrochemical properties compared to α- and δ-MnO2 . Herein, through the electrochemical removal of lithium from LiMn2 O4 , highly crystalline λ-MnO2 was prepared as an efficient electrocatalyst for the oxygen reduction reaction (ORR). The ORR activity of the material was further improved by introducing oxygen vacancies (OVs) that could be achieved by increasing the calcination temperature during LiMn2 O4 synthesis; a concentration of oxygen vacancies in LiMn2 O4 could be characterized by its voltage profile as the cathode in a lithiun-metal half-cell. λ-MnO2-z prepared with the highest OV exhibited the highest diffusion-limited ORR current (5.5 mA cm(-2) ) among a series of λ-MnO2-z electrocatalysts. Furthermore, the number of transferred electrons (n) involved in the ORR was >3.8, indicating a dominant quasi-4-electron pathway. Interestingly, the catalytic performances of the samples were not a function of their surface areas, and instead depended on the concentration of OVs, indicating enhancement in the intrinsic catalytic activity of λ-MnO2 by the generation of OVs. This study demonstrates that differences in the electrochemical behavior of λ-MnO2 depend on the preparation method and provides a mechanism for a unique catalytic behavior of cubic λ-MnO2 . PMID:27254822

  10. High-performance lithium storage in an ultrafine manganese fluoride nanorod anode with enhanced electrochemical activation based on conversion reaction.

    PubMed

    Rui, Kun; Wen, Zhaoyin; Huang, Xiao; Lu, Yan; Jin, Jun; Shen, Chen

    2016-02-01

    A facile, one-step solvothermal reaction route for the preparation of manganese fluoride nanorods is successfully developed using manganese(II) chloride tetrahydrate (MnCl2·4H2O) as the manganese source and the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) as the fluorine source. X-ray diffraction, field-emission scanning electron microscopy and high-resolution transmission electron microscopy (HRTEM) are conducted to characterize the structural and microstructural properties of the synthesized MnF2. The pure-phase tetragonal MnF2 displays nanorod-like morphology with a diameter of about 20 nm and a length of several hundreds of nanometers. The electrochemical performance of the MnF2 nanorod anode for rechargeable lithium batteries is investigated. A reversible discharge capacity as high as 443 mA h g(-1) at 0.1 C is obtained for the lithium uptake reaction with an initial discharge plateau around 0.7 V. The striking enhancement in electrochemical Li storage performance in ultrafine MnF2 nanorods can be attributed to the small diameters of the nanorods and efficient one-dimensional electron transport pathways. Long cycle performance for 2000 cycles at 10 C with a stabilized capacity of about 430 mA h g(-1) after activation is also achieved. Furthermore, lithiated and delithiated MnF2 anodes are analyzed with HRTEM to elucidate the conversion mechanism for the electrochemical reaction of MnF2 nanorods with Li at a microscopic level. PMID:26766389

  11. Octahedral core–shell cuprous oxide/carbon with enhanced electrochemical activity and stability as anode for lithium ion batteries

    SciTech Connect

    Xiang, Jiayuan; Chen, Zhewei; Wang, Jianming

    2015-10-15

    Highlights: • Core–shell octahedral Cu{sub 2}O/C is prepared by a one-step method. • Carbon shell is amorphous and uniformly decorated at the Cu{sub 2}O octahedral core. • Core–shell Cu{sub 2}O/C exhibits markedly enhanced capability and reversibility. • Carbon shell provides fast ion/electron transfer channel. • Core–shell structure is stable during cycling. - Abstract: Core–shell Cu{sub 2}O/C octahedrons are synthesized by a simple hydrothermal method with the help of carbonization of glucose, which reduces Cu(II) to Cu(I) at low temperature and further forms carbon shell coating at high temperature. SEM and TEM images indicate that the carbon shell is amorphous with thickness of ∼20 nm wrapping the Cu{sub 2}O octahedral core perfectly. As anode of lithium ion batteries, the core–shell Cu{sub 2}O/C composite exhibits high and stable columbic efficiency (98%) as well as a reversible capacity of 400 mAh g{sup −1} after 80 cycles. The improved electrochemical performance is attributed to the novel core–shell structure, in which the carbon shell reduces the electrode polarization and promotes the charge transfer at active material/electrolyte interface, and also acts as a stabilizer to keep the octahedral structure integrity during discharge–charge processes.

  12. Nitrogen-doped graphene/ZnSe nanocomposites: hydrothermal synthesis and their enhanced electrochemical and photocatalytic activities.

    PubMed

    Chen, Ping; Xiao, Tian-Yuan; Li, Hui-Hui; Yang, Jing-Jing; Wang, Zheng; Yao, Hong-Bin; Yu, Shu-Hong

    2012-01-24

    Nitrogen-doped graphene (GN) has great potential applications in many fields because doping with nitrogen can alter the electrical properties of graphene. It is still a challenge to develop a convenient method for synthesis of GN sheets. In this paper, we first report the synthesis of a nitrogen-doped graphene/ZnSe nanocomposite (GN-ZnSe) by a one-pot hydrothermal process at low temperature using graphene oxide nanosheets and [ZnSe](DETA)(0.5) nanobelts as precursors. ZnSe nanorods composed of ZnSe nanoparticles were found to deposit on the surface of the GN sheets. The results demonstrated that [ZnSe](DETA)(0.5) nanobelts were used not only as the source of ZnSe nanoparticles but also as the nitrogen source. Interestingly, it was found that the as-prepared nanocomposites exhibit remarkably enhanced electrochemical performance for oxygen reduction reaction and photocatalytic activities for the bleaching of methyl orange dye under visible-light irradiation. This facile and catalyst-free approach for depositing ZnSe nanoparticles onto the graphene sheets may provide an alternative way for preparation of other nanocomposites based on GN sheets under mild conditions, which show their potential applications in wastewater treatment, fuel cells, energy storage, nanodevices, and so on. PMID:22136425

  13. Trends in the electrochemical synthesis of H2O2: enhancing activity and selectivity by electrocatalytic site engineering.

    PubMed

    Verdaguer-Casadevall, Arnau; Deiana, Davide; Karamad, Mohammadreza; Siahrostami, Samira; Malacrida, Paolo; Hansen, Thomas W; Rossmeisl, Jan; Chorkendorff, Ib; Stephens, Ifan E L

    2014-03-12

    The direct electrochemical synthesis of hydrogen peroxide is a promising alternative to currently used batch synthesis methods. Its industrial viability is dependent on the effective catalysis of the reduction of oxygen at the cathode. Herein, we study the factors controlling activity and selectivity for H2O2 production on metal surfaces. Using this approach, we discover two new catalysts for the reaction, Ag-Hg and Pd-Hg, with unique electrocatalytic properties both of which exhibit performance that far exceeds the current state-of-the art. PMID:24506229

  14. ENHANCED ELECTROCHEMICAL PROCESSES IN SUBCRITICAL WATER

    SciTech Connect

    Steven B. Hawthorne

    2000-07-01

    This project involved designing and performing preliminary electrochemical experiments in subcritical water. An electrochemical cell with substantially better performance characteristics than presently available was designed, built, and tested successfully. The electrochemical conductivity of subcritical water increased substantially with temperature, e.g., conductivities increased by a factor of 120 when the temperature was increased from 25 to 250 C. Cyclic voltammograms obtained with platinum and nickel demonstrated that the voltage required to produce hydrogen and oxygen from water can be dropped by a factor of three in subcritical water compared to the voltages required at ambient temperatures. However, no enhancement in the degradation of 1,2-dichlorobenzene and the polychlorinated biphenyl 3,3',4,4'-tetrachlorobiphenyl was observed with applied potential in subcritical water.

  15. Mechanism of Enhanced Electrochemical Oxidation of 2,4-dichlorophenoxyacetic Acid with in situ Microwave Activated Boron-doped Diamond and Platinum Anodes

    NASA Astrophysics Data System (ADS)

    Gao, Junxia; Zhao, Guohua; Liu, Meichuan; Li, Dongming

    2009-09-01

    Remarkable enhancement in degradation effect is achieved at in situ activated boron-doped diamond (BDD) and Pt anodes with different extent through electrochemical oxidation (EC) of 2,4-dichlorophenoxyacetic acid (2,4-D) with microwave (MW) radiation in a flow system. Results show that when EC is activated with MW radiation, the complete mineralization time of 2,4-D at the BDD is reduced quickly from 10 to 4 h while Chemical oxygen demand (COD) removal at Pt is increased from 37.7 to 58.3% at 10 h; the initial current efficiency is both improved about 1.5 times while the pseudo-first-order rate constant is increased by 153 and 119% at the BDD and Pt, respectively. To gain insight into the higher efficiency in microwave activated EC, the mechanism has therefore been systematically evaluated from the essence of electrochemical reaction and the accumulated hydroxyl radical concentration. 2,4-Dichlorophenol, catechol, benquinone, and maleic and oxalic acids are the main intermediates on the Pt anode measured by high performance liquid chromatography (HPLC), while the intermediates on the BDD electrode include 2,4-dichlorophenol, hydroquinone, and maleic and oxalic acids. The reaction pathway with microwave radiation is the same as that in a conventional electrochemical oxidation on both electrodes. While less and lower aromatic intermediates produce at the BDD with MW, which suggests the higher ring-open ratio and the faster oxidation of carboxylic acids. With microwave radiation, the ring-open ratio at the BDD is increased to 98.8% from 85.6%; the value at Pt is increased to 67.3% from 35.9%. So microwave radiation can activate the electrochemical oxidation, which leads to the higher efficiency. This promotion is mainly due to the higher accumulated hydroxyl radical concentration and the effects by microwave radiation. All the results prove that the BDD electrode presents much better mineralization performance with MW. To the best of our knowledge, it is the first

  16. Addition of nitrite enhances the electrochemical defluorination of 2-fluoroaniline.

    PubMed

    Feng, Huajun; Liang, Yuxiang; Guo, Kun; Long, Yuyang; Cong, Yanqing; Shen, Dongsheng

    2015-12-30

    This study introduces a novel approach that uses the interaction of pollutants with added nitrite to produce diazonium salts, which cause in situ self-assembly of the pollutants on carbon electrodes, to improve their 2-fluoroaniline (2-FA) defluorination and removal performance. The 2-FA degradation performance, electrode properties, electrochemical properties and degradation pathway were investigated. The reactor containing NO2(-) achieved a 2-FA removal efficiency of 90.1% and a defluorination efficiency of 38% within 48 h, 1.4 and 2.3 times higher than the corresponding results achieved without NO2(-), respectively. The residual NO2(-) was less than 0.5mg/L in the reactor containing added NO2(-), which would not cause serious secondary pollution. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) results proved that the carbon anode surface was successfully modified with benzene polymer, and electrochemical tests confirmed that the electrochemical activity of the modified anode was enhanced significantly. The C-F bond was weakened by the effect of the positive charge of the benzenediazonium groups, and the high electrochemical activity of the carbon anode enhanced the electrochemical performance of the system to accelerate defluorination. Thus, the present electrical method involving nitrite nitrogen is very promising for the treatment of wastewater containing fluoroaniline compounds. PMID:26266896

  17. Binary and ternary doping of nitrogen, boron, and phosphorus into carbon for enhancing electrochemical oxygen reduction activity.

    PubMed

    Choi, Chang Hyuck; Park, Sung Hyeon; Woo, Seong Ihl

    2012-08-28

    N-doped carbon, a promising alternative to Pt catalyst for oxygen reduction reactions (ORRs) in acidic media, is modified in order to increase its catalytic activity through the additional doping of B and P at the carbon growth step. This additional doping alters the electrical, physical, and morphological properties of the carbon. The B-doping reinforces the sp(2)-structure of graphite and increases the portion of pyridinic-N sites in the carbon lattice, whereas P-doping enhances the charge delocalization of the carbon atoms and produces carbon structures with many edge sites. These electrical and physical alternations of the N-doped carbon are more favorable for the reduction of the oxygen on the carbon surface. Compared with N-doped carbon, B,N-doped or P,N-doped carbon shows 1.2 or 2.1 times higher ORR activity at 0.6 V (vs RHE) in acidic media. The most active catalyst in the reaction is the ternary-doped carbon (B,P,N-doped carbon), which records -6.0 mA/mg of mass activity at 0.6 V (vs RHE), and it is 2.3 times higher than that of the N-doped carbon. These results imply that the binary or ternary doping of B and P with N into carbon induces remarkable performance enhancements, and the charge delocalization of the carbon atoms or number of edge sites of the carbon is a significant factor in deciding the oxygen reduction activity in carbon-based catalysts. PMID:22769428

  18. Shock-activated electrochemical power supplies

    DOEpatents

    Benedick, W.B.; Graham, R.A.; Morosin, B.

    1987-04-20

    A shock-activated electrochemical power supply is provided which is initiated extremely rapidly and which has a long shelf life. Electrochemical power supplies of this invention are initiated much faster than conventional thermal batteries. Power supplies of this invention comprise an inactive electrolyte and means for generating a high-pressure shock wave such that the shock wave is propagated through the electrolyte rendering the electrolyte electrochemically active. 2 figs.

  19. Shock-activated electrochemical power supplies

    DOEpatents

    Benedick, William B.; Graham, Robert A.; Morosin, Bruno

    1988-01-01

    A shock-activated electrochemical power supply is provided which is initiated extremely rapidly and which has a long shelf life. Electrochemical power supplies of this invention are initiated much faster than conventional thermal batteries. Power supplies of this invention comprise an inactive electrolyte and means for generating a high-pressure shock wave such that the shock wave is propagated through the electrolytes rendering the electrolyte electrochemically active.

  20. Shock-activated electrochemical power supplies

    DOEpatents

    Benedick, W.B.; Graham, R.A.; Morosin, B.

    1988-11-08

    A shock-activated electrochemical power supply is provided which is initiated extremely rapidly and which has a long shelf life. Electrochemical power supplies of this invention are initiated much faster than conventional thermal batteries. Power supplies of this invention comprise an inactive electrolyte and means for generating a high-pressure shock wave such that the shock wave is propagated through the electrolytes rendering the electrolyte electrochemically active. 2 figs.

  1. Electrochemical enhanced heterogeneous activation of peroxydisulfate by Fe-Co/SBA-15 catalyst for the degradation of Orange II in water.

    PubMed

    Cai, Chun; Zhang, Hui; Zhong, Xin; Hou, Liwei

    2014-12-01

    Mesoporous silica SBA-15 supported iron and cobalt catalysts (Fe-Co/SBA-15) were prepared and used in the electrochemical (EC) enhanced heterogeneous activation of peroxydisulfate (PDS, S2O8(2-)) process for the removal of Orange II. The effects of some important reaction parameters such as initial pH, current density, PDS concentration and dosage of Fe-Co/SBA-15 catalysts were investigated. The results showed that the decolorization efficiency was not significantly affected by the initial pH value, and it did increase with the higher PDS concentration, current density and Fe-Co/SBA-15 dosage. Both the sulfate radical (SO4(·-)) and the hydroxyl radical (OH) are considered as the primary reactive oxidants for the Orange II decolorization. The Fe-Co/SBA-15 catalyst maintained its high activity during repeated batch experiments. The intermediate products were identified by GC-MS analysis and a plausible degradation pathway is proposed accordingly. The removal efficiencies of chemical oxygen demand (COD) and total organic carbon (TOC) were 52.1% and 31.9%, respectively after 60 min of reaction time but reached 82.9% and 51.5%, respectively when the reaction time was extended to 24 h. Toxicity tests with activated sludge indicated that the toxicity of the solution increased during the first 30 min and then decreased as the oxidation proceeded. PMID:25259475

  2. Electrochemical Tip-Enhanced Raman Spectroscopy.

    PubMed

    Zeng, Zhi-Cong; Huang, Sheng-Chao; Wu, De-Yin; Meng, Ling-Yan; Li, Mao-Hua; Huang, Teng-Xiang; Zhong, Jin-Hui; Wang, Xiang; Yang, Zhi-Lin; Ren, Bin

    2015-09-23

    Interfacial properties are highly important to the performance of some energy-related systems. The in-depth understanding of the interface requires highly sensitive in situ techniques that can provide fingerprint molecular information at nanometer resolution. We developed an electrochemical tip-enhanced Raman spectroscopy (EC-TERS) by introduction of the light horizontally to the EC-STM cell to minimize the optical distortion and to keep the TERS measurement under a well-controlled condition. We obtained potential-dependent EC-TERS from the adsorbed aromatic molecule on a Au(111) surface and observed a substantial change in the molecule configuration with potential as a result of the protonation and deprotonation of the molecule. Such a change was not observable in EC-SERS (surface-enhanced), indicating EC-TERS can more faithfully reflect the fine interfacial structure than EC-SERS. This work will open a new era for using EC-TERS as an important nanospectroscopy tool for the molecular level and nanoscale analysis of some important electrochemical systems including solar cells, lithium ion batteries, fuel cells, and corrosion. PMID:26351986

  3. Electrochemically shape-controlled synthesis in deep eutectic solvents: triambic icosahedral platinum nanocrystals with high-index facets and their enhanced catalytic activity.

    PubMed

    Wei, Lu; Zhou, Zhi-You; Chen, Sheng-Pei; Xu, Chang-Deng; Su, Dangsheng; Schuster, Manfred Erwin; Sun, Shi-Gang

    2013-12-11

    Pt triambic icosahedral nanocrystals (TIH NCs) enclosed by {771} high-index facets were successfully synthesized electrochemically, for the first time, in ChCl-urea based deep eutectic solvents, and exhibited higher electrocatalytic activity and stability towards ethanol electrooxidation than a commercial Pt black catalyst. PMID:24084858

  4. Electrochemical tip-enhanced Raman spectroscopy (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Zeng, Zhicong; Huang, Shengchao; Huang, Tengxiang; Li, Maohua; Ren, Bin

    2015-08-01

    Tip-enhanced Raman spectroscopy (TERS) can not only provide very high sensitivity but also high spatial resolution, and has found applications in various fields, including surface science, materials, and biology. Most of previous TERS studies were performed in air or in the ultrahigh vacuum. If TERS study can be performed in the electrochemical environment, the electronic properties of the surface can be well controlled so that the interaction of the molecules with the substrate and the configuration of the molecules on the surface can also be well controlled. However, the EC-TERS is not just a simple combination of electrochemistry with TERS, or the combination of EC-STM with Raman. It is a merge of STM, electrochemistry and Raman spectroscopy, and the mutual interference among these techniques makes the EC-TERS particularly challenge: the light distortion in EC system, the sensitivity, the tip coating to work under EC-STM and retain the TERS activity and cleanliness. We designed a special spectroelectrochemical cell to eliminate the distortion of the liquid layer to the optical path and obtain TER spectra of reasonably good signal to noise ratio for surface adsorbed molecules under electrochemical potential control. For example, potential dependent TERS signal have been obtained for adsorbed aromatic thiol molecule, and much obvious signal change compared with SERS has been found, manifesting the importance of EC-TERS to reveal the interfacial structure of an electrochemical system. We further extended EC-TERS to electrochemical redox system, and clear dependence of the species during redox reaction can be identified.

  5. Electrochemical 'bubble swarm' enhancement of ultrasonic surface cleaning.

    PubMed

    Birkin, P R; Offin, D G; Vian, C J B; Leighton, T G

    2015-09-01

    An investigation of surface cleaning using a swarm of gas bubbles within an acoustically activated stream is presented. Electrolysis of water at Pt microwires (100 μm diameter) to produce both hydrogen and oxygen bubbles is shown to enhance the extent of ultrasonic surface cleaning in a free flowing water stream containing an electrolyte (0.1 M Na2SO4) and low surfactant concentration (2 mM SDS). The surfactant was employed to allow control of the average size of the bubble population within the swarm. The electrochemical bubble swarm (EBS) is shown to perturb acoustic transmission through the stream. To optimise the cleaning process both the ultrasonic field and the electrochemical current are pulsed and synchronized but with different duty cycles. Cleaning action is demonstrated on structured surfaces (porcine skin and finger mimics) loaded with fluorescent particles. This action is shown to be significantly enhanced compared to that found with an inherent bubble population produced by the flow and acoustic regime alone under the same conditions. PMID:26234563

  6. Characterization of the Electrochemical Interface by Surface Enhanced Raman Scattering

    NASA Astrophysics Data System (ADS)

    Roy, Dipankar

    The electronic and structural properties of an enhanced raman sensitive interface are investigated. As a model system, the Ag (polycrystalline) electrode/electrolyte interface is chosen. Electrochemical control of the interface is used to establish and influence the conditions for surface enhanced Raman scattering (SERS). The molecule and site specific electronic component of SERS is studied under experimental control. This resonance is responsible for enhancement beyond that caused by electromagnetic effects at the surface and is promoted by the presence of the so -called "SERS active sites" (surface defect sites of atomic scale roughness). The results suggest that, these sites are positively charged, resonant Raman active Ag clusters, most likely with the identity of Ag(,4)('+). A partial contribution to the observed electronic enhancement comes from the intrinsic resonance of the clusters. At a given SERS sensitive Ag electrode, this contribution is superimposed on that from the photon driven charge transfer excitation (CTE) resonance, provided the latter is operative in that particular case. In SERS of Cl('-) (a prototypical probe) on Ag, the internal resonance of Ag(,4)('+) appears to be the primary source of the electronic enhancement detected. By noting the known importance of Ag(,4)('+) in silver-halide photography, it is possible to explain the "photoactivation effect" in SERS in terms of the Ag(,4)('+) identity of SERS active sites. These observations indicate how, by SERS, it may be possible to bridge the gap between the catalytic and optical aspects of small metal clusters. The chemisorbed anions which coexist with the active sites at a SERS sensitive interface, are tested for their effects in SERS from Cl('-) and I('-) on Ag. Evidence is presented for mutual "depolarization" effect of the adsorbates. Under voltage control of these interfaces, this depolarization process dominates the Stark effect and bond perturbation. The results point out how the

  7. Nanoparticles for Enhanced Sensitivity in Electrochemical Immunoassays

    SciTech Connect

    Lin, Yuehe; Wang, Jun; Wang, Hua; Wu, Hong; Tang, Zhiwen

    2008-10-12

    In this manuscript, we report on electrochemical biosensors based on various nanoparticles (NPs) as labels for sensitive detection of protein biomarkers. We used silica nanoparticle as a carrier to loading a large amount of electroactive species such as poly(guanine) for sensitive immunoassay of tumor necrosis factor-alpha (TNF-a). We took the advantages of the unique hollow structure and reconstruction properties of apoferritin to prepare Cd3(PO4)2 nanoparticles as labels for sensitive assay of TNF-a. A novel immunochromatographic/electro-chemical biosensor based on quantum dots as labels has also been developed for rapid and sensitive detection of prostate-specific antigen (PSA) in human serum. These biosensors are quite sensitive with the detection limit at pM level and these approaches based on nanoparticle labels offer a new avenue for sensitive detection of protein biomarkers.

  8. A Redox-Active Binder for Electrochemical Capacitor Electrodes.

    PubMed

    Benoit, Corentin; Demeter, Dora; Bélanger, Daniel; Cougnon, Charles

    2016-04-18

    A promising strategy for increasing the performance of supercapacitors is proposed. Until now, a popular strategy for increasing the specific capacity of the electrode consists of grafting redox molecules onto a high surface area carbon structure to add a faradaic contribution to the charge storage. Unfortunately, the grafting of molecules to the carbon surface leads to a dramatic decrease of the electrochemical performances of the composite material. Herein, we used the organic binder as an active material in the charge/discharge process. Redox molecules were attached onto its polymeric skeleton to obtain a redox binder with the dual functionalities of both the binder and the active material. In this way, the electrochemical performance was improved without detrimentally affecting the properties of the porous carbon. Results showed that the use of a redox binder is promising for enhancing both energy and power densities. PMID:26997572

  9. Enhanced electrochemical etching of ion irradiated silicon by localized amorphization

    SciTech Connect

    Dang, Z. Y.; Breese, M. B. H.; Lin, Y.; Tok, E. S.; Vittone, E.

    2014-05-12

    A tailored distribution of ion induced defects in p-type silicon allows subsequent electrochemical anodization to be modified in various ways. Here we describe how a low level of lattice amorphization induced by ion irradiation influences anodization. First, it superposes a chemical etching effect, which is observable at high fluences as a reduced height of a micromachined component. Second, at lower fluences, it greatly enhances electrochemical anodization by allowing a hole diffusion current to flow to the exposed surface. We present an anodization model, which explains all observed effects produced by light ions such as helium and heavy ions such as cesium over a wide range of fluences and irradiation geometries.

  10. Enhanced electrochemical etching of ion irradiated silicon by localized amorphization

    NASA Astrophysics Data System (ADS)

    Dang, Z. Y.; Breese, M. B. H.; Lin, Y.; Tok, E. S.; Vittone, E.

    2014-05-01

    A tailored distribution of ion induced defects in p-type silicon allows subsequent electrochemical anodization to be modified in various ways. Here we describe how a low level of lattice amorphization induced by ion irradiation influences anodization. First, it superposes a chemical etching effect, which is observable at high fluences as a reduced height of a micromachined component. Second, at lower fluences, it greatly enhances electrochemical anodization by allowing a hole diffusion current to flow to the exposed surface. We present an anodization model, which explains all observed effects produced by light ions such as helium and heavy ions such as cesium over a wide range of fluences and irradiation geometries.

  11. In Situ Synthesis of Carbon Nanotube Hybrids with Alternate MoC and MoS2 to Enhance the Electrochemical Activities of MoS2.

    PubMed

    Li, Xin; Zhang, Jinying; Wang, Rui; Huang, Hongyang; Xie, Chong; Li, Zhihui; Li, Jun; Niu, Chunming

    2015-08-12

    Molybdenum disulfides and carbides are effective catalysts for hydrogenation and hydridesulfurization, where MoS2 nanostructures are also highly promising materials for lithium ion batteries. High surface-to-volume ratio and strong interactions with conducting networks are crucial factors for their activities. A new hybrid structure of multiwalled carbon nanotube (MWCNT) with alternate MoC nanoparticles and MoS2 nanosheets (MoS2 + MoC-MWCNT) has been synthesized by controlled carburization of core-shell MoS2-MWCNT hybrid nanotubes and demonstrated by HRTEM, FFT, XRD, and Raman scattering. The MoS2 nanosheets (∼10 nm) remain tightly connected to MWCNT surfaces with {001} planes in parallel to MWCNT walls and the highly crystallized α-MoC particles (∼10 nm) are adhered to MWCNTs at angles of 60-80° between {111} planes and MWCNT walls. The electrochemical performances of the hybrid structures have been demonstrated as anodes for lithium ion batteries to be significantly increased by breaking MoS2 nanotubes into nanosheets (patches) on MWCNT surfaces, especially at high current rates. The specific capacities of MoS2 + MoC-MWCNT sample with ∼23% MoS2 have been demonstrated to be higher than those of MoS2-MWCNTs containing ∼70% MoS2. PMID:26226386

  12. AlOOH-reduced graphene oxide nanocomposites: one-pot hydrothermal synthesis and their enhanced electrochemical activity for heavy metal ions.

    PubMed

    Gao, Chao; Yu, Xin-Yao; Xu, Ren-Xia; Liu, Jin-Huai; Huang, Xing-Jiu

    2012-09-26

    This work described the preparation, characterization, and electrochemical behavior toward heavy metal ions of the AlOOH-reduced graphene oxide nanocomposites. This new material was synthesized through a green one-pot hydrothermal method. The morphologic and structure of the nanocomposites were characterized using atomic force microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoemission spectroscopy, Fourier transform-infrared spectroscopy, and transmission electron microscopy. Electrochemical properties were characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The chemical and electrochemical parameters that have influence on deposition and stripping of metal ions, such as pH value, deposition potential, and deposition time, were also studied. Due to the strong affinity of AlOOH to heavy metal ions and the fast electron-transfer kinetics of graphene, the combination of solid-phase extraction and stripping voltammetric analysis allowed fast and sensitive determination of Cd(II) and Pb(II) in drinking water, making these new nanocomposites promising candidates for practical applications in the fields of detecting heavy metal ions. Most importantly, these new nanocomposites may possess many unknown properties waiting to be explored. PMID:22924704

  13. Electrochemical Processes Enhanced by Acoustic Liquid Manipulation

    NASA Technical Reports Server (NTRS)

    Oeftering, Richard C.

    2004-01-01

    Acoustic liquid manipulation is a family of techniques that employ the nonlinear acoustic effects of acoustic radiation pressure and acoustic streaming to manipulate the behavior of liquids. Researchers at the NASA Glenn Research Center are exploring new methods of manipulating liquids for a variety of space applications, and we have found that acoustic techniques may also be used in the normal Earth gravity environment to enhance the performance of existing fluid processes. Working in concert with the NASA Commercial Technology Office, the Great Lakes Industrial Technology Center, and Alchemitron Corporation (Elgin, IL), researchers at Glenn have applied nonlinear acoustic principles to industrial applications. Collaborating with Alchemitron Corporation, we have adapted the devices to create acoustic streaming in a conventional electroplating process.

  14. Surface enhanced Raman scattering in electrochemical systems: The complex roles of surface roughness

    NASA Astrophysics Data System (ADS)

    Pemberton, Jeanne E.; Guy, Anita L.; Sobocinski, Raymond L.; Tuschel, David D.; Cross, Nathan A.

    1988-06-01

    A series of experiments designed to elucidate the presence and properties of large-scale and atomic-scale roughness produced on Ag electrodes with electrochemical oxidation-reduction cycle (ORC) pretreatments are presented. This report reviews surface enhanced Raman scattering (SERS) and scanning electron microscopic (SEM) characterization of Ag electrodes roughened with controlled-rate ORCs, and presents new results for the laser-induced thermal decay of SERS as a probe of Ag surface active sites and differential reflectance spectroscopy of electrochemically roughened Ag electrodes. These results are interpreted in terms of the presence and properties of both large-scale and atomic-scale roughness on these surfaces.

  15. Magnetic field associated with active electrochemical corrosion

    NASA Astrophysics Data System (ADS)

    Abedi, Afshin

    The purpose of this work is to provide a better understanding of the underlying sources of the magnetic field associated with ongoing electrochemical corrosion, to investigate the spatio-temporal information content of the corrosion magnetic field, and to evaluate its potential utility in non-invasive quantification of hidden corrosion. The importance of this work lies in the fact that conventional electrochemical instruments and techniques are not well suited for non-invasive measurements of the rate and dynamics of corrosion in occluded regions such as in aircraft lap joints. With the increase in the number of aging engineered systems there is an increasing demand for more accurate corrosion predictive models that can improve the probability of detection of corrosion induced flaws in structures, and hence reduce the risk of catastrophic failures. Therefore, such rate information is of great importance to the corrosion community. At the present time, there are no other techniques capable of providing such information. This work is the first successful attempt at quantification of the rate of corrosion through non- invasive measurements of its associated magnetic field. It includes the development of appropriate experimental techniques and associated models. Herein we have reviewed previous experiments, explored various exposure conditions and sample geometries, and discussed appropriate experimental procedures. We have defined quantitative magnetic parameters and, in conjunction with mass loss calibration measurements, have used them to determine non-invasively the rate and dynamics of ongoing hidden corrosion. We conclude that the corrosion magnetic field contains spatial and temporal information that correlate with the distribution, magnitude, and time course of currents associated with electrochemical corrosion. In conjunction with appropriate calibration experiments, sample geometry, and experimental topology, the magnetic activity of a corroding sample can be

  16. Electrochemically reduced graphene oxide on silicon nanowire arrays for enhanced photoelectrochemical hydrogen evolution.

    PubMed

    Meng, Huan; Fan, Ke; Low, Jingxiang; Yu, Jiaguo

    2016-09-21

    Photoelectrochemical (PEC) water splitting into hydrogen and oxygen by sunlight is a promising approach to solve energy and environmental problems. In this work, silicon nanowire arrays (SiNWs) photocathodes decorated with reduced graphene oxide (rGO) for PEC water splitting were successfully prepared by a flexible and scalable electrochemical reduction method. The SiNWs photocathode with the optimized rGO decoration (SiNWs/rGO20) shows an enhanced activity with a much higher photocurrent density and significantly positive shift of onset potential compared to the bare SiNWs arrays for the hydrogen evolution reaction (HER). The enhanced PEC activity is ascribed to the high electrical conductivity of rGO and improved separation of the photogenerated charge carriers. This work not only demonstrates a facile, rapid and tunable electrochemical reduction method to produce rGO, but also exhibits an efficient protocol to enhance the PEC water splitting of silicon-based materials. PMID:27461187

  17. Electrochemically active species and multielectron processes in ionic melts

    NASA Astrophysics Data System (ADS)

    Shapoval, Viktor I.; Solov'ev, Veniamin V.; Malyshev, Viktor V.

    2001-02-01

    The model concepts for the mechanisms of formation of electrochemically active species and multielectron processes in ionic nitrate-, carbonate-, boron- and titanium-containing fluoride melts are generalised. The fundamental importance of the acid-base properties of a melt in the mechanism of formation of electrochemically active species is shown for nitrate- and carbonate-containing melts. This fact is confirmed by electrochemical measurements and by calculations of force constants for oxyanions. The optimum form of electrochemically active species has been established; their reduction abilities depend on the cationic composition of a melt, the adsorption properties of the electrode surface and the electric field strength. The bibliography includes 218 references.

  18. Electrochemical Characterization of Riboflavin-Enhanced Reduction of Trinitrotoluene

    PubMed Central

    Sumner, James J.; Chu, Kevin

    2011-01-01

    There is great interest in understanding trinitrotoluene (TNT) and dinitrotoluene (DNT) contamination, detection and remediation in the environment due to TNT’s negative health effects and security implications. Numerous publications have focused on detecting TNT in groundwater using multiple techniques, including electrochemistry. The main degradation pathway of nitrotoluenes in the environment is reduction, frequently with biological and/or photolytic assistance. Riboflavin has also been noted to aid in TNT remediation in soils and groundwater when exposed to light. This report indicates that adding riboflavin to a TNT or DNT solution enhances redox currents in electrochemical experiments. Here AC voltammetry was performed and peak currents compared with and without riboflavin present. Results indicated that TNT, DNT and riboflavin could be detected using AC voltammetry on modified gold electrodes and the addition of riboflavin affected redox peaks of TNT and DNT. Poised potential experiments indicated that it is possible to enhance reduction of TNT in the presence of riboflavin and light. These results were dramatic enough to explain long term enhancement of bioremediation in environments containing high levels of riboflavin and enhance the limit of detection in electrochemically-based nitrotoluene sensing. PMID:22346674

  19. A Model Approach to the Electrochemical Cell: An Inquiry Activity

    ERIC Educational Resources Information Center

    Cullen, Deanna M.; Pentecost, Thomas C.

    2011-01-01

    In an attempt to address some student misconceptions in electrochemistry, this guided-inquiry laboratory was devised to give students an opportunity to use a manipulative that simulates the particulate-level activity within an electrochemical cell, in addition to using an actual electrochemical cell. Students are led through a review of expected…

  20. In Situ Electrochemical Oxidation Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation

    PubMed Central

    2015-01-01

    The development of catalysts with earth-abundant elements for efficient oxygen evolution reactions is of paramount significance for clean and sustainable energy storage and conversion devices. Our group demonstrated recently that the electrochemical tuning of catalysts via lithium insertion and extraction has emerged as a powerful approach to improve catalytic activity. Here we report a novel in situ electrochemical oxidation tuning approach to develop a series of binary, ternary, and quaternary transition metal (e.g., Co, Ni, Fe) oxides from their corresponding sulfides as highly active catalysts for much enhanced water oxidation. The electrochemically tuned cobalt–nickel–iron oxides grown directly on the three-dimensional carbon fiber electrodes exhibit a low overpotential of 232 mV at current density of 10 mA cm–2, small Tafel slope of 37.6 mV dec–1, and exceptional long-term stability of electrolysis for over 100 h in 1 M KOH alkaline medium, superior to most non-noble oxygen evolution catalysts reported so far. The materials evolution associated with the electrochemical oxidation tuning is systematically investigated by various characterizations, manifesting that the improved activities are attributed to the significant grain size reduction and increase of surface area and electroactive sites. This work provides a promising strategy to develop electrocatalysts for large-scale water-splitting systems and many other applications. PMID:27162978

  1. In Situ Electrochemical Oxidation Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation.

    PubMed

    Chen, Wei; Wang, Haotian; Li, Yuzhang; Liu, Yayuan; Sun, Jie; Lee, Sanghan; Lee, Jang-Soo; Cui, Yi

    2015-08-26

    The development of catalysts with earth-abundant elements for efficient oxygen evolution reactions is of paramount significance for clean and sustainable energy storage and conversion devices. Our group demonstrated recently that the electrochemical tuning of catalysts via lithium insertion and extraction has emerged as a powerful approach to improve catalytic activity. Here we report a novel in situ electrochemical oxidation tuning approach to develop a series of binary, ternary, and quaternary transition metal (e.g., Co, Ni, Fe) oxides from their corresponding sulfides as highly active catalysts for much enhanced water oxidation. The electrochemically tuned cobalt-nickel-iron oxides grown directly on the three-dimensional carbon fiber electrodes exhibit a low overpotential of 232 mV at current density of 10 mA cm(-2), small Tafel slope of 37.6 mV dec(-1), and exceptional long-term stability of electrolysis for over 100 h in 1 M KOH alkaline medium, superior to most non-noble oxygen evolution catalysts reported so far. The materials evolution associated with the electrochemical oxidation tuning is systematically investigated by various characterizations, manifesting that the improved activities are attributed to the significant grain size reduction and increase of surface area and electroactive sites. This work provides a promising strategy to develop electrocatalysts for large-scale water-splitting systems and many other applications. PMID:27162978

  2. Remediation of hexachlorocyclohexanes by electrochemically activated persulfates.

    PubMed

    Wacławek, Stanisław; Antoš, Vojtech; Hrabák, Pavel; Černík, Miroslav; Elliott, Daniel

    2016-01-01

    Hexachlorocyclohexane (HCH) isomers represent a family of formerly widely utilized pesticides that are persistent, capable of undergoing long-range transport and tend to bioaccumulate in human and animal tissue. Their widespread global utilization coupled with a propensity to adversely impact human health and the environment translates into an urgent need to develop feasible methodologies by which to treat HCH-impacted groundwater and soil. The present study was conducted to evaluate the efficacy of two persulfate-based oxidants: peroxydisulfate (S2O8 (2-), PDS) and peroxymonosulfate (HSO5 (-), PMS) activated by electrochemical processes (EC) to treat HCH-impacted environmental media. This research demonstrated that the optimal experimental conditions (oxidant dose and electrical current) were 2 mM PDS and 20 mA for an aqueous solution of 4 μM of summed HCHs (ΣHCH). GC/MS full scan analysis revealed the presence of 2,4,6-trichlorophenol as the only detectable intermediate formed during electro-activated PDS treatment of ΣHCH. The investigated method was tested on leachate from a known HCHs-impacted site in Hajek, Czech Republic which contained 106 μg/l of ΣHCH and 129 μg/l of chlorobenzenes. Results from batch treatment showed positive results for electro-activated PDS but only negligible effectiveness for electro-activated PMS. In addition to explaining the efficacy of the electro-activated PDS, this research also explored the basis for the differing reactivities of these two persulfates. PMID:26336848

  3. Interface Engineering of MoS2 /Ni3 S2 Heterostructures for Highly Enhanced Electrochemical Overall-Water-Splitting Activity.

    PubMed

    Zhang, Jian; Wang, Tao; Pohl, Darius; Rellinghaus, Bernd; Dong, Renhao; Liu, Shaohua; Zhuang, Xiaodong; Feng, Xinliang

    2016-06-01

    To achieve sustainable production of H2 fuel through water splitting, low-cost electrocatalysts for the hydrogen-evolution reaction (HER) and the oxygen-evolution reaction (OER) are required to replace Pt and IrO2 catalysts. Herein, for the first time, we present the interface engineering of novel MoS2 /Ni3 S2 heterostructures, in which abundant interfaces are formed. For OER, such MoS2 /Ni3 S2 heterostructures show an extremely low overpotential of ca. 218 mV at 10 mA cm(-2) , which is superior to that of the state-of-the-art OER electrocatalysts. Using MoS2 /Ni3 S2 heterostructures as bifunctional electrocatalysts, an alkali electrolyzer delivers a current density of 10 mA cm(-2) at a very low cell voltage of ca. 1.56 V. In combination with DFT calculations, this study demonstrates that the constructed interfaces synergistically favor the chemisorption of hydrogen and oxygen-containing intermediates, thus accelerating the overall electrochemical water splitting. PMID:27100374

  4. Poly(3-phenylthiophene) derivatives as active materials for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Eissa, Mona M.

    Poly(3-(4-methylsulfonylphenyl)thiophenes) (PMSPT), (3-(4-cyanophenyl)-thiophene) (PCNPT), (3-(3,4-difluorophenyl)thiophene) (MPFPT), (3-(3,5difluorophenyl)thiophene) (MMFPT), and (3-(3-fluorophenyl)thiophene) (MFPT) polymers were prepared and electrochemically characterized in various organic electrolytes. The morphologies and electrochemical performance of the films were shown to depend on both the growth and cycling electrolytes. Constant current multicycle tests were performed on single cell devices using the type III capacitor configuration at high voltage (2.8-2.9 V) employing MPFPT, PCNPT, PMSPT and PFPT polymers. Energy and power densities of up to 50 Wh/kg and 5 kW/kg were achieved and excellent stabilities (up to 1200 n-doping/dedoping cycles) were demonstrated. Industrial practicum. The industrial practicum report on "Chemical Vapor Deposition of High Performance Polymeric Thin Films for Advanced Interconnect Applications" determined the copolymerization and characterization of four novel copolymers of Parylene-N by a CVD process at low temperature. These copolymers retain the advantages of the CVD process and also modify the properties of the Parylene homopolymer significantly such as lowering the dielectric constant from 2.65 to ˜2.0, increasing the thermal stability and enhancing the adhesion. Apprenticeship practicum. The study on "Synthesis, Characterization, and Catalytic Activity of The Zeolite Encapsulated Ruthenium hexadeca-fluorophthalocyanine Complexes" determined the catalytic activity of this fluorinated ruthenium phthalocyanine which was encapsulated in zeolite NaX during crystallization. Both the free complex RuFsb{16}Pc and the encapsulated (RuFsb{16}Pc-NaX) were found to be effective catalysts for the oxidation of cyclohexane with high efficiency and stability.

  5. Fluctuation enhanced electrochemical reaction rates at the nanoscale.

    PubMed

    García-Morales, Vladimir; Krischer, Katharina

    2010-03-01

    The electrode potential constitutes a dynamical variable whenever an electrode is resistively coupled to the electric circuit. We show that at the nanoscale, the discreteness and stochasticity of an electron transfer event causes fluctuations of the electrode potential that render all elementary electrochemical reactions to be faster on a nanoelectrode than predicted by the macroscopic (Butler-Volmer) electrochemical kinetics. This phenomenon is substantiated by means of a generalized (electro)chemical master equation. PMID:20176966

  6. Graphene from electrochemical exfoliation and its direct applications in enhanced energy storage devices.

    PubMed

    Wei, Di; Grande, Lorenzo; Chundi, Vishnu; White, Richard; Bower, Chris; Andrew, Piers; Ryhänen, Tapani

    2012-01-30

    Graphite was electrochemically exfoliated in mixtures of room temperature ionic liquids and deionized water containing lithium salts to produce functionalized graphenes and such an electrochemical exfoliation technique can be directly used in making primary battery electrodes with significantly enhanced specific energy capacity. PMID:22170354

  7. Enhanced electrochemical detection of quercetin by Natural Deep Eutectic Solvents.

    PubMed

    Gomez, Federico José Vicente; Espino, Magdalena; de Los Angeles Fernandez, María; Raba, Julio; Silva, María Fernanda

    2016-09-14

    New trends in analytical chemistry encourage the development of smart techniques and methods aligned with Green Chemistry. In this sense, Natural Deep Eutectic Solvents represents an excellent opportunity as a new generation of green solvents. In this work a new application for them has been proposed and demonstrated. These solvents were synthesized by combinations of inexpensive and natural components like, Glucose, Fructose, Citric acid and Lactic acid. The different natural solvents were easily prepared and added to buffer solution in different concentrations, allowing the enhancement of electrochemical detection of an important representative antioxidant like quercetin (QR) with improved signal up to 380%. QR is a ubiquitous flavonoid widespread in plants and food of plant origin. The proposed method using phosphate buffer with a eutectic mixture of Citric acid, Glucose and water in combination with carbon screen printed electrodes exhibited a good analytical performance. Detection and quantification limits were of 7.97 and 26.3 nM respectively; and repeatability with %RSDs of 1.41 and 7.49 for peak potential and intensity respectively. In addition, it has proved to be faster, greener and cheaper than other sensors and chromatographic methods available with the additional advantage of being completely portable. Furthermore, the obtained results demonstrated that the proposed method is able for the determination of QR in complex food samples. PMID:27566343

  8. Electrochemically active polymers for rechargeable batteries

    SciTech Connect

    Novak, P.; Haas, O.; Santhanam, K.S.V.; Mueller, K.

    1997-01-01

    Electrochemical energy storage systems (batteries) have a tremendous role in technical applications. In this review the authors examine the prospects of electroactive polymers in view of the properties required for such batteries. Conducting organic polymers are considered here in the light of their rugged chemical environment: organic solvents, acids, and alkalis. The goal of the present article is to provide, first of all in tabular form, a survey of electroactive polymers in view of potential applications in rechargeable batteries. It reviews the preparative methods and the electrochemical performance of polymers as rechargeable battery electrodes. The theoretical values of specific charge of the polymers are comparable to those of metal oxide electrodes, but are not as high as those of most of the metal electrodes normally used in batteries. Therefore, it is an advantage in conventional battery designs to use the conducting polymer as a positive electrode material in combination with a negative electrode such as Li, Na, Mg, Zn, MeH{sub x}, etc. 504 refs.

  9. Electrochemically active biofilms: facts and fiction. A review.

    PubMed

    Babauta, Jerome; Renslow, Ryan; Lewandowski, Zbigniew; Beyenal, Haluk

    2012-01-01

    This review examines the electrochemical techniques used to study extracellular electron transfer in the electrochemically active biofilms that are used in microbial fuel cells and other bioelectrochemical systems. Electrochemically active biofilms are defined as biofilms that exchange electrons with conductive surfaces: electrodes. Following the electrochemical conventions, and recognizing that electrodes can be considered reactants in these bioelectrochemical processes, biofilms that deliver electrons to the biofilm electrode are called anodic, ie electrode-reducing, biofilms, while biofilms that accept electrons from the biofilm electrode are called cathodic, ie electrode-oxidizing, biofilms. How to grow these electrochemically active biofilms in bioelectrochemical systems is discussed and also the critical choices made in the experimental setup that affect the experimental results. The reactor configurations used in bioelectrochemical systems research are also described and the authors demonstrate how to use selected voltammetric techniques to study extracellular electron transfer in bioelectrochemical systems. Finally, some critical concerns with the proposed electron transfer mechanisms in bioelectrochemical systems are addressed together with the prospects of bioelectrochemical systems as energy-converting and energy-harvesting devices. PMID:22856464

  10. Electrochemically active biofilms: facts and fiction. A review

    PubMed Central

    Babauta, Jerome; Renslow, Ryan; Lewandowski, Zbigniew; Beyenal, Haluk

    2014-01-01

    This review examines the electrochemical techniques used to study extracellular electron transfer in the electrochemically active biofilms that are used in microbial fuel cells and other bioelectrochemical systems. Electrochemically active biofilms are defined as biofilms that exchange electrons with conductive surfaces: electrodes. Following the electrochemical conventions, and recognizing that electrodes can be considered reactants in these bioelectrochemical processes, biofilms that deliver electrons to the biofilm electrode are called anodic, ie electrode-reducing, biofilms, while biofilms that accept electrons from the biofilm electrode are called cathodic, ie electrode-oxidizing, biofilms. How to grow these electrochemically active biofilms in bioelec-trochemical systems is discussed and also the critical choices made in the experimental setup that affect the experimental results. The reactor configurations used in bioelectrochemical systems research are also described and the authors demonstrate how to use selected voltammetric techniques to study extracellular electron transfer in bioelectrochemical systems. Finally, some critical concerns with the proposed electron transfer mechanisms in bioelectrochemical systems are addressed together with the prospects of bioelectrochemical systems as energy-converting and energy-harvesting devices. PMID:22856464

  11. Three-dimensionally grown thorn-like Cu nanowire arrays by fully electrochemical nanoengineering for highly enhanced hydrazine oxidation.

    PubMed

    Huang, Jianfei; Zhao, Shunan; Chen, Wei; Zhou, Ying; Yang, Xiaoling; Zhu, Yihua; Li, Chunzhong

    2016-03-21

    This communication reports fully electrochemical nanoengineering toward three-dimensionally grown thorn-like Cu nanowire arrays (CNWAs) as a highly efficient and durable electrocatalyst for hydrazine oxidation. Characterized by substantial negative shifting of the onset potential and an enlarged catalytic current density, the CNWAs afforded greatly enhanced hydrazine oxidation activity, even transcending that of the Pt/C catalyst at a higher reaction rate. The parameters of the electrochemical engineering and metallization methods were found to be essentially influential on the microstructure, and thus the electrocatalytic activity of the CNWAs. The present work typifies a flexible and expandible route toward integrated electrodes of metallic 1D nanostructures which are of interest in advancing the performance of cutting-edge electrochemical applications. PMID:26580842

  12. Three-dimensionally grown thorn-like Cu nanowire arrays by fully electrochemical nanoengineering for highly enhanced hydrazine oxidation

    NASA Astrophysics Data System (ADS)

    Huang, Jianfei; Zhao, Shunan; Chen, Wei; Zhou, Ying; Yang, Xiaoling; Zhu, Yihua; Li, Chunzhong

    2016-03-01

    This communication reports fully electrochemical nanoengineering toward three-dimensionally grown thorn-like Cu nanowire arrays (CNWAs) as a highly efficient and durable electrocatalyst for hydrazine oxidation. Characterized by substantial negative shifting of the onset potential and an enlarged catalytic current density, the CNWAs afforded greatly enhanced hydrazine oxidation activity, even transcending that of the Pt/C catalyst at a higher reaction rate. The parameters of the electrochemical engineering and metallization methods were found to be essentially influential on the microstructure, and thus the electrocatalytic activity of the CNWAs. The present work typifies a flexible and expandible route toward integrated electrodes of metallic 1D nanostructures which are of interest in advancing the performance of cutting-edge electrochemical applications.This communication reports fully electrochemical nanoengineering toward three-dimensionally grown thorn-like Cu nanowire arrays (CNWAs) as a highly efficient and durable electrocatalyst for hydrazine oxidation. Characterized by substantial negative shifting of the onset potential and an enlarged catalytic current density, the CNWAs afforded greatly enhanced hydrazine oxidation activity, even transcending that of the Pt/C catalyst at a higher reaction rate. The parameters of the electrochemical engineering and metallization methods were found to be essentially influential on the microstructure, and thus the electrocatalytic activity of the CNWAs. The present work typifies a flexible and expandible route toward integrated electrodes of metallic 1D nanostructures which are of interest in advancing the performance of cutting-edge electrochemical applications. Electronic supplementary information (ESI) available: Experimental details, additional figures and table. See DOI: 10.1039/c5nr06512g

  13. Methods for enrichment of novel electrochemically-active microorganisms.

    PubMed

    Doyle, Lucinda Elizabeth; Marsili, Enrico

    2015-11-01

    Electrochemically-active microorganisms (EAM) are relevant to metal biogeochemistry and have applications in microbial fuel cells (MFCs), bioremediation, and bioelectrocatalysis. Most research conducted to date focuses on EAM hailing from two distinct genera, namely Shewanella and Geobacter, with a relatively limited number of EAM discovered in recent years. This review article summarises current approaches to novel EAM enrichment, in terms of inoculum choice, growth medium, reactor configuration, electrochemical characterisation and community profiling through metagenomics and metatranscriptomics. A novel roadmap for EAM enrichment and subsequent characterisation using environmental samples as a starting material is provided in order to increase throughput and hence the likelihood of discovering novel EAM. PMID:26189782

  14. Peptide biosensors for the electrochemical measurement of protein kinase activity.

    PubMed

    Kerman, Kagan; Song, Haifeng; Duncan, James S; Litchfield, David W; Kraatz, Heinz-Bernhard

    2008-12-15

    The kinase activities are elucidated using the novel redox-active cosubstrate adenosine 5'-[gamma-ferrocene] triphosphate (Fc-ATP), which enables the kinase-catalyzed transfer of a redox active gamma-phosphate-Fc to a hydroxyamino acid. In this report, a versatile electrochemical biosensor is developed for monitoring the activity and inhibition of a serine/threonine kinase, casein kinase 2 (CK2), and protein tyrosine kinases, Abl1-T315I and HER2, in buffered solutions and in cell lysates. The method is based on the labeling of a specific phosphorylation event with Fc, followed by electrochemical detection. The electrochemical response obtained from the "ferrocenylated" peptides enables monitoring the activity of the kinase and its substrate, as well as the inhibition of small molecule inhibitors on protein phosphorylation. Kinetic information was extracted from the electrochemical measurements for the determination of K(m) and V(m) values, which were in agreement with those previously reported. Kinase reactions were also performed in the presence of well-defined inhibitors of CK2, 4,5,6,7-tetrabromo-2-azabenzimidazole, 2-dimethylamino-4,5,6,7-tetrabromo-1H-benzimidazole, and E-3-(2,3,4,5-tetrabromophenyl)acrylic acid as well as the nonspecific kinase inhibitors, staurosporine and N-benzoylstaurosporine. On the basis of the dependency of the Fc signal on inhibitor concentration, K(i) of the inhibitors was estimated, which were also in agreement with the literature values. The performance of the biosensor was optimized including the kinase reaction, incubation with Fc-ATP, and the small molecule inhibitors. Peptide modified electrochemical biosensors are promising candidates for cost-effective in vitro kinase activity and inhibitor screening assays. PMID:18989981

  15. Synthesis of cobalt oxide-reduced graphene nanocomposite and its enhanced electrochemical properties as negative material for alkaline secondary battery

    NASA Astrophysics Data System (ADS)

    Xu, Yanan; Wang, Xiaofeng; An, Cuihua; Wang, Yijing; Jiao, Lifang; Yuan, Huatang

    2014-12-01

    A potential negative electrode material Co3O4@rGO is synthesized via a facile reflux condensation route. The electrochemical performances of Co3O4@rGO composite for alkaline rechargeable Ni/Co batteries have been systemically investigated for the first time. The reduced-graphene can remarkably enhance the electrochemical activity of Co3O4 materials, leading to a notable improvement of discharge capacity, cycle stability and rate capability. Interestingly, the maximum discharge capacity of Co3O4@rGO-20 (additive amount of GO is 20 mg) electrode can reach 511.4 mAh g-1 with the capacity retention of 89.1% after 100 cycles at a discharge current of 100 mA g-1. A properly electrochemical reaction mechanism of Co3O4@rGO electrode is also constructed in detail.

  16. Self-assembled magnetic bead chains for sensitivity enhancement of microfluidic electrochemical biosensor platforms.

    PubMed

    Armbrecht, L; Dincer, C; Kling, A; Horak, J; Kieninger, J; Urban, G

    2015-11-21

    In this paper, we present a novel approach to enhance the sensitivity of microfluidic biosensor platforms with self-assembled magnetic bead chains. An adjustable, more than 5-fold sensitivity enhancement is achieved by introducing a magnetic field gradient along a microfluidic channel by means of a soft-magnetic lattice with a 350 μm spacing. The alternating magnetic field induces the self-assembly of the magnetic beads in chains or clusters and thus improves the perfusion and active contact between the analyte and the beads. The soft-magnetic lattices can be applied independent of the channel geometry or chip material to any microfluidic biosensing platform. At the same time, the bead-based approach achieves chip reusability and shortened measurement times. The bead chain properties and the maximum flow velocity for bead retention were validated by optical microscopy in a glass capillary. The magnetic actuation system was successfully validated with a biotin-streptavidin model assay on a low-cost electrochemical microfluidic chip, fabricated by dry-film photoresist technology (DFR). Labelling with glucose oxidase (GOx) permits rapid electrochemical detection of enzymatically produced H2O2. PMID:26394820

  17. Electrochemical Proteolytic Beacon for Detection of Matrix Metalloproteinase Activities

    SciTech Connect

    Liu, Guodong; Wang, Jun; Wunschel, David S.; Lin, Yuehe

    2006-09-27

    This communication describes a novel method for detecting of matrix metalloproteinase-7 activity using a peptide substrate labeled with a ferrocene reporter. The substrate serves as a selective ‘electrochemical proteolytic beacon’ (EPB) for this metalloproteinase. The EPB is immobilized on a gold electrode surface to enable ‘on-off’ electrochemical signaling capability for uncleaved and cleaved events. The EPB is efficiently and selectively cleaved by MMP-7 as measured by the rate of decrease in redox current of ferrocene. Direct transduction of a signal corresponding to peptide cleavage events into an electronic signal thus provides a simple, sensitive route for detecting the MMP activity. The new method allows for identification of the activity of MMP-7 in concentrations as low as 3.4 pM. The concept can be extended to design multiple peptide substrate labeled with different electroactive reporters for assaying multiple MMPs activities.

  18. Calcium alloy as active material in secondary electrochemical cell

    DOEpatents

    Roche, Michael F.; Preto, Sandra K.; Martin, Allan E.

    1976-01-01

    Calcium alloys such as calcium-aluminum and calcium-silicon, are employed as active material within a rechargeable negative electrode of an electrochemical cell. Such cells can use a molten salt electrolyte including calcium ions and a positive electrode having sulfur, sulfides, or oxides as active material. The calcium alloy is selected to prevent formation of molten calcium alloys resulting from reaction with the selected molten electrolytic salt at the cell operating temperatures.

  19. Electro-Chemically Enhanced Mechanical Polishing of Nickel Mandrels

    NASA Technical Reports Server (NTRS)

    Gubarev, Mikhail; Ramsey, Brian; Engelhaupt, Darell

    2006-01-01

    Grinding and mechanical polishing techniques used for x-ray optics mandrel figuring lead to mid-frequency surface ripple. These small figure variations have to be addressed in order to improve the performance of the resulting x-ray mirrors. If the electrochemical etching is combined with mechanical polishing, the figuring and the surface finishing cm be done simultaneously and be used to correct the mid-frequency surface ripple. It is shown that the electrochemical mechanical polishing method allows selective removal of nickel alloy without mandrel surface microroughness degradation.

  20. Novel quasi-symmetric solid oxide fuel cells with enhanced electrochemical performance

    NASA Astrophysics Data System (ADS)

    Chen, Yonghong; Cheng, Zhuanxia; Yang, Yang; Gu, Qingwen; Tian, Dong; Lu, Xiaoyong; Yu, Weili; Lin, Bin

    2016-04-01

    Symmetrical solid oxide fuel cell (SSOFC) using same materials as both anode and cathode simultaneously has gained extensively attentions, which can simplify fabrication process, minimize inter-diffusion between components, enhance sulfur and coking tolerance by operating the anode as the cathode in turn. With keeping the SSOFC's advantages, a novel quasi-symmetrical solid oxide fuel cell (Q-SSOFC) is proposed to further improve the performance, which optimally combines two different SSOFC electrode materials as both anode and cathode simultaneously. PrBaFe2O5+δ (PBFO) and PrBaFe1.6Ni0.4O5+δ (PBFNO, Fe is partially substituted by Ni.) are prepared and applied as both cathode and anode for SSOFC, which exhibit desirable chemical and thermal compatibility with Sm0.8Ce0.2O1.9 (SDC) electrolyte. PBFO cathode exhibits higher oxygen reduction reaction (ORR) activity than PBFNO cathode in air, whereas PBFNO anode exhibits higher hydrogen oxidation reaction (HOR) activity than PBFO anode in H2. The as-designed Q-SSOFC of PBFNO/SDC/PBFO exhibits higher electrochemical performance than the conventional SSOFCs of both PBFO/SDC/PBFO and PBFNO/SDC/PBFNO. The superior performance of Q-SSOFC is attributed to the lowest polarization resistance (Rp). The newly developed Q-SSOFCs open doors for further improvement of electrochemical performance in SSOFC, which hold more promise for various potential applications.

  1. Electrochemical activation of carbon cloth in aqueous inorganic salt solution for superior capacitive performance

    NASA Astrophysics Data System (ADS)

    Ye, Dong; Yu, Yao; Tang, Jie; Liu, Lin; Wu, Yue

    2016-05-01

    Carbon cloth (CC) is an inexpensive and highly conductive textile with excellent mechanical flexibility and strength; it holds great promise as an electrode material for flexible supercapacitors. However, pristine CC has such a low surface area and poor electrochemical activity that the energy storage capability is usually very poor. Herein, we report a green method, two-step electrochemical activation in an aqueous solution of inorganic salts, to significantly enhance the capacitance of CC for supercapacitor application. Micro-cracks, exfoliated carbon fiber shells, and oxygen-containing functional groups (OFGs) were introduced onto the surface of the carbon filament. This resulted in an enhancement of over two orders of magnitude in capacitance compared to that of the bare CC electrode, reaching up to a maximum areal capacitance of 505.5 mF cm-2 at the current density of 6 mA cm-2 in aqueous H2SO4 electrolyte. Electrochemical reduction of CC electrodes led to the removal of most electrochemically unstable surface OFGs, resulting in superior charging/discharging rate capability and excellent cycling stability. Although the activated CC electrode contained a high-level of surface oxygen functional groups (~15 at%), it still exhibited a remarkable charging-discharging rate capability, retaining ~88% of the capacitance when the charging rate increased from 6 to 48 mA cm-2. Moreover, the activated CC electrode exhibited excellent cycling stability with ~97% capacitance remaining after 10 000 cycles at a current density of 24 mA cm-2. A symmetrical supercapacitor based on the activated CC exhibited an ideal capacitive behavior and fast charge-discharge properties. Such a simple, environment-friendly, and cost-effective strategy to activate CC shows great potential in the fabrication of high-performance flexible supercapacitors.Carbon cloth (CC) is an inexpensive and highly conductive textile with excellent mechanical flexibility and strength; it holds great promise as

  2. Electrochemical activation of carbon cloth in aqueous inorganic salt solution for superior capacitive performance.

    PubMed

    Ye, Dong; Yu, Yao; Tang, Jie; Liu, Lin; Wu, Yue

    2016-05-21

    Carbon cloth (CC) is an inexpensive and highly conductive textile with excellent mechanical flexibility and strength; it holds great promise as an electrode material for flexible supercapacitors. However, pristine CC has such a low surface area and poor electrochemical activity that the energy storage capability is usually very poor. Herein, we report a green method, two-step electrochemical activation in an aqueous solution of inorganic salts, to significantly enhance the capacitance of CC for supercapacitor application. Micro-cracks, exfoliated carbon fiber shells, and oxygen-containing functional groups (OFGs) were introduced onto the surface of the carbon filament. This resulted in an enhancement of over two orders of magnitude in capacitance compared to that of the bare CC electrode, reaching up to a maximum areal capacitance of 505.5 mF cm(-2) at the current density of 6 mA cm(-2) in aqueous H2SO4 electrolyte. Electrochemical reduction of CC electrodes led to the removal of most electrochemically unstable surface OFGs, resulting in superior charging/discharging rate capability and excellent cycling stability. Although the activated CC electrode contained a high-level of surface oxygen functional groups (∼15 at%), it still exhibited a remarkable charging-discharging rate capability, retaining ∼88% of the capacitance when the charging rate increased from 6 to 48 mA cm(-2). Moreover, the activated CC electrode exhibited excellent cycling stability with ∼97% capacitance remaining after 10 000 cycles at a current density of 24 mA cm(-2). A symmetrical supercapacitor based on the activated CC exhibited an ideal capacitive behavior and fast charge-discharge properties. Such a simple, environment-friendly, and cost-effective strategy to activate CC shows great potential in the fabrication of high-performance flexible supercapacitors. PMID:27141910

  3. Electrochemical synthesis of mesoporous Pt-Au binary alloys with tunable compositions for enhancement of electrochemical performance.

    PubMed

    Yamauchi, Yusuke; Tonegawa, Akihisa; Komatsu, Masaki; Wang, Hongjing; Wang, Liang; Nemoto, Yoshihiro; Suzuki, Norihiro; Kuroda, Kazuyuki

    2012-03-21

    Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors. PMID:22352760

  4. Chemical Potentials and Activities: An Electrochemical Introduction.

    ERIC Educational Resources Information Center

    Wetzel, T. L.; And Others

    1986-01-01

    Describes a laboratory experiment which explores the effects of adding inert salts to electrolytic cells and demonstrates the difference between concentration and chemical activity. Examines chemical potentials as the driving force of reactions. Provides five examples of cell potential and concentration change. (JM)

  5. Catalytic activity of platinum on ruthenium electrodes with modified (electro)chemical states.

    PubMed

    Park, Kyung-Won; Sung, Yung-Eun

    2005-07-21

    Using Pt on Ru thin-film electrodes with various (electro)chemical states designed by the sputtering method, the effect of Ru states on the catalytic activity of Pt was investigated. The chemical and electrochemical properties of Pt/Ru thin-film samples were confirmed by X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry. In addition, Pt nanoparticles on Ru metal or oxide for an actual fuel cell system showed an effect of Ru states on the catalytic activity of Pt in methanol electrooxidation. Finally, it was concluded that such an enhancement of methanol electrooxidation on the Pt is responsible for Ru metallic and/or oxidation sites compared to pure Pt without any Ru state. PMID:16852701

  6. Understanding the mechanism of surface modification through enhanced thermal and electrochemical stabilities of N-doped graphene oxide

    NASA Astrophysics Data System (ADS)

    Mehetre, Shantilal S.; Maktedar, Shrikant S.; Singh, Man

    2016-03-01

    The kinetically active two dimensional surface of graphene oxide (GrO) plays an important role in understanding the chemistry of graphene. The GrO is comprises of carbon and oxygen while the f-(6-AIND) GrO contains nitrogen along with carbon and oxygen. The prominent thermal instability of GrO is widely explored. However, due to the synergistic impact of their constituting elements, the thermal and electrochemical stability of f-(6-AIND) GrO enhances after N-doping with nitrogen containing heterocycles like 6-Aminoindazole. Hence it is essential to probe the mutual impact of various functionalities present over the surface of GrO, to understand the mechanism of direct functionalization of GrO with thermal and electrochemical stabilities. Therefore, the decomposition kinetics of discrete atomic domains and their effect on thermal stability of f-(6-AIND) GrO was revealed with spectroscopic analysis and thermal assessment. Additionally, the mechanism of thermal transformation is precisely developed to demonstrate the impact of heat on weight loss due to the mass transfer. Likewise, the electrochemical properties can be well understood with the help of mechanism of electrochemical activity and cyclic voltammetry experiments. Also, the f-(6-AIND) GrO is confirmed with the help of various surface analysis techniques like FTIR, EDS, HR-XPS, HR-TEM, CV, SAED, TGA, DSC and UV-vis.

  7. Lithium-active molybdenum trioxide coated LiNi0.5Co0.2Mn0.3O2 cathode material with enhanced electrochemical properties for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Wu, Feng; Tian, Jun; Su, Yuefeng; Guan, Yibiao; Jin, Yi; Wang, Zhao; He, Tao; Bao, Liying; Chen, Shi

    2014-12-01

    LiNi0.5Co0.2Mn0.3O2 cathode material was coated with MoO3 via a wet coating process. X-ray diffraction patterns show that the coating surface is composed of MoO3 and Li2MoO4. The 3 wt.% MoO3 coated LiNi0.5Co0.2Mn0.3O2 cathode (Li2MoO4 is treated as equivalent mole of MoO3) exhibits the best improved cycling performance. It performs a capacity retention of 90.9% after 100 cycles while that of the pristine material is only 82.8%. After being coated by 3 wt.% MoO3, the rate performance is also greatly enhanced and the charge transfer resistance is greatly decreased. The improvement of electrochemical performance is related to the fact that the coating layer diminishes the side reactions between the cathode and the electrolyte.

  8. The active site behaviour of electrochemically synthesised gold nanomaterials.

    PubMed

    Plowman, Blake J; O'Mullane, Anthony P; Bhargava, Suresh K

    2011-01-01

    Even though gold is the noblest of metals, a weak chemisorber and is regarded as being quite inert, it demonstrates significant electrocatalytic activity in its nanostructured form. It is demonstrated here that nanostructured and even evaporated thin films of gold are covered with active sites which are responsible for such activity. The identification of these sites is demonstrated with conventional electrochemical techniques such as cyclic voltammetry as well as a large amplitude Fourier transformed alternating current (FT-ac) method under acidic and alkaline conditions. The latter technique is beneficial in determining if an electrode process is either Faradaic or capacitive in nature. The observed behaviour is analogous to that observed for activated gold electrodes whose surfaces have been severely disrupted by cathodic polarisation in the hydrogen evolution region. It is shown that significant electrochemical oxidation responses occur at discrete potential values well below that for the formation of the compact monolayer oxide of bulk gold and are attributed to the facile oxidation of surface active sites. Several electrocatalytic reactions are explored in which the onset potential is determined by the presence of such sites on the surface. Significantly, the facile oxidation of active sites is used to drive the electroless deposition of metals such as platinum, palladium and silver from their aqueous salts on the surface of gold nanostructures. The resultant surface decoration of gold with secondary metal nanoparticles not only indicates regions on the surface which are rich in active sites but also provides a method to form interesting bimetallic surfaces. PMID:22455038

  9. Electrochemical studies on nanometal oxide-activated carbon composite electrodes for aqueous supercapacitors

    NASA Astrophysics Data System (ADS)

    Ho, Mui Yen; Khiew, Poi Sim; Isa, Dino; Chiu, Wee Siong

    2014-11-01

    In present study, the electrochemical performance of eco-friendly and cost-effective titanium oxide (TiO2)-based and zinc oxide-based nanocomposite electrodes were studied in neutral aqueous Na2SO3 electrolyte, respectively. The electrochemical properties of these composite electrodes were studied using cyclic voltammetry (CV), galvanostatic charge-discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that these two nanocomposite electrodes achieve the highest specific capacitance at fairly low oxide loading onto activated carbon (AC) electrodes, respectively. Considerable enhancement of the electrochemical properties of TiO2/AC and ZnO/AC nanocomposite electrodes is achieved via synergistic effects contributed from the nanostructured metal oxides and the high surface area mesoporous AC. Cations and anions from metal oxides and aqueous electrolyte such as Ti4+, Zn2+, Na+ and SO32- can occupy some pores within the high-surface-area AC electrodes, forming the electric double layer at the electrode-electrolyte interface. Additionally, both TiO2 and ZnO nanoparticles can provide favourable surface adsorption sites for SO32- anions which subsequently facilitate the faradaic processes for pseudocapacitive effect. These two systems provide the low cost material electrodes and the low environmental impact electrolyte which offer the increased charge storage without compromising charge storage kinetics.

  10. In situ x-ray, electrochemical, and modeling investigation of the oxygen electrode activation.

    SciTech Connect

    Yildiz, B.; Chang, K.-C.; Meyers, D.; Carter, J. D.; You, H.

    2006-01-01

    Oxygen electrodes of solid oxide electrochemical cells have been shown to improve under strong cathodic and anodic polarization. Our study investigates the mechanism causing such improvement, using in situ x-ray and electrochemical characterization and electrochemical impedance modeling of the oxygen electrodes. Several porous and dense thin-film model electrodes of La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LSM) and La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LCM) on single crystal yttria-stabilized zirconia (YSZ) electrolytes have been analyzed in situ at the Advanced Photon Source (APS) using x-ray reflectivity and x-ray absorption near edge spectroscopy (XANES) at the Mn K-edge and La LII-edge. In situ x-ray reflectivity analysis show that no clear correlation between the polarization of the electrode and any further changes in the roughness of the LSM/YSZ interface exist. XANES measurements illustrate that the cathodic or anodic dc polarization at high temperature induces no detectable changes in Mn chemical state either in the bulk or at the surface of the LCM and LSM electrodes on YSZ, while the La chemical state changes reversibly at the electrode surface. This field-induced chemical change of La at the surface of electrodes is assumed to be a cause of the electrochemical activation through enhanced surface exchange of oxygen on the doped lanthanum manganite electrodes.

  11. Preparation of activated carbon from wet sludge by electrochemical-NaClO activation.

    PubMed

    Miao, Chen; Ye, Caihong; Zhu, Tianxing; Lou, Ziyang; Yuan, Haiping; Zhu, Nanwen

    2014-01-01

    Activated carbon (AC) from sludge is one potential solution for sewage sludge disposal, while the drying sludge is cost and time consuming for preparation. AC preparation from the wet sludge with electrochemical-NaClO activation was studied in this work. Three pretreatment processes, i.e. chemical activation, electrolysis and electrochemical-reagent reaction, were introduced to improve the sludge-derived AC properties, and the optimum dosage of reagent was tested from the 0.1:1 to 1:1 (mass rate, reagent:dried sludge). It was shown that the electrochemical-NaClO preparation is the best method under the test conditions, in which AC has the maximum Brunauer, Emmett and Teller area of 436 m²/g at a mass ratio of 0.7. Extracellular polymeric substances in sludge can be disintegrated by electrochemical-NaClO pretreatment, with a disintegration degree of more than 45%. The percentage of carbon decreased from 34.16 to 8.81 after treated by electrochemical-NaClO activation. Fourier transform infrared spectra showed that a strong C-Cl stretching was formed in electrochemical-NaClO prepared AC. The maximum adsorption capacity of AC reaches 109 mg/g on MB adsorption experiment at pH 10 and can be repeated for three times with high removal efficiency after regeneration. PMID:25176302

  12. DNA Diagnostics: Nanotechnology-enhanced Electrochemical Detection of Nucleic Acids

    PubMed Central

    Wei, Fang; Lillehoj, Peter B.; Ho, Chih-Ming

    2010-01-01

    The detection of mismatched base pairs in DNA plays a crucial role in the diagnosis of genetic-related diseases and conditions, especially for early stage treatment. Among the various biosensors that have been employed for DNA detection, electrochemical sensors show great promise since they are capable of precise DNA recognition and efficient signal transduction. Advancements in micro- and nanotechnologies, specifically fabrication techniques and new nanomaterials, have enabled for the development of highly sensitive, highly specific sensors making them attractive for the detection of small sequence variations. Furthermore, the integration of sensors with sample preparation and fluidic processes enables for rapid, multiplexed DNA detection for point-of-care (POC) clinical diagnostics. PMID:20075759

  13. Fabrication of Flexible, Redoxable, and Conductive Nanopillar Arrays with Enhanced Electrochemical Performance.

    PubMed

    Yang, MinHo; Hong, Seok Bok; Yoon, Jo Hee; Kim, Dong Seok; Jeong, Soon Woo; Yoo, Dong Eun; Lee, Tae Jae; Lee, Kyoung G; Lee, Seok Jae; Choi, Bong Gill

    2016-08-31

    Highly ordered and flexible nanopillar arrays have received considerable interest for many applications of electrochemical devices because of their unique mechanical and structural properties. Here, we report on highly ordered polyoxometalate (POM)-doped polypyrrole (Ppy) nanopillar arrays produced by soft lithography and subsequent electrodeposition. As-prepared POM-Ppy/nanopillar films show superior electrochemical performances for pseudocapacitor and enzymeless electrochemical sensor applications and good mechanical properties, which allowed them to be easily bent and twisted. Regarding electrochemical characteristics for pseudocapacitive electrodes, the POM-Ppy/nanopillar electrodes are capable of delivering high areal capacitance of 77.0 mF cm(-2), high rate performance, and good cycle life of ∼100% retention over 3500 cycles even when bent. Moreover, the study suggests that the POM-Ppy/nanopillar electrodes have an excellent electrocatalytic activity toward hydrogen. PMID:27548355

  14. Microbial solar cells: applying photosynthetic and electrochemically active organisms.

    PubMed

    Strik, David P B T B; Timmers, Ruud A; Helder, Marjolein; Steinbusch, Kirsten J J; Hamelers, Hubertus V M; Buisman, Cees J N

    2011-01-01

    Microbial solar cells (MSCs) are recently developed technologies that utilize solar energy to produce electricity or chemicals. MSCs use photoautotrophic microorganisms or higher plants to harvest solar energy, and use electrochemically active microorganisms in the bioelectrochemical system to generate electrical current. Here, we review the principles and performance of various MSCs in an effort to identify the most promising systems, as well as the bottlenecks and potential solutions, for "real-life" MSC applications. We present an outlook on future applications based on the intrinsic advantages of MSCs, specifically highlighting how these living energy systems can facilitate the development of an electricity-producing green roof. PMID:21067833

  15. Enhanced electrochemical supercapacitor properties with synergistic effect of polyaniline, graphene and AgxO

    NASA Astrophysics Data System (ADS)

    Usman, Muhammad; Pan, Lujun; Asif, Muhammad; Mahmood, Zafar; Khan, M. A.; Fu, Xin

    2016-05-01

    The graphene-Ag2O/polyaniline (GAP) composite has been synthesized by in-situ polymerization. It has been observed that Ag2O nanoparticles exist on the porous spongy background of PANI (polyaniline). The optimized composition of the synthesized composite exhibits an extraordinary specific capacitance of 1572 Fg-1 at 0.05 Ag-1 current density and good cyclic stability of 85% over 3000 charge-discharge cycles. The extraordinary electrochemical performance indicates the positive synergistic effect of PANI, graphene and Ag2O. The Ag2O nanoparticles might be responsible for improved electrical conductivity, and graphene might contribute in enhancing the electrochemical stability of the PANI electrode.

  16. Nanogold/mesoporous carbon foam-mediated silver enhancement for graphene-enhanced electrochemical immunosensing of carcinoembryonic antigen.

    PubMed

    Lin, Dajie; Wu, Jie; Ju, Huangxian; Yan, Feng

    2014-02-15

    Nanogold functionalized mesoporous carbon foam (Au/MCF) coupling with a signal amplification by C-Au synergistic silver enhancement was designed for sensitive electrochemical immunosensing of biomarker. The Au/MCF was prepared by in situ growth of nanogold on carboxylated MCF and used as a tracing tag to label signal antibody via the inherent interaction between protein and nanogold. The immunosensor was prepared by covalently immobilizing capture antibody on an electrochemically reduced graphene oxide/chitosan film modified glassy carbon electrode. Through a sandwich-type immunoreaction, Au/MCF tags were captured on the immunoconjugates to induce a silver deposition process. The electrochemical stripping signal of the deposited silver was used to monitor the immunoreaction. The Au/MCF-mediated silver enhancement along with the graphene-promoted electron transfer led to high detection sensitivity of carcinoembryonic antigen. Under optimal conditions, the proposed immunoassay method showed wide linear range from 0.05 pg mL(-1) to 1 ng mL(-1) and a detection limit down to 0.024 pg mL(-1). The newly designed amplification strategy holds great potential for ultrasensitive electrochemical biosensing of other analytes. PMID:24041661

  17. Chemical splitting of multiwalled carbon nanotubes to enhance electrochemical capacitance for supercapacitors

    NASA Astrophysics Data System (ADS)

    Li, Xinlu; Li, Tongtao; Zhang, Xinlin; Zhong, Qineng; Li, Hongyi; Huang, Jiamu

    2014-06-01

    Multiwalled carbon nanotubes (MWCNTs) were chemically split and self-assembled to a flexible porous paper made of graphene oxide nanoribbons (GONRs). The morphology and microstructure of the pristine MWCNTs and GONRs were analyzed by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Raman spectroscopy and Fourier transform infrared spectroscopy. And the specific surface area and porosity structure were measured by N2 adsorption-desorption. The longitudinally split MWCNTs show an enhancement in specific capacitance from 21 F g-1 to 156 F g-1 compared with the pristine counterpart at 0.1 A g-1 in a 6 M KOH aqueous electrolytes. The electrochemical experiments prove that the chemical splitting of MWCNTs will make inner carbon layers opened and exposed to electrochemical double layers, which can effectively improve the electrochemical capacitance for supercapacitors.

  18. Phenolic compounds as enhancers in enzymatic and electrochemical oxidation of veratryl alcohol and lignins.

    PubMed

    Díaz-González, María; Vidal, Teresa; Tzanov, Tzanko

    2011-03-01

    Sixteen phenolic compounds, 14 of which naturally occurring, were compared to the synthetic 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) and violuric acid (VA) in terms of their ability to act as mediators/enhancers in: (1) laccase oxidation of veratryl alcohol as a lignin model compound, and (2) electrochemical oxidation of kraft and flax lignins. HPLC analysis revealed that the syringyl-type phenols methyl syringate and acetosyringone were the most efficient natural enhancers in the laccase oxidation of veratryl alcohol. Both compounds, though far from the performance of ABTS were able to generate veratraldehyde in amount similar to that obtained with VA. By contrast, the best performing phenolic enhancers for the electrochemical oxidation of lignins were sinapinaldehyde, vanillin, acetovanillone, and syringic acid. Catalytic efficiencies close to those achieved with ABTS and VA were calculated for these phenolic compounds. PMID:21110019

  19. Electrochemical activation of nitrate reduction to nitrogen by Ochrobactrum sp. G3-1 using a noncompartmented electrochemical bioreactor.

    PubMed

    Lee, Woo Jin; Park, Doo Hyun

    2009-08-01

    A denitrification bacterium was isolated from riverbed soil and identified as Ochrobactrum sp., whose specific enzymes for denitrification metabolism were biochemically assayed or confirmed with specific coding genes. The denitrification activity of strain G3-1 was proportional to glucose/nitrate balance, which was consistent with the theoretical balance (0.5). The modified graphite felt cathode with neutral red, which functions as a solid electron mediator, enhanced the electron transfer from electrode to bacterial cell. The porous carbon anode was coated with a ceramic membrane and cellulose acetate film in order to permit the penetration of water molecules from the catholyte to the outside through anode, which functions as an air anode. A non-compartmented electrochemical bioreactor (NCEB) comprised of a solid electron mediator and an air anode was employed for cultivation of G3-1 cells. The intact G3-1 cells were immobilized in the solid electron mediator, by which denitrification activity was greatly increased at the lower glucose/nitrate balance than the theoretical balance (0.5). Metabolic stability of the intact G3-1 cells immobilized in the solid electron mediator was extended to 20 days, even at a glucose/nitrate balance of 0.1. PMID:19734723

  20. Sheath-flow microfluidic approach for combined surface enhanced Raman scattering and electrochemical detection.

    PubMed

    Bailey, Matthew R; Pentecost, Amber M; Selimovic, Asmira; Martin, R Scott; Schultz, Zachary D

    2015-04-21

    The combination of hydrodynamic focusing with embedded capillaries in a microfluidic device is shown to enable both surface enhanced Raman scattering (SERS) and electrochemical characterization of analytes at nanomolar concentrations in flow. The approach utilizes a versatile polystyrene device that contains an encapsulated microelectrode and fluidic tubing, which is shown to enable straightforward hydrodynamic focusing onto the electrode surface to improve detection. A polydimethyslsiloxane (PDMS) microchannel positioned over both the embedded tubing and SERS active electrode (aligned ∼200 μm from each other) generates a sheath flow that confines the analyte molecules eluting from the embedded tubing over the SERS electrode, increasing the interaction between the Riboflavin (vitamin B2) and the SERS active electrode. The microfluidic device was characterized using finite element simulations, amperometry, and Raman experiments. This device shows a SERS and amperometric detection limit near 1 and 100 nM, respectively. This combination of SERS and amperometry in a single device provides an improved method to identify and quantify electroactive analytes over either technique independently. PMID:25815795

  1. Sheath-Flow Microfluidic Approach for Combined Surface Enhanced Raman Scattering and Electrochemical Detection

    PubMed Central

    2015-01-01

    The combination of hydrodynamic focusing with embedded capillaries in a microfluidic device is shown to enable both surface enhanced Raman scattering (SERS) and electrochemical characterization of analytes at nanomolar concentrations in flow. The approach utilizes a versatile polystyrene device that contains an encapsulated microelectrode and fluidic tubing, which is shown to enable straightforward hydrodynamic focusing onto the electrode surface to improve detection. A polydimethyslsiloxane (PDMS) microchannel positioned over both the embedded tubing and SERS active electrode (aligned ∼200 μm from each other) generates a sheath flow that confines the analyte molecules eluting from the embedded tubing over the SERS electrode, increasing the interaction between the Riboflavin (vitamin B2) and the SERS active electrode. The microfluidic device was characterized using finite element simulations, amperometry, and Raman experiments. This device shows a SERS and amperometric detection limit near 1 and 100 nM, respectively. This combination of SERS and amperometry in a single device provides an improved method to identify and quantify electroactive analytes over either technique independently. PMID:25815795

  2. Short thio-multi-walled carbon nanotubes and Au nanoparticles enhanced electrochemical DNA biosensor for DNA hybridization detection

    NASA Astrophysics Data System (ADS)

    Guo, Feng; Zhang, Jimei; Dai, Zhao; Zheng, Guo

    2010-07-01

    A novel and sensitive electrochemical DNA biosensor based on multi-walled carbon nanotubes functionalized with a thio group (MWNTs-SH) and gold nanoparticles (GNPs) for covalent DNA immobilization and enhanced hybridization detection is described. The key step for developing this novel DNA biosensor is to cut the pristine MWNT into short and generate lots of active sites simultaneously. With this approach, the target DNA could be quantified in a linear range from 8.5×10-10 to 1.5×10-5 mol/L, with a detection limit of 1.67×10-11 mol/L by 3σ.

  3. [An electrochemical method for measuring metabolic activity and counting cells].

    PubMed

    Kuznetsov, B a; Khlupova, M e; Shleev, S V; Kaprel'iants, A S; Iaropolov, A I

    2006-01-01

    An express electrochemical method for determining the metabolic activity of live cells based on the possibility of an electron exchange between an electrode and elements of the biological electron transfer chain in the presence of a mediator is proposed. This method is useful for studying any live cells (animal, plant, and microbial), including anaerobic, dormant, and spore cells. The sample preparation and measurement itself does not take more than 30 min. The detection limit in a volume of 15 ml amounts to 10-5 cells/ml. The applicability of the assessment method of the metabolic activity level during the transition of the bacteria Mycobacterium smegmatis into an uncultivable dormant state was demonstrated. This method is of special value for medicine and environmental control, detecting latent forms of pathogens. An optimal combination of the methods for the express analysis of latent pathogens is proposed. PMID:17066962

  4. A label-free ultrasensitive electrochemical DNA sensor based on thin-layer MoS2 nanosheets with high electrochemical activity.

    PubMed

    Wang, Xinxing; Nan, Fuxin; Zhao, Jinlong; Yang, Tao; Ge, Tong; Jiao, Kui

    2015-02-15

    A label-free and ultrasensitive electrochemical DNA biosensor, based on thin-layer molybdenum disulfide (MoS2) nanosheets sensing platform and differential pulse voltammetry detection, is constructed in this paper. The thin-layer MoS2 nanosheets were prepared via a simple ultrasound exfoliation method from bulk MoS2, which is simpler and no distortion compared with mechanical cleavage and lithium intercalation. Most importantly, this procedure allows the formation of MoS2 with enhanced electrochemical activity. Based on the high electrochemical activity and different affinity toward ssDNA versus dsDNA of the thin-layer MoS2 nanosheets sensing platform, the tlh gene sequence assay can be performed label-freely from 1.0 × 10(-16)M to 1.0 × 10(-10)M with a detection limit of 1.9 × 10(-17)M. Without labeling and the use of amplifiers, the detection method described here not only expands the application of MoS2, but also offers a viable alternative for DNA analysis, which has the priority in sensitivity, simplicity, and costs. Moreover, the proposed sensing platform has good electrocatalytic activity, and can be extended to detect more targets, such as guanine and adenine, which further expands the application of MoS2. PMID:25262063

  5. Enhanced Electrochemical Catalytic Efficiencies of Electrochemically Deposited Platinum Nanocubes as a Counter Electrode for Dye-Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Wei, Yu-Hsuan; Tsai, Ming-Chi; Ma, Chen-Chi M.; Wu, Hsuan-Chung; Tseng, Fan-Gang; Tsai, Chuen-Horng; Hsieh, Chien-Kuo

    2015-12-01

    Platinum nanocubes (PtNCs) were deposited onto a fluorine-doped tin oxide glass by electrochemical deposition (ECD) method and utilized as a counter electrode (CE) for dye-sensitized solar cells (DSSCs). In this study, we controlled the growth of the crystalline plane to synthesize the single-crystal PtNCs at room temperature. The morphologies and crystalline nanostructure of the ECD PtNCs were examined by field emission scanning electron microscopy and high-resolution transmission electron microscopy. The surface roughness of the ECD PtNCs was examined by atomic force microscopy. The electrochemical properties of the ECD PtNCs were analyzed by cyclic voltammetry, Tafel polarization, and electrochemical impedance spectra. The Pt loading was examined by inductively coupled plasma mass spectrometry. The DSSCs were assembled via an N719 dye-sensitized titanium dioxide working electrode, an iodine-based electrolyte, and a CE. The photoelectric conversion efficiency (PCE) of the DSSCs with the ECD PtNC CE was examined under the illumination of AM 1.5 (100 mWcm-2). The PtNCs in this study presented a single-crystal nanostructure that can raise the electron mobility to let up the charge-transfer impedance and promote the charge-transfer rate. In this work, the electrocatalytic mass activity (MA) of the Pt film and PtNCs was 1.508 and 4.088 mAmg-1, respectively, and the MA of PtNCs was 2.71 times than that of the Pt film. The DSSCs with the pulse-ECD PtNC CE showed a PCE of 6.48 %, which is higher than the cell using the conventional Pt film CE (a PCE of 6.18 %). In contrast to the conventional Pt film CE which is fabricated by electron beam evaporation method, our pulse-ECD PtNCs maximized the Pt catalytic properties as a CE in DSSCs. The results demonstrated that the PtNCs played a good catalyst for iodide/triiodide redox couple reactions in the DSSCs and provided a potential strategy for electrochemical catalytic applications.

  6. Enhanced Electrochemical Catalytic Efficiencies of Electrochemically Deposited Platinum Nanocubes as a Counter Electrode for Dye-Sensitized Solar Cells.

    PubMed

    Wei, Yu-Hsuan; Tsai, Ming-Chi; Ma, Chen-Chi M; Wu, Hsuan-Chung; Tseng, Fan-Gang; Tsai, Chuen-Horng; Hsieh, Chien-Kuo

    2015-12-01

    Platinum nanocubes (PtNCs) were deposited onto a fluorine-doped tin oxide glass by electrochemical deposition (ECD) method and utilized as a counter electrode (CE) for dye-sensitized solar cells (DSSCs). In this study, we controlled the growth of the crystalline plane to synthesize the single-crystal PtNCs at room temperature. The morphologies and crystalline nanostructure of the ECD PtNCs were examined by field emission scanning electron microscopy and high-resolution transmission electron microscopy. The surface roughness of the ECD PtNCs was examined by atomic force microscopy. The electrochemical properties of the ECD PtNCs were analyzed by cyclic voltammetry, Tafel polarization, and electrochemical impedance spectra. The Pt loading was examined by inductively coupled plasma mass spectrometry. The DSSCs were assembled via an N719 dye-sensitized titanium dioxide working electrode, an iodine-based electrolyte, and a CE. The photoelectric conversion efficiency (PCE) of the DSSCs with the ECD PtNC CE was examined under the illumination of AM 1.5 (100 mWcm(-2)). The PtNCs in this study presented a single-crystal nanostructure that can raise the electron mobility to let up the charge-transfer impedance and promote the charge-transfer rate. In this work, the electrocatalytic mass activity (MA) of the Pt film and PtNCs was 1.508 and 4.088 mAmg(-1), respectively, and the MA of PtNCs was 2.71 times than that of the Pt film. The DSSCs with the pulse-ECD PtNC CE showed a PCE of 6.48 %, which is higher than the cell using the conventional Pt film CE (a PCE of 6.18 %). In contrast to the conventional Pt film CE which is fabricated by electron beam evaporation method, our pulse-ECD PtNCs maximized the Pt catalytic properties as a CE in DSSCs. The results demonstrated that the PtNCs played a good catalyst for iodide/triiodide redox couple reactions in the DSSCs and provided a potential strategy for electrochemical catalytic applications. PMID:26625891

  7. Electrochemical decolorization of dye wastewater by surface-activated boron-doped nanocrystalline diamond electrode.

    PubMed

    Chen, Chienhung; Nurhayati, Ervin; Juang, Yaju; Huang, Chihpin

    2016-07-01

    Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes (EAOPs) to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process. The performance of boron-doped nanocrystalline diamond (BD-NCD) film electrode for decolorization of Acid Yellow (AY-36) azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic. Due to the oxidation of surface functional groups and some portion of sp(2) carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation (EO) capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand (COD) removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species. PMID:27372123

  8. Electrochemical activation of a tetrathiafulvalene halogen bond donor in solution.

    PubMed

    Oliveira, R; Groni, S; Fave, C; Branca, M; Mavré, F; Lorcy, D; Fourmigué, M; Schöllhorn, B

    2016-06-21

    The halogen bond donor properties of iodo-tetrathiafulvalene (I-TTF) can be electrochemically switched and controlled via reversible oxidation in the solution phase. Interestingly the activation of only one single halogen bond yielded already a strong and selective interaction, quantified by cyclic voltammetry. The standard potentials of the redox couples I-TTF(0/1+) and I-TTF(1+/2+) were observed to shift upon the addition of halides. These anions selectively stabilize the cationic I-TTF species through halogen bonding in polar liquid electrolytes. The thermodynamic affinity constants for chloride and bromide binding to the oxidized species have been determined. Competition in halide binding between I-TTF(1+) and other halogen bond donors allowed for comparing the relative donor strength of the respective electrophilic species. Furthermore it has been shown that halogen bonding can prevail over hydrogen bonding in the investigated system. PMID:27231819

  9. Effect of the iridium oxide thin film on the electrochemical activity of platinum nanoparticles.

    PubMed

    Chen, Aicheng; La Russa, Daniel J; Miller, Brad

    2004-10-26

    The influence of the iridium oxide thin film on the electrocatalytic properties of platinum nanoparticles was investigated using the electro-oxidation of methanol and CO as a probe. The presence of the IrO(2) thin film leads to the homogeneous dispersion of Pt nanoparticles. For comparison, polycrystalline platinum and Pt nanoparticles dispersed on a Ti substrate in the absence of an IrO(2) layer (Ti/Pt) were also investigated in this study. Inverted and enhanced CO bipolar peaks were observed using an in situ electrochemical Fourier transform infrared technique during the methanol oxidation on the Pt nanoparticles dispersed on a Ti substrate. Electrochemical impedance studies showed that the charge transfer resistance was significantly lower for the Ti/IrO(2)/Pt electrode compared with that of the massive Pt and Ti/Pt nanoparticles. The presence of the IrO(2) thin film not only greatly increases the active surface area but also promotes CO oxidation at a much lower electrode potential, thus, significantly enhancing the electrocatalytic activity of Pt nanoparticles toward methanol electro-oxidation. PMID:15491204

  10. Removal of Persistent Organic Contaminants by Electrochemically Activated Sulfate.

    PubMed

    Farhat, Ali; Keller, Jurg; Tait, Stephan; Radjenovic, Jelena

    2015-12-15

    Solutions of sulfate have often been used as background electrolytes in the electrochemical degradation of contaminants and have been generally considered inert even when high-oxidation-power anodes such as boron-doped diamond (BDD) were employed. This study examines the role of sulfate by comparing electro-oxidation rates for seven persistent organic contaminants at BDD anodes in sulfate and inert nitrate anolytes. Sulfate yielded electro-oxidation rates 10-15 times higher for all target contaminants compared to the rates of nitrate anolyte. This electrochemical activation of sulfate was also observed at concentrations as low as 1.6 mM, which is relevant for many wastewaters. Electrolysis of diatrizoate in the presence of specific radical quenchers (tert-butanol and methanol) had a similar effect on electro-oxidation rates, illustrating a possible role of the hydroxyl radical ((•)OH) in the anodic formation of sulfate radical (SO4(•-)) species. The addition of 0.55 mM persulfate increased the electro-oxidation rate of diatrizoate in nitrate from 0.94 to 9.97 h(-1), suggesting a nonradical activation of persulfate. Overall findings indicate the formation of strong sulfate-derived oxidant species at BDD anodes when polarized at high potentials. This may have positive implications in the electro-oxidation of wastewaters containing sulfate. For example, the energy required for the 10-fold removal of diatrizoate was decreased from 45.6 to 2.44 kWh m(-3) by switching from nitrate to sulfate anolyte. PMID:26572594

  11. Enhanced performance of gas diffusion electrode for electrochemical reduction of carbon dioxide to formate by adding polytetrafluoroethylene into catalyst layer

    NASA Astrophysics Data System (ADS)

    Wang, Qinian; Dong, Heng; Yu, Han; Yu, Hongbing

    2015-04-01

    Gas diffusion electrode (GDE) with Nafion bonded catalyst layer (CL) for electrochemical reduction of CO2 to formate (ERCF) suffers from CO2 mass transfer limitation. In this work, polytetrafluoroethylene (PTFE) with contents of 5.9 wt%, 7.7 wt%, 11.1 wt% and 20 wt% are added into the CL of the GDE with Sn catalyst (P-SGDE) for ERCF. The morphologies and porous structures of the P-SGDEs are examined by scanning electron microscope and mercury intrusion measurement, respectively. The electrochemical performances of the P-SGDEs are investigated by linear sweep voltammetry, electrochemical impedance spectroscopy and constant potential electrolysis. The results show that the Faraday efficiency (86.75 ± 2.89%) and current density (21.67 ± 1.29 mA cm-2) for ERCF were improved by 25.4% and 25.8% respectively when the content of PTFE is 11.1 wt%, probably owing to the enhancement in the catalyst active surface area and CO2 diffusion. This Faraday efficiency is the highest one found for ERCF with Sn GDE under similar conductions.

  12. Enhancing the Sensitivity of Needle-Implantable Electrochemical Glucose Sensors via Surface Rebuilding

    PubMed Central

    Vaddiraju, Santhisagar; Legassey, Allen; Qiang, Liangliang; Wang, Yan; Burgess, Diane J.; Papadimitrakopoulos, Fotios

    2013-01-01

    Background Needle-implantable sensors have shown to provide reliable continuous glucose monitoring for diabetes management. In order to reduce tissue injury during sensor implantation, there is a constant need for device size reduction, which imposes challenges in terms of sensitivity and reliability, as part of decreasing signal-to-noise and increasing layer complexity. Herein, we report sensitivity enhancement via electrochemical surface rebuilding of the working electrode (WE), which creates a three-dimensional nanoporous configuration with increased surface area. Methods The gold WE was electrochemically rebuilt to render its surface nanoporous followed by decoration with platinum nanoparticles. The efficacy of such process was studied using sensor sensitivity against hydrogen peroxide (H2O2). For glucose detection, the WE was further coated with five layers, namely, (1) polyphenol, (2) glucose oxidase, (3) polyurethane, (4) catalase, and (5) dexamethasone-releasing poly(vinyl alcohol)/poly(lactic-co-glycolic acid) composite. The amperometric response of the glucose sensor was noted in vitro and in vivo. Results Scanning electron microscopy revealed that electrochemical rebuilding of the WE produced a nanoporous morphology that resulted in a 20-fold enhancement in H2O2 sensitivity, while retaining >98% selectivity. This afforded a 4–5-fold increase in overall glucose response of the glucose sensor when compared with a control sensor with no surface rebuilding and fittable only within an 18 G needle. The sensor was able to reproducibly track in vivo glycemic events, despite the large background currents typically encountered during animal testing. Conclusions Enhanced sensor performance in terms of sensitivity and large signal-to-noise ratio has been attained via electrochemical rebuilding of the WE. This approach also bypasses the need for conventional and nanostructured mediators currently employed to enhance sensor performance. PMID:23567003

  13. Rolling chain amplification based signal-enhanced electrochemical aptasensor for ultrasensitive detection of ochratoxin A.

    PubMed

    Huang, Lin; Wu, Jingjing; Zheng, Lei; Qian, Haisheng; Xue, Feng; Wu, Yucheng; Pan, Daodong; Adeloju, Samuel B; Chen, Wei

    2013-11-19

    A novel electrochemical aptasensor is described for rapid and ultrasensitive detection of ochratoxin A (OTA) based on signal enhancement with rolling circle amplification (RCA). The primer for RCA was designed to compose of a two-part sequence, one part of the aptamer sequence directed against OTA while the other part was complementary to the capture probe on the electrode surface. In the presence of target OTA, the primer, originally hybridized with the RCA padlock, is replaced to combine with OTA. This induces the inhibition of RCA and decreases the OTA sensing signal obtained with the electrochemical aptasensor. Under the optimized conditions, ultrasensitive detection of OTA was achieved with a limit of detection (LOD) of 0.065 ppt (pg/mL), which is much lower than previously reported. The electrochemical aptasensor was also successfully applied to the determination of OTA in wine samples. This ultrasensitive electrochemical aptasensor is of great practical importance in food safety and could be widely extended to the detection of other toxins by replacing the sequence of the recognition aptamer. PMID:24206525

  14. Effect of nano-scale characteristics of graphene on electrochemical performance of activated carbon supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Jasni, M. R. M.; Deraman, M.; Suleman, M.; Hamdan, E.; Sazali, N. E. S.; Nor, N. S. M.; Shamsudin, S. A.

    2016-02-01

    Graphene with its typical nano-scale characteristic properties has been widely used as an additive in activated carbon electrodes in order to enhance the performance of the electrodes for their use in high performance supercapacitors. Activated carbon monoliths (ACMs) electrodes have been prepared by carbonization and activation of green monoliths (GMs) of pre-carbonized fibers of oil palm empty fruit bunches or self-adhesive carbon grains (SACGs) and SACGs added with 6 wt% of KOH-treated multi-layer graphene. ACMs electrodes have been assembled in symmetrical supercapacitor cells that employed aqueous KOH electrolyte (6 M). The cells have been tested with cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge discharge methods to investigate the effect of graphene addition on the specific capacitance (Csp), specific energy (E), specific power (P), equivalent series resistance (ESR) and response time (τo) of the supercapacitor cells. The results show that the addition of graphene in the GMs change the values of Csp, Emax, Pmax, ESR and τo from (61-96) F/g, 2 Wh/kg, 104 W/kg, 2.6 Ω and 38 s, to the respective values of (110-124) F/g, 3 Wh/kg, 156 W/kg, 3.4 Ω and 63 s. This study demonstrates that the graphene addition in the GMs has a significant effect on the electrochemical behavior of the electrodes.

  15. [Nonequilibrium state of electrochemically activated water and its biological activity].

    PubMed

    Petrushanko, I Iu; Lobyshev, V I

    2001-01-01

    Changes in the physicochemical parameters (pH, redox potential and electroconductivity) of catholyte and anolyte produced by membrane electrolysis of distilled water and dilute (c < 10(-3) M) sodium chloride solutions were studied. The relaxation of these parameters after electrolysis and the influence of catholyte and anolyte on the growth of roots of Tradescantia viridis grafts, the development of duckweed, and the motive activity of infusoria Spirostomum ambiguum were investigated. It was found that the anolyte of distilled water stimulated development of these biological objects. The direction of shift of physicochemical parameters of catholyte and anolyte from equilibrium values and the type of their biological activity (stimulation or inhibition) depend on salt concentration in initial solution. Barbotage of initial distilled water with argon or nitrogen leads to a greater decrease in the redox potential of catholyte during electrolysis. The physicochemical parameters relax to equilibrium values, and the biological activity of catholite and anolyte decreases with time and practically disappears by the end of the day. It was found that the oxidation of reducing agent by atmospheric oxygen is not the sole cause of the relaxation of catalyte redox potential. The increase in the ionic strength of catholite and anolyte by the addition of concentrated sodium chloride after electrolysis decreases the rate of redox potential relaxation several times. The redox potential can be maintained for long periods by freezing. PMID:11449536

  16. Significantly enhanced robustness and electrochemical performance of flexible carbon nanotube-based supercapacitors by electrodepositing polypyrrole

    NASA Astrophysics Data System (ADS)

    Chen, Yanli; Du, Lianhuan; Yang, Peihua; Sun, Peng; Yu, Xiang; Mai, Wenjie

    2015-08-01

    Here, we report robust, flexible CNT-based supercapacitor (SC) electrodes fabricated by electrodepositing polypyrrole (PPy) on freestanding vacuum-filtered CNT film. These electrodes demonstrate significantly improved mechanical properties (with the ultimate tensile strength of 16 MPa), and greatly enhanced electrochemical performance (5.6 times larger areal capacitance). The major drawback of conductive polymer electrodes is the fast capacitance decay caused by structural breakdown, which decreases cycling stability but this is not observed in our case. All-solid-state SCs assembled with the robust CNT/PPy electrodes exhibit excellent flexibility, long lifetime (95% capacitance retention after 10,000 cycles) and high electrochemical performance (a total device volumetric capacitance of 4.9 F/cm3). Moreover, a flexible SC pack is demonstrated to light up 53 LEDs or drive a digital watch, indicating the broad potential application of our SCs for portable/wearable electronics.

  17. Enhanced Conversion Efficiency of Cu(In,Ga)Se2 Solar Cells via Electrochemical Passivation Treatment.

    PubMed

    Tsai, Hung-Wei; Thomas, Stuart R; Chen, Chia-Wei; Wang, Yi-Chung; Tsai, Hsu-Sheng; Yen, Yu-Ting; Hsu, Cheng-Hung; Tsai, Wen-Chi; Wang, Zhiming M; Chueh, Yu-Lun

    2016-03-30

    Defect control in Cu(In,Ga)Se2 (CIGS) materials, no matter what the defect type or density, is a significant issue, correlating directly to PV performance. These defects act as recombination centers and can be briefly categorized into interface recombination and Shockley-Read-Hall (SRH) recombination, both of which can lead to reduced PV performance. Here, we introduce an electrochemical passivation treatment for CIGS films that can lower the oxygen concentration at the CIGS surface as observed by X-ray photoelectron spectrometer analysis. Temperature-dependent J-V characteristics of CIGS solar cells reveal that interface recombination is suppressed and an improved rollover condition can be achieved following our electrochemical treatment. As a result, the surface defects are passivated, and the power conversion efficiency performance of the solar cell devices can be enhanced from 4.73 to 7.75%. PMID:26815164

  18. Enhanced NIF neutron activation diagnostics

    SciTech Connect

    Yeamans, C. B.; Bleuel, D. L.; Bernstein, L. A.

    2012-10-15

    The NIF neutron activation diagnostic suite relies on removable activation samples, leading to operational inefficiencies and a fundamental lower limit on the half-life of the activated product that can be observed. A neutron diagnostic system measuring activation of permanently installed samples could remove these limitations and significantly enhance overall neutron diagnostic capabilities. The physics and engineering aspects of two proposed systems are considered: one measuring the {sup 89}Zr/{sup 89m}Zr isomer ratio in the existing Zr activation medium and the other using potassium zirconate as the activation medium. Both proposed systems could improve the signal-to-noise ratio of the current system by at least a factor of 5 and would allow independent measurement of fusion core velocity and fuel areal density.

  19. Polypyrrole coated carbon nanotubes for supercapacitor devices with enhanced electrochemical performance

    NASA Astrophysics Data System (ADS)

    Zhu, Yeling; Shi, Kaiyuan; Zhitomirsky, Igor

    2014-12-01

    Polypyrrole (PPy) electrodes for electrochemical supercapacitors (ES) are prepared using amaranth as a new redox-active anionic dopant for chemical polymerization of PPy. The use of amaranth allows excellent electrochemical performance of electrodes with high mass loading and high PPy to current collector mass ratio. The specific capacitance of 4.2 F cm-2 is achieved at a scan rate of 2 mV s-1. The analysis of electrochemical testing results provides an insight into the influence of the chemical structure of amaranth on microstructure, electrochemical properties and cycling stability of PPy. New method is introduced for the fabrication of PPy coated multiwalled carbon nanotubes (MWCNT). The use of amaranth allows fine microstructure of PPy coatings formed on MWCNT, which are well dispersed in the presence of pyrocatechol violet dispersant. The use of PPy coated MWCNT allows significant improvement in capacitance retention at high charge-discharge rates, compared to pure PPy material, and good cycling stability of individual electrodes and ES cells. The ES cells, based on PPy show specific capacitance of 1.3-1.6 F cm-2 at discharge current densities of 1-33 mA cm-2.

  20. Combined geochemical and electrochemical methodology to quantify corrosion of carbon steel by bacterial activity.

    PubMed

    Schütz, Marta K; Moreira, Rebeca; Bildstein, Olivier; Lartigue, Jean-Eric; Schlegel, Michel L; Tribollet, Bernard; Vivier, Vincent; Libert, Marie

    2014-06-01

    The availability of respiratory substrates, such as H2 and Fe(II,III) solid corrosion products within nuclear waste repository, will sustain the activities of hydrogen-oxidizing bacteria (HOB) and iron-reducing bacteria (IRB). This may have a direct effect on the rate of carbon steel corrosion. This study investigates the effects of Shewanella oneidensis (an HOB and IRB model organism) on the corrosion rate by looking at carbon steel dissolution in the presence of H2 as the sole electron donor. Bacterial effect is evaluated by means of geochemical and electrochemical techniques. Both showed that the corrosion rate is enhanced by a factor of 2-3 in the presence of bacteria. The geochemical experiments indicated that the composition and crystallinity of the solid corrosion products (magnetite and vivianite) are modified by bacteria. Moreover, the electrochemical experiments evidenced that the bacterial activity can be stimulated when H2 is generated in a small confinement volume. In this case, a higher corrosion rate and mineralization (vivianite) on the carbon steel surface were observed. The results suggest that the mechanism likely to influence the corrosion rate is the bioreduction of Fe(III) from magnetite coupled to the H2 oxidation. PMID:24064199

  1. Methylene blue not ferrocene: Optimal reporters for electrochemical detection of protease activity.

    PubMed

    González-Fernández, Eva; Avlonitis, Nicolaos; Murray, Alan F; Mount, Andrew R; Bradley, Mark

    2016-10-15

    Electrochemical peptide-based biosensors are attracting significant attention for the detection and analysis of proteins. Here we report the optimisation and evaluation of an electrochemical biosensor for the detection of protease activity using self-assembled monolayers (SAMs) on gold surfaces, using trypsin as a model protease. The principle of detection was the specific proteolytic cleavage of redox-tagged peptides by trypsin, which causes the release of the redox reporter, resulting in a decrease of the peak current as measured by square wave voltammetry. A systematic enhancement of detection was achieved through optimisation of the properties of the redox-tagged peptide; this included for the first time a side-by-side study of the applicability of two of the most commonly applied redox reporters used for developing electrochemical biosensors, ferrocene and methylene blue, along with the effect of changing both the nature of the spacer and the composition of the SAM. Methylene blue-tagged peptides combined with a polyethylene-glycol (PEG) based spacer were shown to be the best platform for trypsin detection, leading to the highest fidelity signals (characterised by the highest sensitivity (signal gain) and a much more stable background than that registered when using ferrocene as a reporter). A ternary SAM (T-SAM) configuration, which included a PEG-based dithiol, minimised the non-specific adsorption of other proteins and was sensitive towards trypsin in the clinically relevant range, with a Limit of Detection (LoD) of 250pM. Kinetic analysis of the electrochemical response with time showed a good fit to a Michaelis-Menten surface cleavage model, enabling the extraction of values for kcat and KM. Fitting to this model enabled quantitative determination of the solution concentration of trypsin across the entire measurement range. Studies using an enzyme inhibitor and a range of real world possible interferents demonstrated a selective response to trypsin

  2. Enhanced electrochemical performance and manganese redox activity of LiFe0.4Mn0.6PO4 by iodine anion substitution as cathode material for Li-ion battery

    NASA Astrophysics Data System (ADS)

    Sin, Byung Cheol; Singh, Laxman; An, JiEun; Lee, Hansol; Lee, Hyung-il; Lee, Youngil

    2016-05-01

    For the first time, an attempt has been made for the possible augmentation and exploration of iodine substitution into LiFe0.4Mn0.6PO4 (LFMP) material is assessed as a cathode material for lithium ion batteries. Iodine substituted LiFe0.4Mn0.6(PO4)1-xIx (LFMPI, x = 0, 0.01, 0.015, and 0.02) have been synthesized by a solid-state reaction without any external carbon source. X-ray diffraction shows that the LFMP and LFMPI cathode materials have formed the same single crystalline phase; the values of lattice parameters and unit cell volume have been insignificantly changed by I- anion substitution. Uniformly distributed grains of the LFMPI samples with grain sizes in the range of 250 nm to 0.9 μm have been obtained by scanning electron microscopy. X-ray photoelectron spectroscopy for the LFMPI with x = 0.02 have clearly observed at 619.5 and 630.7 eV for I 3d5/2 and I 3d3/2, respectively. The electrochemical properties of the pure LFMP cathode material have been compared with those of I- anion substituted LFMPI samples. LFMPI with x = 0.015 has delivered the highest discharge capacity of 141.5 mAh g-1 at 0.1C, and LFMPI with x = 0.01 has 102.1 mAh g-1 at high rate of 3C. Iodine substituted LFMPI have demonstrated improved electrochemical properties with excellent reversible cycling.

  3. Hierarchical nanostructured conducting polymer hydrogel with high electrochemical activity

    PubMed Central

    Pan, Lijia; Yu, Guihua; Zhai, Dongyuan; Lee, Hye Ryoung; Zhao, Wenting; Liu, Nian; Wang, Huiliang; Tee, Benjamin C.-K.; Shi, Yi; Cui, Yi; Bao, Zhenan

    2012-01-01

    Conducting polymer hydrogels represent a unique class of materials that synergizes the advantageous features of hydrogels and organic conductors and have been used in many applications such as bioelectronics and energy storage devices. They are often synthesized by polymerizing conductive polymer monomer within a nonconducting hydrogel matrix, resulting in deterioration of their electrical properties. Here, we report a scalable and versatile synthesis of multifunctional polyaniline (PAni) hydrogel with excellent electronic conductivity and electrochemical properties. With high surface area and three-dimensional porous nanostructures, the PAni hydrogels demonstrated potential as high-performance supercapacitor electrodes with high specific capacitance (∼480 F·g-1), unprecedented rate capability, and cycling stability (∼83% capacitance retention after 10,000 cycles). The PAni hydrogels can also function as the active component of glucose oxidase sensors with fast response time (∼0.3 s) and superior sensitivity (∼16.7 μA·mM-1). The scalable synthesis and excellent electrode performance of the PAni hydrogel make it an attractive candidate for bioelectronics and future-generation energy storage electrodes. PMID:22645374

  4. Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

    PubMed

    He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

    2016-06-01

    Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability. PMID:27180820

  5. Microstructured photopolymer films of electrochemically active monomers. Fabrication of an electrochemically switchable phase grating

    SciTech Connect

    Schanze, K.S.; Bergstedt, T.S.; Hauser, B.T.

    1995-12-01

    Contact photolithography is used to create thin polymeric films comprised of viologen and co-monomer (1:1 mole ratio). The poly-1/2 films are 100 - 150 nm thick with 5 {mu}m linewidths. Films of poly-1/2 supported on In-SnO{sub 2} display a quasi-reversible wave at -0.25 V vs. Ag/AgCl for the (2+/1+{sm_bullet}) couple of the viologen. Grating patterned poly-1/2 films with a spatial frequency of 100 lines/mm diffract light. The diffraction efficiency of these phase gratings increases substantially concomitant with electrochemical reduction of the viologen sites. The change in diffraction efficiency is reversible and is attributed to an electrochemically induced change in refractive index of the film.

  6. Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge.

    PubMed

    Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D; Boettcher, Shannon W

    2015-01-01

    Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg(-1) based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30-50 Wh kg(-1) is possible with optimization. PMID:26239891

  7. Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge

    PubMed Central

    Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D.; Boettcher, Shannon W.

    2015-01-01

    Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg−1 based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30–50 Wh kg−1 is possible with optimization. PMID:26239891

  8. Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge

    NASA Astrophysics Data System (ADS)

    Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D.; Boettcher, Shannon W.

    2015-08-01

    Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ~14 Wh kg-1 based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30-50 Wh kg-1 is possible with optimization.

  9. The electrochemical oxidation of methanol on a Pt/TNTs/Ti electrode enhanced by illumination

    NASA Astrophysics Data System (ADS)

    Wang, Y. Q.; Wei, Z. D.; Gao, B.; Qi, X. Q.; Li, L.; Zhang, Q.; Xia, M. R.

    A Pt/TNTs/Ti electrode is prepared by electrochemically depositing Pt using the modulated pulse current method onto high density, well ordered and uniformly distributed TiO 2 nanotubes (TNTs) on a Ti substrate. The results show that the performance and anti-poison ability of the Pt/TNTs/Ti electrode for methanol electro-oxidation under illumination is remarkably enhanced and is even better than the best bi-metallic Pt-Ru catalysts. CO poisoning is no longer a problem during methanol electro-oxidation with the Pt/TNTs/Ti electrode under illumination.

  10. Probing Redox Reactions at the Nanoscale with Electrochemical Tip-Enhanced Raman Spectroscopy.

    PubMed

    Kurouski, Dmitry; Mattei, Michael; Van Duyne, Richard P

    2015-12-01

    A fundamental understanding of electrochemical processes at the nanoscale is crucial to solving problems in research areas as diverse as electrocatalysis, energy storage, biological electron transfer, and plasmon-driven chemistry. However, there is currently no technique capable of directly providing chemical information about molecules undergoing heterogeneous charge transfer at the nanoscale. Tip-enhanced Raman spectroscopy (TERS) uniquely offers subnanometer spatial resolution and single-molecule sensitivity, making it the ideal tool for studying nanoscale electrochemical processes with high chemical specificity. In this work, we demonstrate the first electrochemical TERS (EC-TERS) study of the nanoscale redox behavior of Nile Blue (NB), and compare these results with conventional cyclic voltammetry (CV). We successfully monitor the disappearance of the 591 cm(-1) band of NB upon reduction and its reversible reappearance upon oxidation during the CV. Interestingly, we observe a negative shift of more than 100 mV in the onset of the potential response of the TERS intensity of the 591 cm(-1) band, compared to the onset of faradaic current in the CV. We hypothesize that perturbation of the electrical double-layer by the TERS tip locally alters the effective potential experienced by NB molecules in the tip-sample junction. However, we demonstrate that the tip has no effect on the local charge transfer kinetics. Additionally, we observe step-like behavior in some TERS voltammograms corresponding to reduction and oxidation of single or few NB molecules. We also show that the coverage of NB is nonuniform across the ITO surface. We conclude with a discussion of methods to overcome the perturbation of the double-layer and general considerations for using TERS to study nanoscale electrochemical processes. PMID:26580153

  11. Electrodeposition and Screening of Photoelectrochemical Activity in Conjugated Polymers Using Scanning Electrochemical Cell Microscopy.

    PubMed

    Aaronson, Barak D B; Garoz-Ruiz, Jesus; Byers, Joshua C; Colina, Alvaro; Unwin, Patrick R

    2015-11-24

    A number of renewable energy systems require an understanding and correlation of material properties and photoelectrochemical activity on the micro to nanoscale. Among these, conducting polymer electrodes continue to be important materials. In this contribution, an ultrasensitive scanning electrochemical cell microscopy (SECCM) platform is used to electrodeposit microscale thin films of poly(3-hexylthiophene) (P3HT) on an optically transparent gold electrode and to correlate the morphology (film thickness and structural order) with photoactivity. The electrochemical growth of P3HT begins with a thin ordered film up to 10 nm thick, after which a second more disordered film is deposited, as revealed by micro-Raman spectroscopy. A decrease in photoactivity for the thicker films, measured in situ immediately following film deposition, is attributed to an increase in bulk film disorder that limits charge transport. Higher resolution ex situ SECCM phototransient measurements, using a smaller diameter probe, show local variations in photoactivity within a given deposit. Even after aging, thinner, more ordered regions within a deposit exhibit sustained enhanced photocurrent densities compared to areas where the film is thicker and more disordered. The platform opens up new possibilities for high-throughput combinatorial correlation studies, by allowing materials fabrication and high spatial resolution probing of processes in photoelectrochemical materials. PMID:26502089

  12. Inhibited Ru(bpy)3 2+ electrochemiluminescence related to electrochemical oxidation activity of inhibitors.

    PubMed

    Chi, Yuwu; Dong, Yongqiang; Chen, Guonan

    2007-06-15

    Electrochemiluminescence (ECL) has been accepted by the analytical chemist as a powerful tool for detection of many inorganic and organic compounds. Ru(bpy)3 2+ has been the most popular ECL system, and many investigations have been focused on the application based on the enhancement or inhibition of Ru(bpy)3 2+ ECL system. However, not much attention has been paid to the theoretical investigation of this ECL system, especially to the inhibiting mechanism for the Ru(bpy)3 2+ ECL system. In the present study, many of the inorganic and organic compounds with electrochemical oxidation activity were found to strongly inhibit Ru(bpy)3 2+ ECL. To explain these inhibited ECL phenomena, a new "electrochemical oxidation inhibiting" mechanism has been proposed via the establishment of a corresponding model. The effects of applied potential, uncompensated resistance, and concentration of inhibitor on the inhibited ECL derived from the model have been verified by experiments. The new ECL inhibition mechanism can be commonly used to explain many kinds of inhibited ECL presently observed, and it is envisioned to result in finding of more inhibitors of this type and establishment of new sensitive ECL detection methods for them. PMID:17489558

  13. Electrochemical flow injection analysis of hydrazine in an excess of an active pharmaceutical ingredient: achieving pharmaceutical detection limits electrochemically.

    PubMed

    Channon, Robert B; Joseph, Maxim B; Bitziou, Eleni; Bristow, Anthony W T; Ray, Andrew D; Macpherson, Julie V

    2015-10-01

    The quantification of genotoxic impurities (GIs) such as hydrazine (HZ) is of critical importance in the pharmaceutical industry in order to uphold drug safety. HZ is a particularly intractable GI and its detection represents a significant technical challenge. Here, we present, for the first time, the use of electrochemical analysis to achieve the required detection limits by the pharmaceutical industry for the detection of HZ in the presence of a large excess of a common active pharmaceutical ingredient (API), acetaminophen (ACM) which itself is redox active, typical of many APIs. A flow injection analysis approach with electrochemical detection (FIA-EC) is utilized, in conjunction with a coplanar boron doped diamond (BDD) microband electrode, insulated in an insulating diamond platform for durability and integrated into a two piece flow cell. In order to separate the electrochemical signature for HZ such that it is not obscured by that of the ACM (present in excess), the BDD electrode is functionalized with Pt nanoparticles (NPs) to significantly shift the half wave potential for HZ oxidation to less positive potentials. Microstereolithography was used to fabricate flow cells with defined hydrodynamics which minimize dispersion of the analyte and optimize detection sensitivity. Importantly, the Pt NPs were shown to be stable under flow, and a limit of detection of 64.5 nM or 0.274 ppm for HZ with respect to the ACM, present in excess, was achieved. This represents the first electrochemical approach which surpasses the required detection limits set by the pharmaceutical industry for HZ detection in the presence of an API and paves the wave for online analysis and application to other GI and API systems. PMID:26302058

  14. Beneficial effect of Re doping on the electrochemical HER activity of MoS2 fullerenes.

    PubMed

    Chhetri, Manjeet; Gupta, Uttam; Yadgarov, Lena; Rosentsveig, Rita; Tenne, Reshef; Rao, C N R

    2015-10-01

    Electrochemical generation of hydrogen by non-precious metal electrocatalysts at a lower overpotential is a focus area of research directed towards sustainable energy. The exorbitant costs associated with Pt-based catalysts is the major bottleneck associated with commercial-scale hydrogen generation. Strategies for the synthesis of cost-effective and stable catalysts are thus key for a prospective 'hydrogen economy'. In this report, we highlight a novel and general strategy to enhance the electrochemical activity of molybdenum disulfide (MoS2) in a fullerene structure (IF-). In particular, pristine (undoped) and rhenium-doped nanoparticles of MoS2 with fullerene-like structures (IF-MoS2) were studied, and their performance as catalysts for the hydrogen evolution reaction (HER) was compared to that of 2H-MoS2 particles (platelets). The current density of the IF-MoS2 was higher by one order of magnitude than that of few-layer (FL-) MoS2, due to the enhanced density of the edge sites. Furthermore, Re doping of as low as 100 ppm in IF-MoS2 decreased the onset potential by 60-80 mV and increased the activity by 60 times compared with that of the FL-MoS2. The combined synergistic effect of Re doping and the IF structure not only changes the intrinsic nature of the MoS2 but also increases its reactivity. This strategy highlights the potential use of the IF structure and Re doping in electrocatalytic hydrogen evolution using MoS2-based catalysts. PMID:26308554

  15. Influence of reactivation on the electrochemical performances of activated carbon based on coconut shell.

    PubMed

    Geng, Xin; Li, Lixiang; Zhang, Meiling; An, Baigang; Zhu, Xiaoming

    2013-12-01

    Coconut shell-based activated carbon (AC) were prepared by CO2 activation, and then the ACs with higher mesopore ratio were obtained by steam activation and by impregnating iron catalyst followed by steam activation, respectively. The AC with the highest mesopore ratio (AChmr) shows superior capacitive behavior, power output and high-frequency performance in supercapacitors. The results should attribute to the connection of its wide micropores and mesopores larger than 3 nm, which is more favorable for fast ionic transportation. The pore size distribution exhibits that the mesopore ratios of the ACs are significantly increased by reactivation of steam or catalyst up to 75% and 78%, respectively. As evidenced by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic measurements, the AChmr shows superior capacitive behaviors, conductivity and performance of electrolytic ionic transportation. The response current densities are evidently enhanced through the cyclic voltammery test at 50 mV/sec scan rate. The electrochemical impedance spectroscopy demonstrates that the conductivity and ion transport performance of the ACs are improved. The specific capacitances of the ACs were increased from 140 to 240 F/g at 500 mA/g current density. The AChmr can provide much higher power density while still maintaining good energy density, and demonstrate excellent high-frequency performances. The pore structure and conductivity of the AChmr also improve the cycleability and self-discharge of supercapacitors. Such AChmr exhibits a great potential in supercapacitors, particularly for applications where high power output and good high-frequency capacitive performances are required. PMID:25078811

  16. CuO nanowire/microflower/nanowire modified Cu electrode with enhanced electrochemical performance for non-enzymatic glucose sensing.

    PubMed

    Li, Changli; Yamahara, Hiroyasu; Lee, Yaerim; Tabata, Hitoshi; Delaunay, Jean-Jacques

    2015-07-31

    CuO nanowire/microflower structure on Cu foil is synthesized by annealing a Cu(OH)2 nanowire/CuO microflower structure at 250 °C in air. The nanowire/microflower structure with its large surface area leads to an efficient catalysis and charge transfer in glucose detection, achieving a high sensitivity of 1943 μA mM(-1) cm(-2), a wide linear range up to 4 mM and a low detection limit of 4 μM for amperometric glucose sensing in alkaline solution. With a second consecutive growth of CuO nanowires on the microflowers, the sensitivity of the obtained CuO nanowire/microflower/nanowire structure further increases to 2424 μA mM(-1) cm(-2), benefiting from an increased number of electrochemically active sites. The enhanced electrocatalytic performance of the CuO nanowire/microflower/nanowire electrode compared to the CuO nanowire/microflower electrode, CuO nanowire electrode and CuxO film electrode provides evidence for the significant role of available surface area for electrocatalysis. The rational combination of CuO nanowire and microflower nanostructures into a nanowire supporting microflower branching nanowires structure makes it a promising composite nanostructure for use in CuO based electrochemical sensors with promising analytical properties. PMID:26159235

  17. CuO nanowire/microflower/nanowire modified Cu electrode with enhanced electrochemical performance for non-enzymatic glucose sensing

    NASA Astrophysics Data System (ADS)

    Li, Changli; Yamahara, Hiroyasu; Lee, Yaerim; Tabata, Hitoshi; Delaunay, Jean-Jacques

    2015-07-01

    CuO nanowire/microflower structure on Cu foil is synthesized by annealing a Cu(OH)2 nanowire/CuO microflower structure at 250 °C in air. The nanowire/microflower structure with its large surface area leads to an efficient catalysis and charge transfer in glucose detection, achieving a high sensitivity of 1943 μA mM-1 cm-2, a wide linear range up to 4 mM and a low detection limit of 4 μM for amperometric glucose sensing in alkaline solution. With a second consecutive growth of CuO nanowires on the microflowers, the sensitivity of the obtained CuO nanowire/microflower/nanowire structure further increases to 2424 μA mM-1 cm-2, benefiting from an increased number of electrochemically active sites. The enhanced electrocatalytic performance of the CuO nanowire/microflower/nanowire electrode compared to the CuO nanowire/microflower electrode, CuO nanowire electrode and CuxO film electrode provides evidence for the significant role of available surface area for electrocatalysis. The rational combination of CuO nanowire and microflower nanostructures into a nanowire supporting microflower branching nanowires structure makes it a promising composite nanostructure for use in CuO based electrochemical sensors with promising analytical properties.

  18. Ultra-high electrochemical catalytic activity of MXenes

    PubMed Central

    Pan, Hui

    2016-01-01

    Cheap and abundant electrocatalysts for hydrogen evolution reactions (HER) have been widely pursued for their practical application in hydrogen-energy technologies. In this work, I present systematical study of the hydrogen evolution reactions on MXenes (Mo2X and W2X, X = C and N) based on density-functional-theory calculations. I find that their HER performances strongly depend on the composition, hydrogen adsorption configurations, and surface functionalization. I show that W2C monolayer has the best HER activity with near-zero overpotential at high hydrogen density among all of considered pure MXenes, and hydrogenation can efficiently enhance its catalytic performance in a wide range of hydrogen density further, while oxidization makes its activity reduced significantly. I further show that near-zero overpotential for HER on Mo2X monolayers can be achieved by oxygen functionalization. My calculations predict that surface treatment, such as hydrogenation and oxidization, is critical to enhance the catalytic performance of MXenes. I expect that MXenes with HER activity comparable to Pt in a wide range of hydrogen density can be realized by tuning composition and functionalizing, and promotes their applications into hydrogen-energy technologies. PMID:27604848

  19. Ultra-high electrochemical catalytic activity of MXenes.

    PubMed

    Pan, Hui

    2016-01-01

    Cheap and abundant electrocatalysts for hydrogen evolution reactions (HER) have been widely pursued for their practical application in hydrogen-energy technologies. In this work, I present systematical study of the hydrogen evolution reactions on MXenes (Mo2X and W2X, X = C and N) based on density-functional-theory calculations. I find that their HER performances strongly depend on the composition, hydrogen adsorption configurations, and surface functionalization. I show that W2C monolayer has the best HER activity with near-zero overpotential at high hydrogen density among all of considered pure MXenes, and hydrogenation can efficiently enhance its catalytic performance in a wide range of hydrogen density further, while oxidization makes its activity reduced significantly. I further show that near-zero overpotential for HER on Mo2X monolayers can be achieved by oxygen functionalization. My calculations predict that surface treatment, such as hydrogenation and oxidization, is critical to enhance the catalytic performance of MXenes. I expect that MXenes with HER activity comparable to Pt in a wide range of hydrogen density can be realized by tuning composition and functionalizing, and promotes their applications into hydrogen-energy technologies. PMID:27604848

  20. One-step electrochemical synthesis of a graphene–ZnO hybrid for improved photocatalytic activity

    SciTech Connect

    Wei, Ang; Xiong, Li; Sun, Li; Liu, Yanjun; Li, Weiwei; Lai, Wenyong; Liu, Xiangmei; Wang, Lianhui; Huang, Wei; Dong, Xiaochen

    2013-08-01

    Graphical abstract: - Highlights: • Graphene–ZnO hybrid was synthesized by one-step electrochemical deposition. • Graphene–ZnO hybrid presents a special structure and wide UV–vis absorption spectra. • Graphene–ZnO hybrid exhibits an exceptionally higher photocatalytic activity for the degradation of dye methylene blue. - Abstract: A graphene–ZnO (G-ZnO) hybrid was synthesized by one-step electrochemical deposition. During the formation of ZnO nanostructure by cathodic electrochemical deposition, the graphene oxide was electrochemically reduced to graphene simultaneously. Scanning electron microscope images, X-ray photoelectron spectroscopy, X-ray diffraction, Raman spectra, and UV–vis absorption spectra indicate the resulting G-ZnO hybrid presents a special structure and wide UV–vis absorption spectra. More importantly, it exhibits an exceptionally higher photocatalytic activity for the degradation of dye methylene blue than that of pure ZnO nanostructure under both ultraviolet and sunlight irradiation.

  1. Enhanced molten salt purification by electrochemical methods: feasibility experiments with flibe

    SciTech Connect

    Alan K Wertsching; Brandon S Grover; Pattrick Calderoni

    2010-09-01

    -chemistry properties in heat transport systems’ describes the options available to reach such objectives and contains extended references to published work. The report highlights how electrochemical methods are the most promising techniques for the development of instrumentation aimed at the measurement of melts composition and for enhanced purification systems. The purpose of this work is to summarize preliminary experimental activities performed at the INL Safety and Tritium Applied Research facility in support of the development of electrochemistry based instrumentation and purification systems. The experiments have been focused on the LiF-BeF2 eutectic (67 and 33 mol%, respectively), also known as flibe.

  2. Large-Scale Synthesis of Metal-Ion-Doped Manganese Dioxide for Enhanced Electrochemical Performance.

    PubMed

    Peng, Ruichao; Wu, Nian; Zheng, Yu; Huang, Yangbo; Luo, Yunbai; Yu, Ping; Zhuang, Lin

    2016-04-01

    One-dimensional (1D) MnO2 was widely applied in areas of enzyme biosensors, industrial sieves, and energy storage materials owing to its excellent thermal, optical, magnetic, and chemical features. However, its practical application into energy storage devices is often hindered by the bad electronic conductivity (from 10(-5) to 10(-6) S cm(-1)). As is widely known, doping with hetero elements is an efficient way to enhance the electronic conductivity of metal oxides. Herein, a novel and simple molten-salt method is developed to achieve a large-scale preparation of 1D MnO2 nanowires. Such an approach also realizes the easy tuning of electrical properties through doping with different transition metal ions. On the basis of first-principle calculation as well as four-probe measurement, we determined that the conductivity of the doped MnO2 nanowires can be promoted efficiently by utilizing such protocol. Meanwhile, a possible doping route is discussed in detail. As a result, a superior electrochemical performance can be observed in such metal ions (M(+))-doped nanowires. Such high-quality M(+)-doped MnO2 nanowires can satisfy a broad range of application needs beyond the electrochemical capacitors. PMID:26996352

  3. Hydrothermal synthesis of mesoporous metal oxide arrays with enhanced properties for electrochemical energy storage

    SciTech Connect

    Xiao, Anguo Zhou, Shibiao; Zuo, Chenggang; Zhuan, Yongbing; Ding, Xiang

    2015-01-15

    Highlights: • NiO mesoporous nanowall arrays are prepared via hydrothermal method. • Mesoporous nanowall arrays are favorable for fast ion/electron transfer. • NiO mesoporous nanowall arrays show good supercapacitor performance. - Abstract: Mesoporous nanowall NiO arrays are prepared by a facile hydrothermal synthesis method with a following annealing process. The NiO nanowall shows continuous mesopores ranging from 5 to 10 nm and grows vertically on the substrate forming a porous net-like structure with macropores of 20–300 nm. A plausible mechanism is proposed for the growth of mesoporous nanowall NiO arrays. As cathode material of pseudocapacitors, the as-prepared mesoporous nanowall NiO arrays show good pseudocapacitive performances with a high capacitance of 600 F g{sup −1} at 2 A g{sup −1} and impressive high-rate capability with a specific capacitance of 338 F g{sup −1} at 40 A g{sup −1}. In addition, the mesoporous nanowall NiO arrays possess good cycling stability. After 6000 cycles at 2 A g{sup −1}, a high capacitance of 660 F g{sup −1} is attained, and no obvious degradation is observed. The good electrochemical performance is attributed to its highly porous morphology, which provides large reaction surface and short ion diffusion paths, leading to enhanced electrochemical properties.

  4. A Facile Electrochemical Sensor for Nonylphenol Determination Based on the Enhancement Effect of Cetyltrimethylammonium Bromide

    PubMed Central

    Lu, Qing; Zhang, Weina; Wang, Zhihui; Yu, Guangxia; Yuan, Yuan; Zhou, Yikai

    2013-01-01

    A facile electrochemical sensor for the determination of nonylphenol (NP) was fabricated in this work. Cetyltrimethylammonium bromide (CTAB), which formed a bilayer on the surface of the carbon paste (CP) electrode, displayed a remarkable enhancement effect for the electrochemical oxidation of NP. Moreover, the oxidation peak current of NP at the CTAB/CP electrode demonstrated a linear relationship with NP concentration, which could be applied in the direct determination of NP. Some experimental parameters were investigated, such as external solution pH, mode and time of accumulation, concentration and modification time of CTAB and so on. Under optimized conditions, a wide linear range from 1.0 × 10−7 mol·L−1 to 2.5 × 10−5 mol·L−1 was obtained for the sensor, with a low limit of detection at 1.0 × 10−8 mol·L−1. Several distinguishing advantages of the as-prepared sensor, including facile fabrication, easy operation, low cost and so on, suggest a great potential for its practical applications. PMID:23296332

  5. Enhancement of SOFC Cathode Electrochemical Performance Using Multi-Phase Interfaces

    SciTech Connect

    Morgan, Dane

    2015-09-30

    This work explored the use of oxide heterostructures for enhancing the catalytic and degradation properties of solid oxide fuel cell (SOFC) cathode electrodes. We focused on heterostructures of Ruddlesden-Popper and perovskite phases. Building on previous work showing enhancement of the Ruddlesden-Popper (La,Sr)2CoO4 / perovskite (La,Sr)CoO3 heterostructure compared to pure (La,Sr)CoO3 we explored the application of related heterostructures of Ruddlesden-Popper phases on perovskite (La,Sr)(Co,Fe)O3. Our approaches included thin-film electrodes, physical and electrochemical characterization, elementary reaction kinetics modeling, and ab initio simulations. We demonstrated that Sr segregation to surfaces is likely playing a critical role in the performance of (La,Sr)CoO3 and (La,Sr)(Co,Fe)O3 and that modification of this Sr segregation may be the mechanism by which Ruddlesden-Popper coatings enhance performances. We determined that (La,Sr)(Co,Fe)O3 could be enhanced in thin films by about 10× by forming a heterostructure simultaneously with (La,Sr)2CoO4 and (La,Sr)CoO3. We hope that future work will develop this heterostructure for use as a bulk porous electrode.

  6. Enhanced electrochemical methanation of carbon dioxide with a dispersible nanoscale copper catalyst.

    PubMed

    Manthiram, Karthish; Beberwyck, Brandon J; Alivisatos, A Paul

    2014-09-24

    Although the vast majority of hydrocarbon fuels and products are presently derived from petroleum, there is much interest in the development of routes for synthesizing these same products by hydrogenating CO2. The simplest hydrocarbon target is methane, which can utilize existing infrastructure for natural gas storage, distribution, and consumption. Electrochemical methods for methanizing CO2 currently suffer from a combination of low activities and poor selectivities. We demonstrate that copper nanoparticles supported on glassy carbon (n-Cu/C) achieve up to 4 times greater methanation current densities compared to high-purity copper foil electrodes. The n-Cu/C electrocatalyst also exhibits an average Faradaic efficiency for methanation of 80% during extended electrolysis, the highest Faradaic efficiency for room-temperature methanation reported to date. We find that the level of copper catalyst loading on the glassy carbon support has an enormous impact on the morphology of the copper under catalytic conditions and the resulting Faradaic efficiency for methane. The improved activity and Faradaic efficiency for methanation involves a mechanism that is distinct from what is generally thought to occur on copper foils. Electrochemical data indicate that the early steps of methanation on n-Cu/C involve a pre-equilibrium one-electron transfer to CO2 to form an adsorbed radical, followed by a rate-limiting non-electrochemical step in which the adsorbed CO2 radical reacts with a second CO2 molecule from solution. These nanoscale copper electrocatalysts represent a first step toward the preparation of practical methanation catalysts that can be incorporated into membrane-electrode assemblies in electrolyzers. PMID:25137433

  7. Enhanced catalysis of the electrochemical hydrogen evolution reaction using composites of molybdenum-based compounds, gold nanoparticles and carbon.

    PubMed

    Joshi, Ubisha; Lee, Jing; Giordano, Cristina; Malkhandi, Souradip; Yeo, Boon Siang

    2016-08-21

    Molybdenum nitride has been recently reported to interact synergistically with gold to show an enhanced activity for the electrochemical hydrogen evolution reaction (2H(+) + 2e(-)→ H2, HER). In this work, we elucidated the roles of nitrogen, carbon, molybdenum and gold on this observed phenomenon. Composites of Mo-based compounds, carbon black (black pearl 2000) and/or Au nanoparticles (AuNP) were prepared, and their activities for the HER in a 0.5 M H2SO4 electrolyte were measured using linear sweep voltammetry. We show and discuss here for the first time that, while the presence of carbon is necessary for the synergy phenomenon, the nitrogen atoms present in the compounds play no apparent role in this synergy. In fact, all the compounds containing Mo, namely Mo2N, MoB and metallic Mo(0), exhibited extensive synergy with Au for the HER. A hypothesis for the enhanced catalysis of H2 evolution by the mixed metal composites is proposed and discussed. PMID:27424516

  8. High catalytic activity of electrochemically reduced graphene composite toward electrochemical sensing of Orange II.

    PubMed

    Yun, Mira; Choe, Ju Eun; You, Jung-Min; Ahmed, Mohammad Shamsuddin; Lee, Kyungmi; Ustündağ, Zafer; Jeon, Seungwon

    2015-02-15

    Orange II, an azo dye, is sometimes illegally used as a red dye in food products despite its adverse health effects if consumed. Therefore, the determination of low concentrations of Orange II is an important target. An Orange II sensor was prepared using electrochemically reduced graphene oxide grafted with 5-amino-1,3,4-thiadiazole-2-thiol-Pt nanoparticles (denoted as ERGO-ATDT-Pt) onto a glassy carbon electrode (GCE) and investigated for Orange II detection in 0.1M acetate buffer solution (ABS at pH 4.5) with prominent reversible redox peaks. A wide linear range of 1×10(-)(8)-6×10(-)(7)M with a low detection limit of 3.4×10(-)(10)M (s/n=3) was found for Orange II detection. This developed ERGO-ATDT-Pt/GCE sensor showed good selectivity, excellent stability and better response to the real sample analysis with excellent recovery. PMID:25236205

  9. Peroxidase-encapsulated cyclodextrin nanosponge immunoconjugates as a signal enhancement tool in optical and electrochemical assays.

    PubMed

    Wajs, Ewelina; Caldera, Fabrizio; Trotta, Francesco; Fragoso, Alex

    2014-01-21

    Cyclodextrin nanosponges bearing carboxylate groups have been prepared by crosslinking β-cyclodextrin with pyromellitic dianhydride to form a carboxylic acid terminated nanoporous material. The surface of the particles was covalently modified with an anti-IgG antibody and then loaded with horseradish peroxidase. The structures of unmodified and protein modified nanosponge particles were investigated by Raman spectroscopy and imaging methods. Confocal microscopy indicates that the antibody is located in the outside of the particle while HRP is encapsulated in the inner part. The possibility to use these modified nanosponges as a signal enhancement tool in enzyme-linked colorimetric and electrochemical assays was evaluated using a sandwich format comprising immobilised gliadin as an antigen, a target anti-gliadin antibody and an anti-IgG antibody conjugated to the enzyme-loaded nanosponge immunoconjugates. PMID:24276364

  10. Cuprous Sulfide/Reduced Graphene Oxide Hybrid Nanomaterials: Solvothermal Synthesis and Enhanced Electrochemical Performance

    NASA Astrophysics Data System (ADS)

    He, Zhanjun; Zhu, Yabo; Xing, Zheng; Wang, Zhengyuan

    2016-01-01

    The cuprous sulfide nanoparticles (CuS NPs)-decorated reduced graphene oxide (rGO) nanocomposites have been successfully prepared via a facile and efficient solvothermal synthesis method. Scanning electron microscopy and transmission electron microscopy images demonstrated that CuS micronspheres composed of nanosheets and distributed on the rGO layer in well-monodispersed form. Fourier-transform infrared spectroscopy analyses and x-ray photoelectron spectroscopy showed that graphene oxide (GO) had been reduced to rGO. The electrochemical performances of CuS/rGO nanocomposites were investigated by cyclic voltammetry and charge/discharge techniques, which showed that the specific capacitance of CuS/rGO nanocomposites was enhanced because of the introduction of rGO.

  11. Enhanced Luminance of Electrochemical Cells with a Rationally Designed Ionic Iridium Complex and an Ionic Additive.

    PubMed

    Suhr, Kristin J; Bastatas, Lyndon D; Shen, Yulong; Mitchell, Lauren A; Holliday, Bradley J; Slinker, Jason D

    2016-04-13

    Light-emitting electrochemical cells (LEECs) offer the potential for high efficiency operation from an inexpensive device. However, long turn-on times and low luminance under steady-state operation are longstanding LEEC issues. Here, we present a single-layer LEEC with a custom-designed iridium(III) complex and a lithium salt additive for enhanced device performance. These devices display reduced response times, modest lifetimes, and peak luminances as high as 5500 cd/m(2), 80% higher than a comparable device from an unoptimized complex and 50% higher than the salt-free device. Improved device efficiency suggests that salt addition balances space charge effects at the interfaces. Extrapolation suggests favorable half-lives of 120 ± 10 h at 1000 cd/m(2) and 3800 ± 400 h at 100 cd/m(2). Overall, complex design and device engineering produce competitive LEECs from simple, single-layer architectures. PMID:27023074

  12. Electrochemical deposition of silver on manganese dioxide coated reduced graphene oxide for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Lee, Kyungmi; Ahmed, Mohammad Shamsuddin; Jeon, Seungwon

    2015-08-01

    We have prepared a reduced graphene oxide (rGO)-supported silver (Ag) and manganese dioxide (MnO2) deposited porous-like catalyst (denoted as rGO/MnO2/Ag) through a facile electrochemical deposition route and have been used as a cathode catalyst for oxygen reduction reaction (ORR) in alkaline fuel cells. The physical properties of rGO/MnO2/Ag have been investigated via several instrumental methods. This material exhibits a polycrystalline structure characterized by Ag/MnO2 microsphere formation as a result of Ostwald ripening. The X-ray diffraction and X-ray photoelectron spectroscopy data reveal that the MnO2 and Ag have been slightly alloyed and Mn presents with the dioxide form on rGO. The electrochemical properties of the electrocatalyst have been studied via several voltammetric methods. The results demonstrated that the rGO/MnO2/Ag has an excellent catalytic activity for ORR in alkaline media compared to the other tested electrodes. Particularly, it shows 1.2 times higher current density and better electron transfer rate at 0.3 V per O2 than that of 20 wt% Pt/C. The other kinetic analysis reveals that the O2 has reduced directly to H2O through a nearly four-electron pathway with better anodic fuel tolerance and duration performance than that of 20% Pt/C.

  13. Stability enhancement of an electrically tunable colloidal photonic crystal using modified electrodes with a large electrochemical potential window

    SciTech Connect

    Shim, HongShik; Gyun Shin, Chang; Heo, Chul-Joon; Jeon, Seog-Jin; Jin, Haishun; Woo Kim, Jung; Jin, YongWan; Lee, SangYoon; Gyu Han, Moon E-mail: jinklee@snu.ac.kr; Lim, Joohyun; Lee, Jin-Kyu E-mail: jinklee@snu.ac.kr

    2014-02-03

    The color tuning behavior and switching stability of an electrically tunable colloidal photonic crystal system were studied with particular focus on the electrochemical aspects. Photonic color tuning of the colloidal arrays composed of monodisperse particles dispersed in water was achieved using external electric field through lattice constant manipulation. However, the number of effective color tuning cycle was limited due to generation of unwanted ions by electrolysis of the water medium during electrical switching. By introducing larger electrochemical potential window electrodes, such as conductive diamond-like carbon or boron-doped diamond, the switching stability was appreciably enhanced through reducing the number of ions generated.

  14. Highly visible light active Ag@TiO2 nanocomposites synthesized using an electrochemically active biofilm: a novel biogenic approach

    NASA Astrophysics Data System (ADS)

    Khan, M. Mansoob; Ansari, Sajid A.; Amal, M. Ikhlasul; Lee, Jintae; Cho, Moo Hwan

    2013-05-01

    Titanium dioxide (TiO2) nanoparticles were decorated with different amounts of silver nanoparticles (AgNPs) using an electrochemically active biofilm (EAB), which is a biogenic approach that leads to the formation of Ag@TiO2 nanocomposites. UV-vis spectroscopy, photoluminescence, X-ray diffraction and electron microscopy showed AgNPs, 2-5 nm in size, well-dispersed and anchored to the TiO2 surface and overall synthesis of Ag@TiO2 nanocomposites. The photocatalytic performance of the as-synthesized Ag@TiO2 nanocomposites was evaluated in terms of their efficiency for the photodecomposition of methylene blue (MB) in an aqueous solution under visible light irradiation. The nanocomposites showed exceptionally high photodecomposition efficiency (>7 times) compared to commercial TiO2 (Sigma). The enhanced photocatalytic activity was attributed to the synergistic contribution of both a delayed charge recombination rate caused by the high electronic mobility of the AgNPs and the increased surface area originating from the nanometer sized AgNPs on TiO2. The nanocomposites also showed exceptionally high stability and reusability under similar experimental conditions.Titanium dioxide (TiO2) nanoparticles were decorated with different amounts of silver nanoparticles (AgNPs) using an electrochemically active biofilm (EAB), which is a biogenic approach that leads to the formation of Ag@TiO2 nanocomposites. UV-vis spectroscopy, photoluminescence, X-ray diffraction and electron microscopy showed AgNPs, 2-5 nm in size, well-dispersed and anchored to the TiO2 surface and overall synthesis of Ag@TiO2 nanocomposites. The photocatalytic performance of the as-synthesized Ag@TiO2 nanocomposites was evaluated in terms of their efficiency for the photodecomposition of methylene blue (MB) in an aqueous solution under visible light irradiation. The nanocomposites showed exceptionally high photodecomposition efficiency (>7 times) compared to commercial TiO2 (Sigma). The enhanced

  15. Antileishmanial activity of quinazoline derivatives: synthesis, docking screens, molecular dynamic simulations and electrochemical studies.

    PubMed

    Mendoza-Martínez, Cesar; Galindo-Sevilla, Norma; Correa-Basurto, José; Ugalde-Saldivar, Victor Manuel; Rodríguez-Delgado, Rosa Georgina; Hernández-Pineda, Jessica; Padierna-Mota, Cecilia; Flores-Alamo, Marcos; Hernández-Luis, Francisco

    2015-03-01

    A series of quinazoline-2,4,6-triamine were synthesized and evaluated in vitro against Leishmania mexicana. Among them, N(6)-(ferrocenmethyl)quinazolin-2,4,6-triamine (H2) showed activity on promastigotes and intracellular amastigotes, as well as low cytotoxicity in mammalian cells. Docking and electrochemical studies showed the importance of both the ferrocene and the heterocyclic nucleus to the observed activity. H2 is readily oxidized electrochemically, indicating that the mechanism of action probably involves redox reactions. PMID:25576738

  16. Micro and nanoscale electrochemical systems for reagent generation, coupled electrokinetic transport and enhanced detection

    NASA Astrophysics Data System (ADS)

    Contento, Nicholas M.

    Chemical analysis is being performed in devices operated at ever decreasing length scales in order to harness the fundamental benefits of micro and nanoscale phenomena while minimizing operating footprint and sample size. The advantages of moving traditional sample or chemical processing steps (e.g. separation, detection, and reaction) into micro- and nanofluidic devices have been demonstrated, and they arise from the relatively rapid rates of heat and mass transport at small length scales. The use of electrochemical methods in micro/nanoscale systems to control and improve these processes holds great promise. Unfortunately, much is still not understood about the coupling of multiple electrode driven processes in a confined environment nor about the fundamental changes in device performance that occur as geometries approach the nanoscale regime. At the nanoscale a significant fraction of the sample volume is in close contact with the device surface, i.e. most of the sample is contained within electronic or diffusion layers associated with surface charge or surface reactions, respectively. The work presented in this thesis aims to understand some fundamental different behaviors observed in micro/nanofluidic structures, particularly those containing one or more embedded, metallic electrode structures. First, a quantitative method is devised to describe the impact of electric fields on electrochemistry in multi-electrode micro/nanofluidic systems. Next the chemical manipulation of small volumes (≤ 10-13 L) in micro/nanofluidic structures is explored by creating regions of high pH and high dissolved gas (H 2) concentration through the electrolysis of H2O. Massively parallel arrays of nanochannel electrodes, or embedded annular nanoband electrodes (EANEs), are then studied with a focus on achieving enhanced signals due to coupled electrokinetic and electrochemical effects. In EANE devices, electroosmotic flow results from the electric field generated between the

  17. Impact of electrolyte composition on the reactivity of a redox active polymer studied through surface interrogation and ion-sensitive scanning electrochemical microscopy.

    PubMed

    Burgess, Mark; Hernández-Burgos, Kenneth; Cheng, Kevin J; Moore, Jeffrey S; Rodríguez-López, Joaquín

    2016-06-21

    Elucidating the impact of interactions between the electrolyte and electroactive species in redox active polymers is key to designing better-performing electrodes for electrochemical energy storage and conversion. Here, we present on the improvement of the electrochemical activity of poly(para-nitrostyrene) (PNS) in solution and as a film by exploiting the ionic interactions between reduced PNS and K(+), which showed increased reactivity when compared to tetrabutylammonium (TBA(+))- and Li(+)-containing electrolytes. While cyclic voltammetry enabled the study of the effects of cations on the electrochemical reversibility and the reduction potential of PNS, scanning electrochemical microscopy (SECM) provided new tools to probe the ionic and redox reactivity of this system. Using an ion-sensitive Hg SECM tip allowed to probe the ingress of ions into PNS redox active films, while surface interrogation SECM (SI-SECM) measured the specific kinetics of PNS and a solution phase mediator in the presence of the tested electrolytes. SI-SECM measurements illustrated that the interrogation kinetics of PNS in the presence of K(+) compared to TBA(+) and Li(+) are greatly enhanced under the same surface concentration of adsorbed radical anion, exhibiting up to a 40-fold change in redox kinetics. We foresee using this new application of SECM methods for elucidating optimal interactions that enhance polymer reactivity for applications in redox flow batteries. PMID:27064026

  18. Prussian blue mediated amplification combined with signal enhancement of ordered mesoporous carbon for ultrasensitive and specific quantification of metolcarb by a three-dimensional molecularly imprinted electrochemical sensor.

    PubMed

    Yang, Yukun; Cao, Yaoyu; Wang, Xiaomin; Fang, Guozhen; Wang, Shuo

    2015-02-15

    In this work, we presented a three-dimensional (3D) molecularly imprinted electrochemical sensor (MIECS) with novel strategy for ultrasensitive and specific quantification of metolcarb based on prussian blue (PB) mediated amplification combined with signal enhancement of ordered mesoporous carbon. The molecularly imprinted polymers were synthesized by electrochemically induced redox polymerization of para aminobenzoic acid (p-ABA) in the presence of template metolcarb. Ordered mesoporous carbon material (CMK-3) was introduced to enhance the electrochemical response by improving the structure of the modified electrodes and facilitating charge transfer processes of PB which was used as an inherent electrochemical active probe. The modification process for the working electrodes of the MIECS was characterized by scanning electron microscope (SEM) and cyclic voltammetry (CV), and several important parameters controlling the performance of the MIECS were investigated and optimized in detail. The MIECS with 3D structure had the advantages of ease of preparation, high porous surface structure, speedy response, ultrasensitivity, selectivity, reliable stability, good reproducibility and repeatability. Under the optimal conditions, the MIECS offered an excellent current response for metolcarb in the linear response range of 5.0 × 10(-10)-1.0 × 10(-4) mol L(-1) and the limit of detection (LOD) was calculated to be 9.3 × 10 (-11)mol L(-1) (S/N = 3). The proposed MIECS has been successfully applied for the determination of metolcarb in real samples with satisfactory recoveries. Furthermore, the construction route of this ultrasensitive 3D MIECS may provide a guideline for the determination of non-electroactive analytes in environmental control and food safety. PMID:25240126

  19. Enhanced capacitive properties of commercial activated carbon by re-activation in molten carbonates

    NASA Astrophysics Data System (ADS)

    Lu, Beihu; Xiao, Zuoan; Zhu, Hua; Xiao, Wei; Wu, Wenlong; Wang, Dihua

    2015-12-01

    Simple, affordable and green methods to improve capacitive properties of commercial activated carbon (AC) are intriguing since ACs possess a predominant role in the commercial supercapacitor market. Herein, we report a green reactivation of commercial ACs by soaking ACs in molten Na2CO3-K2CO3 (equal in mass ratios) at 850 °C combining the merits of both physical and chemical activation strategies. The mechanism of molten carbonate treatment and structure-capacitive activity correlations of the ACs are rationalized. Characterizations show that the molten carbonate treatment increases the electrical conductivity of AC without compromising its porosity and wettability of electrolytes. Electrochemical tests show the treated AC exhibited higher specific capacitance, enhanced high-rate capability and excellent cycle performance, promising its practical application in supercapacitors. The present study confirms that the molten carbonate reactivation is a green and effective method to enhance capacitive properties of ACs.

  20. Electrochemically Active Polyaniline (PANi) Coated Carbon Nanopipes and PANi Nanofibers Containing Composite.

    PubMed

    Ramana, G Venkata; Kumar, P Sampath; Srikanth, Vadali V S S; Padya, Balaji; Jain, P K

    2015-02-01

    A composite constituted by carbon nanopipes (CNPs) and polyaniline nanofibers (PANi NFs) is synthesized using in-situ chemical oxidative polymerization. Owing to its electrochemical activity the composite is found to be suitable as a working electrode material in hybrid type supercapacitors. Microstructural and phase analyses of the composite showed that (i) CNP surfaces are coated with PANi and (ii) PANi coated CNPs are distributed among PANi NFs. The composite shows an excellent electrochemical activity and a high specific capacitance of ~224.39 F/g. The electro-chemical activity of the composite is explicated in correlation with crystallinity, intrinsic oxidation state, and doping degree of PANi in the composite. The electro-chemical activity of the composite is also explicated in correlation with BET surface area and ordered meso-porosity pertaining to the composite. Charge/discharge curves indicate that the specific capacitance of the composite is a result of electric double-layer capacitance offered by CNPs and Faradaic pseudo capacitance offered by PANi NFs. PMID:26353652

  1. Electrochemical detection of protein kinase activity based on carboxypeptidase Y digestion triggered signal amplification.

    PubMed

    Yin, Huanshun; Wang, Xinxu; Guo, Yunlong; Zhou, Yunlei; Ai, Shiyun

    2015-04-15

    An effective assay method for monitoring protein kinase activity and screening inhibitors is greatly beneficial to kinase-related drug discovery, early diagnosis of diseases, and therapeutic effect evaluation. Herein, we develop a simple electrochemical method for detecting the activity of casein kinase II (CK2) based on phosphorylation against carboxypeptidase Y (CPY) digestion triggered signal amplification, where CK2 catalyzed phosphorylation event protects the substrate peptide from the digestion of CPY, maintains the repulsive force of the substrate peptide towards the redox probe, and results in a weak electrochemical signal. Whereas, without phosphorylation, the substrate peptide is digested by CPY and a strong electrochemical signal is obtained. The detection feasibility is demonstrated for the assay of CK2 activity with low detection limit of 0.047unit/mL. Moreover, the biosensor was used for the analysis of kinase inhibition. Based on the electrochemical signal dependent inhibitor concentration, the IC50 value of ellagic acid was estimated to be 39.77nM. The proposed method is also successfully applied to analyze CK2 activity in cell lysates, proving the applicability in complex biological samples. PMID:25460885

  2. Relationship between the electrochemical activity of Raney nickel and the rate of hydrogenation of maleic acid

    SciTech Connect

    Pervii, E.N.; Sofronkov, A.N.; Fedyshina, N.M.

    1986-02-10

    The purpose of this investigation was to determine the conditions in which a direct correlation exists between the rate of hydrogenation of maleic acid and the electrochemical activity of catalysts of hydrogen ionization. The rate of maleic acid hydrogenation in presence of Raney nickel catalyst was studied by a combination of volumetric and potentiometric methods.

  3. Electrochemical analyses of redox-active iron minerals: a review of nonmediated and mediated approaches.

    PubMed

    Sander, Michael; Hofstetter, Thomas B; Gorski, Christopher A

    2015-05-19

    Redox-active minerals are ubiquitous in the environment and are involved in numerous electron transfer reactions that significantly affect biogeochemical processes and cycles as well as pollutant dynamics. As a consequence, research in different scientific disciplines is devoted to elucidating the redox properties and reactivities of minerals. This review focuses on the characterization of mineral redox properties using electrochemical approaches from an applied (bio)geochemical and environmental analytical chemistry perspective. Establishing redox equilibria between the minerals and working electrodes is a major challenge in electrochemical measurements, which we discuss in an overview of traditional electrochemical techniques. These issues can be overcome with mediated electrochemical analyses in which dissolved redox mediators are used to increase the rate of electron transfer and to facilitate redox equilibration between working electrodes and minerals in both amperometric and potentiometric measurements. Using experimental data on an iron-bearing clay mineral, we illustrate how mediated electrochemical analyses can be employed to derive important thermodynamic and kinetic data on electron transfer to and from structural iron. We summarize anticipated methodological advancements that will further contribute to advance an improved understanding of electron transfer to and from minerals in environmentally relevant redox processes. PMID:25856208

  4. Silicon nanowire based biosensing platform for electrochemical sensing of Mebendazole drug activity on breast cancer cells.

    PubMed

    Shashaani, Hani; Faramarzpour, Mahsa; Hassanpour, Morteza; Namdar, Nasser; Alikhani, Alireza; Abdolahad, Mohammad

    2016-11-15

    Electrochemical approaches have played crucial roles in bio sensing because of their Potential in achieving sensitive, specific and low-cost detection of biomolecules and other bio evidences. Engineering the electrochemical sensing interface with nanomaterials tends to new generations of label-free biosensors with improved performances in terms of sensitive area and response signals. Here we applied Silicon Nanowire (SiNW) array electrodes (in an integrated architecture of working, counter and reference electrodes) grown by low pressure chemical vapor deposition (LPCVD) system with VLS procedure to electrochemically diagnose the presence of breast cancer cells as well as their response to anticancer drugs. Mebendazole (MBZ), has been used as antitubulin drug. It perturbs the anodic/cathodic response of the cell covered biosensor by releasing Cytochrome C in cytoplasm. Reduction of cytochrome C would change the ionic state of the cells monitored by SiNW biosensor. By applying well direct bioelectrical contacts with cancer cells, SiNWs can detect minor signal transduction and bio recognition events, resulting in precise biosensing. Our device detected the trace of MBZ drugs (with the concentration of 2nM) on electrochemical activity MCF-7 cells. Also, experimented biological analysis such as confocal and Flowcytometry assays confirmed the electrochemical results. PMID:27196254

  5. Multifunctional g-C(3)N(4) nanofibers: a template-free fabrication and enhanced optical, electrochemical, and photocatalyst properties.

    PubMed

    Tahir, Muhammad; Cao, Chuanbao; Mahmood, Nasir; Butt, Faheem K; Mahmood, Asif; Idrees, Faryal; Hussain, Sajad; Tanveer, M; Ali, Zulfiqar; Aslam, Imran

    2014-01-22

    We have developed a facile, scale up, and efficient method for the preparation of graphitic-C3N4 nanofibers (GCNNFs) as electrodes for supercapacitors and photocatalysts. The as-synthesized GCNNFs have 1D structure with higher concentration of nitrogen that is favorable for higher conductivity and electrochemical performance. Secondly, the high surface area of GCNNF provides a large electrode-electrolyte contact area, sufficient light harvesting and mass transfer, as well as increased redox potential. Thus, the GCNNF supercapacitor electrode shows high capacitance of 263.75 F g(-1) and excellent cyclic stability in 0.1 M Na2SO4 aqueous electrolyte with the capacitance retention of 93.6% after 2000 cycles at 1 A g(-1) current density. GCNNFs exhibit high capacitance of 208 F g(-1) even at 10 A g(-1), with the appreciable capacitance retention of 89.5%, which proves its better rate capability. Moreover, the GCNNF shows enhanced photocatalytic activity in the photodegradation of RhB in comparison to the bulk graphitic-C3N4 (GCN). The degradation rate constant of GCNNF photocatalyst is almost 4 times higher than GCN. The enhanced photocatalytic activity of GCNNF is mainly due to the higher surface area, appropriate bandgap, and fewer defects in GCNNF as compared to GCN. As an economical precursor (melamine) and harmless, facile, and template-free synthesis method with excellent performance both in supercapacitors and in photodegradation, GCNNF is a strong candidate for energy storage and environment protection applications. PMID:24354285

  6. Mechanism of enhanced removal of quinonic intermediates during electrochemical oxidation of Orange II under ultraviolet irradiation.

    PubMed

    Li, Fazhan; Li, Guoting; Zhang, Xiwang

    2014-03-01

    The effect of ultraviolet irradiation on generation of radicals and formation of intermediates was investigated in electrochemical oxidation of the azo-dye Orange II using a TiO2-modified β-PbO2 electrode. It was found that a characteristic absorbance of quinonic compounds at 255 nm, which is responsible for the rate-determining step during aromatics degradation, was formed only in electrocatalytic oxidation. The dye can be oxidized by either HO radicals or direct electron transfer. Quinonic compounds were produced concurrently. The removal of TOC by photo-assisted electrocatalytic oxidation was 1.56 times that of the sum of the other two processes, indicating a significant synergetic effect. In addition, once the ultraviolet irradiation was introduced into the process of electrocatalytic oxidation, the degradation rate of quinonic compounds was enhanced by as much as a factor of two. The more efficient generation of HO radicals resulted from the introduction of ultraviolet irradiation in electrocatalytic oxidation led to the significant synergetic effect as well as the inhibiting effect on the accumulation of quinonic compounds. PMID:25079285

  7. Enhanced Conductivity and Electrochemical Performance of Electrode Material Based on Multifunctional Dye Doped Polypyrrole.

    PubMed

    Zang, Limin; Qiu, Jianhui; Yang, Chao; Sakai, Eiichi

    2016-03-01

    Polypyrrole were prepared via in-situ chemical oxidative polymerization in the presence of multisulfonate acid dye (acid violet 19). In this work, acid violet 19 could play the role as dopant, surfactant and physical cross-linker for pyrrole polymerization, and had impact on the morphology, dispersion stability, thermal stability, electrical conductivity and electrochemical behavior of the samples. The thermal stability of the dye doped polypyrrole was enhanced than pure polypyrrole due to the strong interactions between polypyrrole and acid violet 19. The dispersion stability of the samples in water was also improved by incorporating an appropriate amount of acid violet 19. The sample with 20% of acid violet 19 showed granular morphology with the smallest diameter of -50 nm and possessed the maximum electrical conductivity of 39.09 S/cm. The as-prepared multifunctional dye doped polypyrrole samples were used to fabricate electrodes and exhibited a mass specific capacitance of 379-206 F/g in the current density range of 0.2-1.0 A/g. The results indicated that the multifunctional dye could improve the performances of polypyrrole as electrode material for supercapacitors. PMID:27455670

  8. Nanoprobe-Enhanced, Split Aptamer-Based Electrochemical Sandwich Assay for Ultrasensitive Detection of Small Molecules.

    PubMed

    Zhao, Tao; Liu, Ran; Ding, Xiaofan; Zhao, Juncai; Yu, Haixiang; Wang, Lei; Xu, Qing; Wang, Xuan; Lou, Xinhui; He, Miao; Xiao, Yi

    2015-08-01

    It is quite challenging to improve the binding affinity of antismall molecule aptamers. We report that the binding affinity of anticocaine split aptamer pairs improved by up to 66-fold by gold nanoparticles (AuNP)-attached aptamers due to the substantially increased local concentration of aptamers and multiple and simultaneous ligand interactions. The significantly improved binding affinity enables the detection of small molecule targets with unprecedented sensitivity, as demonstrated in nanoprobe-enhanced split aptamer-based electrochemical sandwich assays (NE-SAESA). NE-SAESA replaces the traditional molecular reporter probe with AuNPs conjugated to multiple reporter probes. The increased binding affinity allowed us to use 1,000-fold lower reporter probe concentrations relative to those employed in SAESA. We show that the near-elimination of background in NE-SAESA effectively improves assay sensitivity by ∼1,000-100,000-fold for ATP and cocaine detection, relative to equivalent SAESA. With the ongoing development of new strategies for the selection of aptamers, we anticipate that our sensor platform should offer a generalizable approach for the high-sensitivity detection of diverse targets. More importantly, we believe that NE-SAESA represents a novel strategy to improve the binding affinity between a small molecule and its aptamer and potentially can be extended to other detection platforms. PMID:26171721

  9. Effects of CO2 activation on electrochemical performance of microporous carbons derived from poly(vinylidene fluoride)

    NASA Astrophysics Data System (ADS)

    Lee, Seul-Yi; Park, Soo-Jin

    2013-11-01

    In this work, we have prepared microporous carbons (MPCs) derived from poly(vinylidene fluoride) (PVDF), and the physical activation of MPCs using CO2 gas is subsequently carried out with various activation temperatures to investigate the electrochemical performance. PVDF is successfully converted into MPCs with a high specific surface area and well-developed micropores. After CO2 activation, the specific surface areas of MPCs (CA-MPCs) are enhanced by 12% compared with non-activated MPCs. With increasing activation temperature, the micropore size distributions of A-MPCs also become narrower and shift to larger pore size. It is also confirmed that the CO2 activation had developed the micropores and introduced the oxygen-containing groups to MPCs‧ surfaces. From the results, the specific capacitances of the electrodes in electric double layer capacitors (EDLCs) based on CA-MPCs are distinctly improved through CO2 activation. The highest specific capacitance of the A-MPCs activated at 700 °C is about 125 F/g, an enhancement of 74% in comparison with NA-MPCs, at a discharge current of 2 A/g in a 6 M KOH electrolyte solution. We also found that micropore size of 0.67 nm has a specific impact on the capacitance behaviors, besides the specific surface area of the electrode samples.

  10. One-step carbonization synthesis of hollow carbon nanococoons with multimodal pores and their enhanced electrochemical performance for supercapacitors.

    PubMed

    Zhang, Jianan; Wang, Kaixi; Guo, Shaojun; Wang, Shoupei; Liang, Zhiqiang; Chen, Zhimin; Fu, Jianwei; Xu, Qun

    2014-02-12

    Hollow carbon capsules with multimodal pores are highly promising for developing novel electrode materials for high-performance electrochemical devices due to their more active sites for ion and electron transfer. However, at present, most of the previous efforts are focused on the multistep process for the synthesis of hollow carbon nanostructures with individual pores. Herein, hollow carbon nanococoons (HCNCs) with non-spherical cavity and multimodal hierarchical pores have been facilely synthesized via a one-step carbonization of a Fe2O3/carbon precursor core/shell nanospindle at 850 °C. We interestingly found that during the carbonization, Fe2O3 was automatically "escaped" from the inside nanospindle, leading to the formation of new HCNCs. Most importantly, the spindle-shaped cavity of the obtained HCNCs with high conductivity can offer a multimodal ion diffusion pathway, which can facilitate the reaction kinetics in a supercapacitor. As a result, the HCNCs-based supacapacitor exhibits the capacitance of 220.0 F g(-1) at a given scan rate of 5 mV s(-1), 3.5 times higher than that of hollow carbon spheres, high stability with 98% of the initial capacity maintained even after 1000 cycles, and high rate capability. This work provides a new and facile avenue for enhancing performance of a HCNCs-based supercapacitor by using the non-spherical hollow structures with multimodal pores. PMID:24433086

  11. Nano nickel oxide modified non-enzymatic glucose sensors with enhanced sensitivity through an electrochemical process strategy at high potential.

    PubMed

    Mu, Ying; Jia, Dongling; He, Yayun; Miao, Yuqing; Wu, Hai-Long

    2011-02-15

    Development of fast and sensitive sensors for glucose determination is important in food industry, clinic diagnostics, biotechnology and many other areas. In these years, considerable attention has been paid to develop non-enzymatic electrodes to solve the disadvantages of the enzyme-modified electrodes, such as instability, high cost, complicated immobilization procedure and critical operating situation et al. Nano nickel oxide (NiO) modified non-enzymatic glucose sensors with enhanced sensitivity were investigated. Potential scanning nano NiO modified carbon paste electrodes up to high potential in alkaline solution greatly increases the amount of redox couple Ni(OH)(2)/NiOOH derived from NiO, and thus improves their electrochemical properties and electrocatalytical performance toward the oxidation of glucose. The non-enzymatic sensors response quickly to glucose and the response time is less than 5s, demonstrating excellent electrocatalytical activity and assay performance. The calibration plot is linear over the wide concentration range of 1-110 μM with a sensitivity of 43.9 nA/μM and a correlation coefficient of 0.998. The detection limit of the electrode was found to be 0.16 μM at a signal-to-noise ratio of 3. The proposed non-enzymatic sensors can be used for the assay of glucose in real sample. PMID:21167705

  12. Environment-friendly cathodes using biopolymer chitosan with enhanced electrochemical behavior for use in lithium ion batteries.

    PubMed

    Prasanna, K; Subburaj, T; Jo, Yong Nam; Lee, Won Jong; Lee, Chang Woo

    2015-04-22

    The biopolymer chitosan has been investigated as a potential binder for the fabrication of LiFePO4 cathode electrodes in lithium ion batteries. Chitosan is compared to the conventional binder, polyvinylidene fluoride (PVDF). Dispersion of the active material, LiFePO4, and conductive agent, Super P carbon black, is tested using a viscosity analysis. The enhanced structural and morphological properties of chitosan are compared to the PVDF binder using X-ray diffraction analysis (XRD) and field emission scanning electron microscopy (FE-SEM). Using an electrochemical impedance spectroscopy (EIS) analysis, the LiFePO4 electrode with the chitosan binder is observed to have a high ionic conductivity and a smaller increase in charge transfer resistance based on time compared to the LiFePO4 electrode with the PVDF binder. The electrode with the chitosan binder also attains a higher discharge capacity of 159.4 mAh g(-1) with an excellent capacity retention ratio of 98.38% compared to the electrode with the PVDF binder, which had a discharge capacity of 127.9 mAh g(-1) and a capacity retention ratio of 85.13%. Further, the cycling behavior of the chitosan-based electrode is supported by scrutinizing its charge-discharge behavior at specified intervals and by a plot of dQ/dV. PMID:25822540

  13. Quantitative detection of uric acid by electrochemical-surface enhanced Raman spectroscopy using a multilayered Au/Ag substrate.

    PubMed

    Zhao, Lili; Blackburn, Jonathan; Brosseau, Christa L

    2015-01-01

    Uric acid is a potential important biomarker in urine and serum samples for early diagnosis of preeclampsia, a life-threatening hypertensive disorder that occurs during pregnancy. Preeclampsia is a leading cause of maternal death, especially in developing nation settings. Quantitative detection of uric acid for rapid and routine diagnosis of early preeclampsia using electrochemical-surface enhanced Raman spectroscopy (EC-SERS) is presented herein. A uniform EC-SERS active Au/Ag substrate was developed by depositing nearly monodisperse gold and silver nanoparticles on the carbon working electrode surface of screen printed electrodes. The multilayered Au/Ag substrates were characterized by electron microscopy and used for quantitative detection of uric acid in 0.1 M NaF and synthetic urine at clinically relevant concentrations. These results showed a linear relationship between the EC-SERS signal intensity and the uric acid concentration. Relative errors calculated for selected concentrations were all within the Clinical Laboratory Improvement Amendments (CLIA) criterion for uric acid analysis (±17%). It is believed that routine and early diagnosis of disease could be possible through such quantitative detection of biomarkers in patient samples using this EC-SERS method. PMID:25483146

  14. Great-enhanced performance of Pt nanoparticles by the unique carbon quantum dot/reduced graphene oxide hybrid supports towards methanol electrochemical oxidation

    NASA Astrophysics Data System (ADS)

    Hong, Tian-Zeng; Xue, Qiong; Yang, Zhi-Yong; Dong, Ya-Ping

    2016-01-01

    The Pt-carbon quantum dot (CQD)/reduced graphene oxide (RGO) catalysts are prepared by one pot reduction method and demonstrate ultraefficient performance towards methanol oxidation reaction (MOR). In the high content CQD products, Pt nanoparticles around 2-3 nm are dispersed uniformly on supporting materials. And the X-ray photoelectron spectroscopy analysis indicates that in the high content CQD products a large part of surface oxygen groups is contributed by CQD. The electrochemical tests reveal that the catalyst with the saturated CQD exhibits best performance in MOR: the mass and specific activity at forward peak position, the potential close to fuel cell operation and 3600 s of chronoamperometric curve are roughly 2-3 folds of the commercial Pt/C. Furthermore, the electrochemical data on the series of catalysts with different quantity of CQD disclose the improving tendency of MOR performance with the increasing content of CQD evidently. Overview the electrochemical and characterization results, we suggest CQD play multiple roles in the enhancement of Pt performance: present abundant nucleating and anchoring points to facilitate the formation of small size and uniform distributed Pt particles; act as spacer to alleviate restacking of RGO sheets; and provide fruitful surface oxygen groups to improve the antipoisonous ability of Pt.

  15. Formation of Co3O4 microframes from MOFs with enhanced electrochemical performance for lithium storage and water oxidation.

    PubMed

    Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

    2016-05-01

    Co3O4 microframes are synthesized through a template-engaged strategy via the etching of Co-Co Prussian blue analogue microcubes with ammonia solution and subsequent annealing treatment. Benefitting from their unique structural merits including 3D open structure and high porosity, these Co3O4 microframes exhibit enhanced electrochemical properties for both lithium-ion batteries and water oxidation. PMID:27078114

  16. Electrochemical assay of active prostate-specific antigen (PSA) using ferrocene-functionalized peptide probes

    SciTech Connect

    Zhao, Ning; He, Yuqing; Mao, Xun; Sun, Yuhan; Zhang, Xibao; Li, Chen-Zhong; Lin, Yuehe; Liu, Guodong

    2010-03-24

    This paper presents a novel approach to electrochemically determine enzymatically active PSA using ferrocene-functionalized helix peptide (CHSSLKQK). The principle of electrochemical measurement is based on the specific proteolytic cleavage events of the FC-peptide on the gold electrode surface in the presence of PSA, resulting the change of the current signal of the electrode. The percentage of the decreased current is linear with the concentration of active PSA at the range of 0.5-40 ng/mL with a detection limit of 0.2 ng/mL. The direct transduction of peptide cleavage events into an electrical signal provides a simple, sensitive method for detecting the enzymatic activity of PSA and determining the active PSA concentration.

  17. The Effect of CO2 Activation on the Electrochemical Performance of Coke-Based Activated Carbons for Supercapacitors.

    PubMed

    Lee, Hye-Min; Kim, Hong-Gun; An, Kay-Hyeok; Kim, Byung-Joo

    2015-11-01

    The present study developed electrode materials for supercapacitors by activating coke-based activated carbons with CO2. For the activation reaction, after setting the temperature at 1,000 degrees C, four types of activated carbons were produced, over an activation time of 0-90 minutes and with an interval of 30 minutes as the unit. The electrochemical performance of the activated carbons produced was evaluated to examine the effect of CO2 activation. The surface structure of the porous carbons activated through CO2 activation was observed using a scanning electron microscope (SEM). To determine the N2/77 K isothermal adsorption characteristics, the Brunauer-Emmett-Teller (BET) equation and the Barrett-Joyner-Halenda (BJH) equation were used to analyze the pore characteristics. In addition, charge and discharge tests and cyclic voltammetry (CV) were used to analyze the electrochemical characteristics of the changed pore structure. According to the results of the experiments, the N2 adsorption isotherm curves of the porous carbons produced belonged to Type IV in the International Union of Pore and Applied Chemistry (IUPAC) classification and consisted of micropores and mesopores, and, as the activation of CO2 progressed, micropores decreased and mesopores developed. The specific surface area of the porous carbons activated by CO2 was 1,090-1,180 m2/g and thus showed little change, but those of mesopores were 0.43-0.85 cm3/g, thus increasing considerably. In addition, when the electrochemical characteristics were analyzed, the specific capacity was confirmed to have increased from 13.9 F/g to 18.3 F/g. From these results, the pore characteristics of coke-based activated carbons changed considerably because of CO2 activation, and it was therefore possible to increase the electrochemical characteristics. PMID:26726596

  18. Correlating Local Structure with Electrochemical Activity in Li2MnO3

    DOE PAGESBeta

    Nanda, Jagjit; Sacci, Robert L.; Veith, Gabriel M.; Dixit, Hemant M.; Cooper, Valentino R.; Pezeshki, Alan M.; Ruther, Rose E.

    2015-07-31

    Li2MnO3 is of interest as one component of the composite lithium-rich oxides, which are under development for high capacity, high voltage cathodes in lithium ion batteries. Despite such practical importance, the mechanism of electrochemical activity in Li2MnO3 is contested in the literature, as are the effects of long-term electrochemical cycling. Here, Raman spectroscopy and mapping are used to follow the chemical and structural changes that occur in Li2MnO3. Both conventional slurry electrodes and thin films are studied as a function of the state of charge (voltage) and cycle number. Thin films have similar electrochemical properties as electrodes prepared from slurries,more » but allow for spectroscopic investigations on uniform samples without carbon additives. Spectral changes correlate well with electrochemical activity and support a mechanism whereby capacity is lost upon extended cycling due to the formation of new manganese oxide phases. Raman mapping of both thin film and slurry electrodes charged to different voltages reveals significant variation in the local structure. Poor conductivity and slow kinetics associated with a two-phase reaction mechanism contribute to the heterogeneity.« less

  19. DNA-gold nanoparticles network based electrochemical biosensors for DNA MTase activity.

    PubMed

    Hong, Lu; Wan, Jing; Zhang, Xiaojun; Wang, Guangfeng

    2016-05-15

    In this work, a highly sensitive electrochemical DNA methyltransferase (MTase) activity assay was fabricated with DNA-gold nanoparticles (Au NPs) network as signal amplification unit and an easy assembly method by the linkage of benzenedithiol bridge. By two complementary AuNPs modified single-stranded DNA, DNA-gold nanoparticles network was self-assembled. With the linkage of benzenedithiol bridge, the DNA network structure was immobilized on the surface of gold electrode through the covalent Au-S bond. In the presence of Dam MTase, the special sites of DNA-AuNPs network were methylated and could not be digested by restriction endonuclease Mbo I. Thus the loaded electrochemical indicator Methylene blue (MB) was MB molecules still remained on the DNA-Au NPs network. The electrochemical response depended on the methylated degree, which could be used to detect MTase activity. By the differential pulse voltammetry (DPV), it was demonstrated that a linear relationship between the DPV response and logarithm of Dam concentration ranged from 0.075 to 30U/mL, achieving a low detection limit of 0.02U/mL. The use of benzenedithiol avoided the direct incubation of the solid electrode with the capture DNA probe under complex and harsh conditions. Therefore the immobilization of DNA-AuNPs network was easy to be carried out, which is favorable for the specially high stability and reproducibility of the electrochemical biosensor. PMID:26992515

  20. Sensitive electrochemical aptasensor for thrombin detection based on graphene served as platform and graphene oxide as enhancer.

    PubMed

    He, Chun; Xu, Zenghong; Sun, Tao; Wang, Li

    2014-01-01

    A sensitive electrochemical aptasensor was developed with conductive graphene served as platform and inert graphene oxide (GO) as enhancer. An electrodeposited nano-Au layer was firstly formed on conductive graphene modified glass carbon electrode surface for further immobilizing of electrochemical redox probe hexacyanoferrates nanoparticles (NiHCFNPs). Subsequently, another nano-Au layer was formed for immobilizing of thrombin aptamer (TBA). In the presence of thrombin, the TBA on the electrode surface could bind with thrombin, which made a barrier for electrons and inhibited the electro-transfer, resulting in the decreased electrochemical signals of NiHCFNPs. Owing to the non-conductivity property of graphene oxide, further decreased electrochemical signals of NiHCFNPs could be obtained via the sandwich reaction with GO-labeled TBA. According to the signal changes before the thrombin recognition and after sandwich reaction, trace detection of thrombin could be achieved. As a result, the proposed approach showed a high sensitivity and a wider linearity to thrombin in the range from 0.005 nM to 50 nM with a detection limit of 1 pM. PMID:24142359

  1. Facile route to covalently-jointed graphene/polyaniline composite and it's enhanced electrochemical performances for supercapacitors

    NASA Astrophysics Data System (ADS)

    Qiu, Hanxun; Han, Xuebin; Qiu, Feilong; Yang, Junhe

    2016-07-01

    A polyaniline/graphene composite with covalently-bond is synthesized by a novel approach. In this way, graphene oxide is functionalized firstly by introducing amine groups onto the surface with the reduction of graphene oxide in the process and then served as the anchor sites for the growth of polyaniline (PANI) via in-situ polymerization. The composite material is characterized by electron microscopy, the resonant Raman spectra, X-ray diffraction, transform infrared spectroscopy and X-ray photoelectron spectroscopy. The electrochemical properties of the composite are measured by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charging/discharging. With the functionalization process, the graphene/polyaniline composite electrode exhibits remarkably enhanced electrochemical performance with specific capacitance of 489 F g-1 at 0.5 A g-1, which is superior to those of its individual components. The outstanding electrochemical performance of the hybrid can be attributed to its covalently synergistic effect between graphene and polyaniline, suggesting promising potentials for supercapacitors.

  2. Enhancement of electrochemical behavior of nanostructured LiFePO4/Carbon cathode material with excess Li

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Nazri, M.; Naik, V. M.; Garg, V. K.; Oliveira, A. C.; Vaishnava, P. P.; Nazri, G. A.; Naik, R.

    2016-02-01

    We have synthesized carbon coated LiFePO4 (C-LiFePO4) and C-Li1.05FePO4 with 5 mol% excess Li via sol-gel method using oleic acid as a source of carbon for enhancing electronic conductivity and reducing the average particle size. Although the phase purity of the crystalline samples was confirmed by x-ray diffraction (XRD), the 57Fe Mössbauer spectroscopy analyses show the presence of ferric impurity phases in both stoichiometric and non-stoichiometric C-LiFePO4 samples. Transmission electron microscopy measurements show nanosized C-LiFePO4 particles uniformly covered with carbon, with average particle size reduced from ∼100 nm to ∼50 nm when excess lithium is used. Electrochemical measurements indicate a lower charge transfer resistance and better electrochemical performance for C-Li1.05FePO4 compared to that of C-LiFePO4. The aim of this work is to systematically analyze the nature of impurities formed during synthesis of LiFePO4 cathode material, and their impact on electrochemical performance. The correlation between the morphology, charge transfer resistance, diffusion coefficient and electrochemical performance of C-LiFePO4 and C- Li1.05FePO4 cathode materials are discussed.

  3. Coralloid Co2P2O7 Nanocrystals Encapsulated by Thin Carbon Shells for Enhanced Electrochemical Water Oxidation.

    PubMed

    Chang, Yingxue; Shi, Nai-En; Zhao, Shulin; Xu, Dongdong; Liu, Chunyan; Tang, Yu-Jia; Dai, Zhihui; Lan, Ya-Qian; Han, Min; Bao, Jianchun

    2016-08-31

    Core-shell nanohybrids containing cheap inorganic nanocrystals and nanocarbon shells are promising electrocatalysts for water splitting or other renewable energy options. Despite that great progress has been achieved, biomimetic synthesis of metal phosphates@nanocarbon core-shell nanohybrids remains a challenge, and their use for electrocatalytic oxygen evolution reaction (OER) has not been explored. In this paper, novel nanohybrids composed of coralloid Co2P2O7 nanocrystal cores and thin porous nanocarbon shells are synthesized by combination of the structural merits of supramolecular polymer gels and a controllable thermal conversion technique, i.e., temperature programmable annealing of presynthesized supramolecular polymer gels that contain cobalt salt and phytic acid under a proper gas atmosphere. Electrocatalytic tests in alkaline solution show that such nanohybrids exhibit greatly enhanced electrocatalytic OER performance compared with that of Co2P2O7 nanostructure. At a current density of 10 mA cm(-2), their overpotential is 0.397 V, which is much lower than that of Co2P2O7 nanostructures, amorphous Co-Pi nanomaterials, Co(PO3)2 nanosheets, Pt/C, and some reported OER catalysts, and close to that of commercial IrO2. Most importantly, both of their current density at the overpotential over 0.40 V and durability are superior to those of IrO2 catalyst. As revealed by a series of spectroscopic and electrochemical analyses, their enhanced electrocatalytic performance results from the presence of thin porous nanocarbon shells, which not only improve interfacial electron penetration or transfer dynamics but also vary the coordination environment and increase the number of active 5-coordinated Co(2+) sites in Co2P2O7 cores. PMID:27500553

  4. Electrochemical Cathodic Polarization, a Simplified Method That Can Modified and Increase the Biological Activity of Titanium Surfaces: A Systematic Review

    PubMed Central

    2016-01-01

    Background The cathodic polarization seems to be an electrochemical method capable of modifying and coat biomolecules on titanium surfaces, improving the surface activity and promoting better biological responses. Objective The aim of the systematic review is to assess the scientific literature to evaluate the cellular response produced by treatment of titanium surfaces by applying the cathodic polarization technique. Data, Sources, and Selection The literature search was performed in several databases including PubMed, Web of Science, Scopus, Science Direct, Scielo and EBSCO Host, until June 2016, with no limits used. Eligibility criteria were used and quality assessment was performed following slightly modified ARRIVE and SYRCLE guidelines for cellular studies and animal research. Results Thirteen studies accomplished the inclusion criteria and were considered in the review. The quality of reporting studies in animal models was low and for the in vitro studies it was high. The in vitro and in vivo results reported that the use of cathodic polarization promoted hydride surfaces, effective deposition, and adhesion of the coated biomolecules. In the experimental groups that used the electrochemical method, cellular viability, proliferation, adhesion, differentiation, or bone growth were better or comparable with the control groups. Conclusions The use of the cathodic polarization method to modify titanium surfaces seems to be an interesting method that could produce active layers and consequently enhance cellular response, in vitro and in vivo animal model studies. PMID:27441840

  5. Sensitive electrochemical assaying of DNA methyltransferase activity based on mimic-hybridization chain reaction amplified strategy.

    PubMed

    Zhang, Linqun; Liu, Yuanjian; Li, Ying; Zhao, Yuewu; Wei, Wei; Liu, Songqin

    2016-08-24

    A mimic-hybridization chain reaction (mimic-HCR) amplified strategy was proposed for sensitive electrochemically detection of DNA methylation and methyltransferase (MTase) activity In the presence of methylated DNA, DNA-gold nanoparticles (DNA-AuNPs) were captured on the electrode by sandwich-type assembly. It then triggered mimic-HCR of two hairpin probes to produce many long double-helix chains for numerous hexaammineruthenium (III) chloride ([Ru(NH3)6](3+), RuHex) inserting. As a result, the signal for electrochemically detection of DNA MTase activity could be amplified. If DNA was non-methylated, however, the sandwich-type assembly would not form because the short double-stranded DNAs (dsDNA) on the Au electrode could be cleaved and digested by restriction endonuclease HpaII (HapII) and exonuclease III (Exo III), resulting in the signal decrement. Based on this, an electrochemical approach for detection of M.SssI MTase activity with high sensitivity was developed. The linear range for M.SssI MTase activity was from 0.05 U mL(-1) to 10 U mL(-1), with a detection limit down to 0.03 U mL(-1). Moreover, this detecting strategy held great promise as an easy-to-use and highly sensitive method for other MTase activity and inhibition detection by exchanging the corresponding DNA sequence. PMID:27496999

  6. Hydrothermal synthesis of reduced graphene sheets/Fe2O3 nanorods composites and their enhanced electrochemical performance for supercapacitors

    NASA Astrophysics Data System (ADS)

    Yang, Wanlu; Gao, Zan; Wang, Jun; Wang, Bin; Liu, Lianhe

    2013-06-01

    Reduced graphene nanosheets/Fe2O3 nanorods (GNS/Fe2O3) composite has been fabricated by a hydrothermal route for supercapacitor electrode materials. The obtained GNS/Fe2O3 composite formed a uniform structure with the Fe2O3 nanorods grew on the graphene surface and/or filled between the graphene sheets. The electrochemical performances of the GNS/Fe2O3 hybrid supercapacitor were tested by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge tests in 6 M KOH electrolyte. Comparing with the pure Fe2O3 electrode, GNS/Fe2O3 composite electrode exhibits an enhanced specific capacitance of 320 F g-1 at 10 mA cm-2 and an excellent cycle-ability with capacity retention of about 97% after 500 cycles. The simple and cost-effective preparation technique of this composite with good capacitive behavior encourages its potential commercial application.

  7. Theoretical approach for optical response in electrochemical systems: Application to electrode potential dependence of surface-enhanced Raman scattering

    SciTech Connect

    Iida, Kenji; Noda, Masashi; Nobusada, Katsuyuki

    2014-09-28

    We propose a theoretical approach for optical response in electrochemical systems. The fundamental equation to be solved is based on a time-dependent density functional theory in real-time and real-space in combination with its finite temperature formula treating an electrode potential. Solvation effects are evaluated by a dielectric continuum theory. The approach allows us to treat optical response in electrochemical systems at the atomistic level of theory. We have applied the method to surface-enhanced Raman scattering (SERS) of 4-mercaptopyridine on an Ag electrode surface. It is shown that the SERS intensity has a peak as a function of the electrode potential. Furthermore, the real-space computational approach facilitates visualization of variation of the SERS intensity depending on an electrode potential.

  8. Enhancement of electrochemical performance of LiFePO4 nanoparticles by direct nanocoating with conductive carbon layers

    NASA Astrophysics Data System (ADS)

    Świder, Joanna; Molenda, Marcin; Kulka, Andrzej; Molenda, Janina

    2016-07-01

    The results of simple and environmental-friendly method of the carbon nanocoatings on low-conductive cathode material have been shown in this work. The carbon nanocoatings were prepared during wet impregnation process of precursor derived from hydrophilic polymer based on poly(N-vinylformamide) modified by pyromellitic acid. The crystal structures and morphology of all composites were characterized by X-ray powder diffraction (XRD), low temperature nitrogen adsorption/desorption measurements (N2-BET) and transmission electronic microscopy (TEM). The electrical properties of the obtained composites were examined by EC studies. The electrochemical performance was carried out in galvanostatic mode with stable charge-discharge current and performed in Li/Li+/(CCL/LiFePO4) type cells. The process of formation CCL/LiFePO4 nanocomposite significantly enhances the electrical conductivity of the material and improves its capacity retention and electrochemical performance.

  9. Electrochemical oxidation of fluoroquinolone antibiotics: Mechanism, residual antibacterial activity and toxicity change.

    PubMed

    Zhu, Linyan; Santiago-Schübel, Beatrix; Xiao, Hongxia; Hollert, Henner; Kueppers, Stephan

    2016-10-01

    In this paper, we studied the electrochemical oxidation mechanisms of three typical fluoroquinolone antibiotics (FQs), and investigated residual antibacterial activity and toxicity changes after oxidation processes. Electrochemistry coupled to mass spectrometry (EC-MS) was used to study the oxidation processes of ciprofloxacin (CIP), norfloxacin (NOR) and ofloxacin (OFL). Eight oxidation products for each parent compound were identified and their chemical structures were elucidated. The transformation trend of each product, with the continuous increase of voltage from 0 to 3000 mV, was recorded by online EC-MS. The oxidation pathways were proposed based on the structural information and transformation trends of oxidation products. We found the oxidation mechanisms of FQs consisted of the hydroxylation and cleavage of piperazinyl ring via reactions with hydroxyl radicals, while the fluoroquinolone core remained intact. The antibacterial activity of the parent compounds and their oxidation mixtures was estimated using zone inhibition tests for gram-negative bacteria Salmonella typhimurium. It was found that the oxidation mixtures of CIP and NOR retained the antibacterial properties with lower activity compared to their parent compounds, while the antibacterial activity of OFL was almost eliminated after oxidation. Furthermore, the toxicity of the three FQs and their oxidation mixtures were evaluated using algal growth inhibition test (Desmodesmus subspicatus). The median effective concentration (EC50) values for the algal inhibition tests were calculated for the end point of growth rate. The toxicity of CIP and NOR to green algae after electrochemical oxidation, remained unchanged, while that of OFL significantly increased. The results presented in this paper contribute to an understanding of the electrochemical oxidation mechanisms of FQs, and highlight the potential environmental risks of FQs after electrochemical oxidation processes. PMID:27318447

  10. Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li-O2 battery capacity.

    PubMed

    Burke, Colin M; Pande, Vikram; Khetan, Abhishek; Viswanathan, Venkatasubramanian; McCloskey, Bryan D

    2015-07-28

    Among the "beyond Li-ion" battery chemistries, nonaqueous Li-O2 batteries have the highest theoretical specific energy and, as a result, have attracted significant research attention over the past decade. A critical scientific challenge facing nonaqueous Li-O2 batteries is the electronically insulating nature of the primary discharge product, lithium peroxide, which passivates the battery cathode as it is formed, leading to low ultimate cell capacities. Recently, strategies to enhance solubility to circumvent this issue have been reported, but rely upon electrolyte formulations that further decrease the overall electrochemical stability of the system, thereby deleteriously affecting battery rechargeability. In this study, we report that a significant enhancement (greater than fourfold) in Li-O2 cell capacity is possible by appropriately selecting the salt anion in the electrolyte solution. Using (7)Li NMR and modeling, we confirm that this improvement is a result of enhanced Li(+) stability in solution, which, in turn, induces solubility of the intermediate to Li2O2 formation. Using this strategy, the challenging task of identifying an electrolyte solvent that possesses the anticorrelated properties of high intermediate solubility and solvent stability is alleviated, potentially providing a pathway to develop an electrolyte that affords both high capacity and rechargeability. We believe the model and strategy presented here will be generally useful to enhance Coulombic efficiency in many electrochemical systems (e.g., Li-S batteries) where improving intermediate stability in solution could induce desired mechanisms of product formation. PMID:26170330

  11. Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O2 battery capacity

    PubMed Central

    Burke, Colin M.; Pande, Vikram; Khetan, Abhishek; Viswanathan, Venkatasubramanian; McCloskey, Bryan D.

    2015-01-01

    Among the “beyond Li-ion” battery chemistries, nonaqueous Li–O2 batteries have the highest theoretical specific energy and, as a result, have attracted significant research attention over the past decade. A critical scientific challenge facing nonaqueous Li–O2 batteries is the electronically insulating nature of the primary discharge product, lithium peroxide, which passivates the battery cathode as it is formed, leading to low ultimate cell capacities. Recently, strategies to enhance solubility to circumvent this issue have been reported, but rely upon electrolyte formulations that further decrease the overall electrochemical stability of the system, thereby deleteriously affecting battery rechargeability. In this study, we report that a significant enhancement (greater than fourfold) in Li–O2 cell capacity is possible by appropriately selecting the salt anion in the electrolyte solution. Using 7Li NMR and modeling, we confirm that this improvement is a result of enhanced Li+ stability in solution, which, in turn, induces solubility of the intermediate to Li2O2 formation. Using this strategy, the challenging task of identifying an electrolyte solvent that possesses the anticorrelated properties of high intermediate solubility and solvent stability is alleviated, potentially providing a pathway to develop an electrolyte that affords both high capacity and rechargeability. We believe the model and strategy presented here will be generally useful to enhance Coulombic efficiency in many electrochemical systems (e.g., Li–S batteries) where improving intermediate stability in solution could induce desired mechanisms of product formation. PMID:26170330

  12. The self-assembly of redox active peptides: Synthesis and electrochemical capacitive behavior.

    PubMed

    Piccoli, Julia P; Santos, Adriano; Santos-Filho, Norival A; Lorenzón, Esteban N; Cilli, Eduardo M; Bueno, Paulo R

    2016-05-01

    The present work reports on the synthesis of a redox-tagged peptide with self-assembling capability aiming applications in electrochemically active capacitive surfaces (associated with the presence of the redox centers) generally useful in electroanalytical applications. Peptide containing ferrocene (fc) molecular (redox) group (Ac-Cys-Ile-Ile-Lys(fc)-Ile-Ile-COOH) was thus synthesized by solid phase peptide synthesis (SPPS). To obtain the electrochemically active capacitive interface, the side chain of the cysteine was covalently bound to the gold electrode (sulfur group) and the side chain of Lys was used to attach the ferrocene in the peptide chain. After obtaining the purified redox-tagged peptide, the self-assembly and redox capability was characterized by cyclic voltammetry (CV) and electrochemical impedance-based capacitance spectroscopy techniques. The obtained results confirmed that the redox-tagged peptide was successfully attached by forming an electroactive self-assembled monolayer onto gold electrode. The design of redox active self-assembly ferrocene-tagged peptide is predictably useful in the development of biosensor devices precisely to detect, in a label-free platform, those biomarkers of clinical relevance. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 357-367, 2016. PMID:26832983

  13. Repeated in vivo electrochemical activation and the biological effects of microelectromechanical systems drug delivery device.

    PubMed

    Shawgo, Rebecca S; Voskerician, Gabriela; Duc, Hong Linh Ho; Li, Yawen; Lynn, Aaron; MacEwan, Matthew; Langer, Robert; Anderson, James M; Cima, Michael J

    2004-12-15

    The repeated activation of a microelectromechanical systems (MEMS) drug delivery device was studied in vivo in rats to examine the effect of implantation on the device operation and the effect of electrochemical activation on the inflammatory and wound-healing response. The MEMS devices were fabricated from a silicon wafer into which reservoirs were etched and covered with gold membranes. The membranes were electrochemically removed when an anodic voltage was applied. Devices were implanted subcutaneously both with and without stainless steel mesh cages for 4, 7, 14, 21, or 28 days before activation. Devices were activated every other day for five activations. Leukocyte concentrations indicated that both the application of voltage and the gold corrosion products elevated the inflammatory response which was resolved within 48 h after each activation. The efficiency of gold membrane removal was not impaired throughout the implantation, although a bimodal distribution of background current densities was observed after long implantation times. The thickness of the fibrous capsule surrounding the MEMS devices was similar between activated and control devices explanted at each time point. It was concluded that the repeated activation of MEMS drug delivery devices was successful and the activation produced an acceptable biological response that resolved promptly. PMID:15508122

  14. Enhanced electrochemical supercapacitance of binder-free nanoporous ternary metal oxides/metal electrode.

    PubMed

    Gao, J J; Qiu, H-J; Wen, Y R; Chiang, F-K; Wang, Y

    2016-07-15

    Free-standing nanoporous Ni-Cu-Mn mixed metal oxides on metal with a high surface area was fabricated by chemically dealloying a Ni8Cu12Mn80 single-phase precursor, followed by electrochemical oxidation in an alkaline solution. Electrochemical analysis shows that first Cu and Mn-based metal oxides formed by the electrochemical oxidation. Ni-based oxides grow later with the increase of electrochemical CV cycles and mix with the Cu/Mn oxides, forming a relatively stable mixed metal oxides thin film on metal ligament network. Due to the different electrochemical properties of each metal and the synergetic effect between them, the mixed ternary metal oxides formed on metal nano-ligament can operate stably between a wide potential window (1.5V) in 1.0M KOH aqueous solution when tested as a free-standing supercapacitor electrode. Due to the high volumetric surface area, wide operating potential window and excellent conductivity, the nanoporous metal oxides@metal composite exhibits a high volumetric capacitance (∼500Fcm(-3)), high energy density (∼38mWhcm(-3)) and good cycling stability. PMID:27089016

  15. Antioxidant activity of betanidin: electrochemical study in aqueous media.

    PubMed

    Wybraniec, Sławomir; Stalica, Paweł; Spórna, Aneta; Nemzer, Boris; Pietrzkowski, Zbigniew; Michałowski, Tadeusz

    2011-11-23

    The antioxidative mechanism of action of betalains is of significant interest because these pigments are recently emerging as highly bio-active natural compounds with potential benefits to human health. Betanidin, the basic betacyanin, comprises the 5,6-dihydroxyl moiety, which results in its high antioxidant activity. Oxidation of betanidin by voltammetric techniques and chro matographic identification of the oxidation products with spectrophotometric and mass spectrometric detection (LC-DAD-MS/MS) were performed. Two main oxidation peaks for betanidin are observable at pH 3-5. These peaks become merged at higher pH, suggesting a different mechanism of oxidation at higher and lower pH values. The low oxidation potential of betanidin confirms its very strong reduction properties. The presence of two prominent oxidized products, 2-decarboxy-2,3-dehydrobetanidin and 2,17-bidecarboxy-2,3-dehydrobetanidin, indicates their generation through two reaction routes with two different quinonoid intermediates: dopachrome derivative and quinone methide. Both lead to the decarboxylative dehydrogenation of betanidin. Subsequent oxidation and rearrangement of the conjugated chromophoric system results in formation of 14,15-dehydrogenated derivatives. PMID:21913685

  16. Structural and Electrochemical Impacts of Oxygen Doped and Surfactant Coated Activated Carbon Electrodes in Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    Collins, John; Gourdin, Gerald; Qu, Deyang; Foster, Michelle

    2013-03-01

    Passive charge and discharge dynamics are necessary for advancing Li-ion batteries. Surfactant adsorption on activated carbon has been shown to promote advancements in the discharge capacity, time and cycle-ability of electrochemical systems--specifically by enhancing diffusion pathways for ion insertion/de-insertion and suppressing pore blockage from precipitates known to form during charge/discharge states. Enhancement of surfactant chemisorption on activated carbon is achieved through oxygen doping of the carbon surface. In addition, doping alters the degree of Faradaic processes occurring in solution, resulting in prolonged reduction at the carbon surface. The work presented describes how surface oxygen groups on a granulated activated carbon have been manipulated using nitric acid in a controlled, stepwise fashion. A nonionic surfactant was applied to oxidized and non-oxidized samples at various concentrations. The composition and structure of the activated carbon surface was characterized using DRIFTS, Raman Spectroscopy, SEM and Porosimetry. The charge/discharge Li insertion capacities along with correlating surface microstructure changes were analyzed for all treated electrodes at progressive oxidation stages.

  17. Activated mesoporous carbon nanofibers fabricated using water etching-assisted templating for high-performance electrochemical capacitors.

    PubMed

    An, Geon-Hyoung; Koo, Bon-Ryul; Ahn, Hyo-Jin

    2016-03-01

    Activated mesoporous carbon nanofibers (AMCNFs) are synthesized by a sequential process of electrospinning, water etching-assisted templating, and acid treatment. Their morphologies, crystal structures, melting behavior, chemical bonding states, surface properties, and electrochemical performance are investigated for three different polyacrylonitrile (PAN) to polyvinylpyrrolidone (PVP) weight ratios - PAN : PVP = 8 : 2, 7 : 3, and 6 : 4. Compared to other samples, the AMCNFs with an optimum weight ratio of 6 : 4 show the highest specific surface area of 692 m(2) g(-1), a high volume percentage of mesopores of 43.9%, and an increased amount of carboxyl groups (10.5%). This results in a high specific capacitance of 207 F g(-1), a high-rate capability with a capacitance retention of 93%, a high energy density of 24.8-23.1 W h kg(-1), and an excellent cycling durability of up to 3000 cycles. The electrochemical performance improvement can be explained by the combined effect of the high surface area relative to the increased electrical double-layers, the high volume fraction of mesopores relative to shorter diffusion routes and low resistance pathways for ions, and the increased amount of carboxyl groups on the CNF surface relative to enhanced wettability. PMID:26866359

  18. Enhancing electrochemical detection on graphene oxide-CNT nanostructured electrodes using magneto-nanobioprobes.

    PubMed

    Sharma, Priyanka; Bhalla, Vijayender; Dravid, Vinayak; Shekhawat, Gajendera; Jinsong-Wu; Prasad, E Senthil; Suri, C Raman

    2012-01-01

    Graphene and related materials have come to the forefront of research in electrochemical sensors during recent years due to the promising properties of these nanomaterials. Further applications of these nanomaterials have been hampered by insufficient sensitivity offered by these nanohybrids for the type of molecules requiring lower detection ranges. Here, we report a signal amplification strategy based on magneto-electrochemical immunoassay which combines the advantages of carbon nanotube and reduced graphene oxide together with electrochemical bursting of magnetic nanoparticles into a large number of metal ions. Sensitive detection was achieved by precisely designing the nanohybrid and correlating the available metal ions with analyte concentration. We confirmed the ultrahigh sensitivity of this method for a new generation herbicide diuron and its analogues up to sub-picomolar concentration in standard water samples. The novel immune-detection platform showed the excellent potential applicability in rapid and sensitive screening of environmental pollutants or toxins in samples. PMID:23166860

  19. Enhancing electrochemical detection on graphene oxide-CNT nanostructured electrodes using magneto-nanobioprobes

    PubMed Central

    Sharma, Priyanka; Bhalla, Vijayender; Dravid, Vinayak; Shekhawat, Gajendera; Jinsong-Wu, J W; Prasad, E. Senthil; Suri, C. Raman

    2012-01-01

    Graphene and related materials have come to the forefront of research in electrochemical sensors during recent years due to the promising properties of these nanomaterials. Further applications of these nanomaterials have been hampered by insufficient sensitivity offered by these nanohybrids for the type of molecules requiring lower detection ranges. Here, we report a signal amplification strategy based on magneto-electrochemical immunoassay which combines the advantages of carbon nanotube and reduced graphene oxide together with electrochemical bursting of magnetic nanoparticles into a large number of metal ions. Sensitive detection was achieved by precisely designing the nanohybrid and correlating the available metal ions with analyte concentration. We confirmed the ultrahigh sensitivity of this method for a new generation herbicide diuron and its analogues up to sub-picomolar concentration in standard water samples. The novel immune-detection platform showed the excellent potential applicability in rapid and sensitive screening of environmental pollutants or toxins in samples. PMID:23166860

  20. A 96-well electrochemical method for the screening of enzymatic activities.

    PubMed

    Abdellaoui, Sofiène; Noiriel, Alexandre; Henkens, Robert; Bonaventura, Celia; Blum, Loïc J; Doumèche, Bastien

    2013-04-01

    The rapid electrochemical screening of enzyme activities in bioelectronics is still a challenging issue. In order to solve this problem, we propose to use a 96-well electrochemical assay. This system is composed of 96 screen-printed electrodes on a printed circuit board adapted from a commercial system (carbon is used as the working electrode and silver chloride as the counter/reference electrode). The associated device allows for the measurements on the 96 electrodes to be performed within a few seconds. In this work, we demonstrate the validity of the screening method with the commercial laccase from the fungus Trametes versicolor. The signal-to-noise ratio (S/N) is found to be the best way to analyze the electrochemical signals. The S/N follows a saturation-like mechanism with a dynamic linear range of two decades ranging from 0.5 to 75 ng of laccase (corresponding to enzymatic activities from 62 × 10(-6) to 9.37 × 10(-3) μmol min(-1)) and a sensitivity of 3027 μg(-1) at +100 mV versus Ag/AgCl. Laccase inhibitors (azide and fluoride anions), pH optima, and interfering molecules could also be identified within a few minutes. PMID:23461701

  1. Electrochemical activity of holotransferrin and its electrocatalysis-mediated process of artemisinin.

    PubMed

    Cai, Huai-Hong; Cai, Jiye; Yang, Pei-Hui

    2009-02-01

    Holotransferrin, the iron (III) transport protein in the blood, can significantly increase the anticancer activity of artemisinin, which is isolated from the Chinese plant qinghaosu. This paper investigates the action process of holotransferrin-induced electrocatalytic reduction of artemisinin by spectroscopic and electrochemical techniques. Results show that holotransferrin(Fe(III)) is the electrochemical sites of holotransferrin, which can catalyze the reduction of artemisinin through lowering the overpotential by about 80 mV. Compared with the different electrochemical behaviors of artemisinin with apotransferrin and holoprotein (apotransferrin in the presence of Fe(III)), respectively, it demonstrates that holotransferrin(Fe(III)) plays an important role in the electrocatalytic reduction of artemisinin, which can catalyze the cleavage of the endoperoxide bridge in artemisinin. A reliable two-step process is proposed to explain that artemisinin is activated by holotransferrin(Fe(III))-mediated electrocatalytic reduction. These results can provide further information for better understanding the anticancer action of holotransferrin-conjugated artemisinin. PMID:19117755

  2. Scanning electrochemical microscopy of living cells: different redox activities of nonmetastatic and metastatic human breast cells.

    PubMed

    Liu, B; Rotenberg, S A; Mirkin, M V

    2000-08-29

    Electrochemical methods have been widely used to monitor physiologically important molecules in biological systems. This report describes the first application of the scanning electrochemical microscope (SECM) to probe the redox activity of individual living cells. The possibilities of measuring the rate and investigating the pathway of transmembrane charge transfer are demonstrated. By this approach, significant differences are detected in the redox responses given by nonmotile, nontransformed human breast epithelial cells, breast cells with a high level of motility (engendered by overexpression of protein kinase Calpha), and highly metastatic breast cancer cells. SECM analysis of the three cell lines reveals reproducible differences with respect to the kinetics of charge transfer by several redox mediators. PMID:10963658

  3. Scanning electrochemical microscopy of living cells: Different redox activities of nonmetastatic and metastatic human breast cells

    PubMed Central

    Liu, Biao; Rotenberg, Susan A.; Mirkin, Michael V.

    2000-01-01

    Electrochemical methods have been widely used to monitor physiologically important molecules in biological systems. This report describes the first application of the scanning electrochemical microscope (SECM) to probe the redox activity of individual living cells. The possibilities of measuring the rate and investigating the pathway of transmembrane charge transfer are demonstrated. By this approach, significant differences are detected in the redox responses given by nonmotile, nontransformed human breast epithelial cells, breast cells with a high level of motility (engendered by overexpression of protein kinase Cα), and highly metastatic breast cancer cells. SECM analysis of the three cell lines reveals reproducible differences with respect to the kinetics of charge transfer by several redox mediators. PMID:10963658

  4. Real space mapping of ionic diffusion and electrochemical activity in energy storage and conversion materials

    DOEpatents

    Kalinin, Sergei V; Balke, Nina; Kumar, Amit; Dudney, Nancy J; Jesse, Stephen

    2014-05-06

    A method and system for probing mobile ion diffusivity and electrochemical reactivity on a nanometer length scale of a free electrochemically active surface includes a control module that biases the surface of the material. An electrical excitation signal is applied to the material and induces the movement of mobile ions. An SPM probe in contact with the surface of the material detects the displacement of mobile ions at the surface of the material. A detector measures an electromechanical strain response at the surface of the material based on the movement and reactions of the mobile ions. The use of an SPM tip to detect local deformations allows highly reproducible measurements in an ambient environment without visible changes in surface structure. The measurements illustrate effective spatial resolution comparable with defect spacing and well below characteristic grain sizes of the material.

  5. A comparison of the electrochemical behavior of carbon aerogels and activated carbon fiber cloths

    SciTech Connect

    Tran, T.D.; Alviso, C.T.; Hulsey, S.S.; Nielsen, J.K.; Pekala, R.W.

    1996-05-10

    Electrochemical capacitative behavior of carbon aerogels and commercial carbon fiber cloths was studied in 5M KOH, 3M sulfuric acid, and 0.5M tetrethylammonium tetrafluoroborate/propylene carbonate electrolytes. The resorcinol-formaldehyde based carbon aerogels with a range of denisty (0.2-0.85 g/cc) have open-cell structures with ultrafine pore sizes (5-50 nm), high surface area (400-700 m{sup 2}/g), and a solid matrix composed of interconnected particles or fibers with characteristic diameters of 10 nm. The commercial fiber cloths in the density range 0.2-04g/cc have high surface areas (1000-2500 m{sup 2}/g). The volumetric capacitances of high-density aerogels are shown to be comparable to or exceeding those from activated carbon fibers. Electrochemical behavior of these materials in various electrolytes is compared and related to their physical properties.

  6. Improvement in electrochemical capacitance of activated carbon from scrap tires by nitric acid treatment

    NASA Astrophysics Data System (ADS)

    Han, Yan; Zhao, Ping-Ping; Dong, Xiao-Ting; Zhang, Cui; Liu, Shuang-Xi

    2014-12-01

    Activated carbon (AC) obtained from the industrial pyrolytic tire char is treated by concentrated nitric acid (AC-HNO3) and then used as the electrode material for supercapacitors. Surface properties and electrochemical capacitances of AC and ACHNO3 are studied. It is found that the morphology and the porous texture for AC and AC-HNO3 have little difference, while the oxygen content increases and functional groups change after the acid treatment. Electrochemical results demonstrate that the AC-HNO3 electrode displays higher specific capacitance, better stability and cycling performance, and lower equivalent series resistance, indicating that AC obtained from the industrial pyrolytic tire char treated by concentrated nitric acid is applicable for supercapacitors.

  7. Label-free electrochemical lead (II) aptasensor using thionine as the signaling molecule and graphene as signal-enhancing platform.

    PubMed

    Gao, Feng; Gao, Cai; He, Suyu; Wang, Qingxiang; Wu, Aiqun

    2016-07-15

    A label-free and highly sensitive electrochemical aptasensor for Pb(2+) was constructed using thionine (TH) as the signaling molecule and graphene (GR) as the signal-enhancing platform. The electrochemical sensing interface was fabricated by stepwise assembly of GR and TH on the lead (II) specific aptamer (LSA) modified electrode. Upon interaction with Pb(2+), the aptamer probe on the sensor underwent conformational switch from a single-stranded DNA form to the G-quadruplex structure, causing the GR with assembled TH released from the electrode surface into solution. As a result, the electrochemical signal of TH on the aptasensor was substantially reduced. Under the optimal experimental conditions, the attenuation of peak currents presented a good linear relationship with the logarithm of Pb(2+) concentrations over the range from 1.6×10(-13) to 1.6×10(-10)M. The detection limit was estimated to be 3.2×10(-14)M. The aptasensor also exhibited good regenerability, excellent selectivity, and acceptable reproducibility, indicating promising application in environment monitoring of lead. PMID:26913503

  8. Enhanced electrochemical performance of mesoporous NiCo2O4 as an excellent supercapacitive alternative energy storage material

    NASA Astrophysics Data System (ADS)

    Bhojane, Prateek; Sen, Somaditya; Shirage, Parasharam M.

    2016-07-01

    Here we report the supercapacitive properties of mesoporous nickel cobalt oxide (NiCo2O4) synthesized by fast, inexpensive and facile chemical bath method, by avoiding high pressure, high temperature and chemical complexity. Physico-chemical characterization techniques such as X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), Raman Spectra, and nitrogen adsorption-desorption isotherm analysis is performed to characterize the electrode material. Brunauer-Emmett-Teller (BET) measurements reveal the surface area 52.86 m2 g-1 and from Barrett-Joyner-Halenda (BJH), typical pores size ranges between 10 and 50 nm, also confirms the mesoporosity. The electrochemical properties are measured by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charging/discharging. The synthesized material exhibits remarkably enhanced electrochemical performance with specific capacitance of 1130 F g-1 at 1 mV s-1 sweep rate and 1125 F g-1 at current density of 0.05 A g-1, highest without supporting base like carbon cloth, Ni-foam, Ti- foil used for direct growth (deposition) of electrode material. It is superior to those of its individual and hybrid components prepared by similar technique. Ragone plot shows high specific energy density (49.25 Wh kg-1) and corresponding specific power density (1851.31 W kg-1) even at high current density of 0.5 A g-1.

  9. Electrochemically exfoliated graphene anodes with enhanced biocurrent production in single-chamber air-breathing microbial fuel cells.

    PubMed

    Najafabadi, Amin Taheri; Ng, Norvin; Gyenge, Előd

    2016-07-15

    Microbial fuel cells (MFCs) present promising options for environmentally sustainable power generation especially in conjunction with waste water treatment. However, major challenges remain including low power density, difficult scale-up, and durability of the cell components. This study reports enhanced biocurrent production in a membrane-free MFC, using graphene microsheets (GNs) as anode and MnOx catalyzed air cathode. The GNs are produced by ionic liquid assisted simultaneous anodic and cathodic electrochemical exfoliation of iso-molded graphite electrodes. The GNs produced by anodic exfoliation increase the MFC peak power density by over 300% compared to plain carbon cloth (i.e., 2.85Wm(-2) vs 0.66Wm(-2), respectively), and by 90% compared to conventional carbon black (i.e., Vulcan XC-72) anode. These results exceed previously reported power densities for graphene-containing MFC anodes. The fuel cell polarization results are corroborated by electrochemical impedance spectroscopy indicating three times lower charge transfer resistance for the GN anode. Material characterizations suggest that the best performing GN samples were of relatively smaller size (~500nm), with higher levels of ionic liquid induced surface functionalization during the electrochemical exfoliation process. PMID:26926591

  10. Electrochemical properties of small clusters of metal atoms and their role in the surface-enhanced Raman scattering

    SciTech Connect

    Plieth, W.J.

    1981-06-01

    Starting with equations for the shift of the reversible redox potential of small metal particles with size, the electrochemical properties of these particles are discussed. Approximate equations are given for the relationship between the particle size and the surface charge, the potential of zero charge, the surface potential, work function and quantities related to this function. The influence of these properties on redox reactions, electrosorption and chemi-sorption are discussed. The results are used to explain experimental observation in connection with the surface enhanced Raman effect.

  11. Nanocrystals of Uranium Oxide: Controlled Synthesis and Enhanced Electrochemical Performance of Hydrogen Evolution by Ce Doping.

    PubMed

    Hu, Shi; Li, Haoyi; Liu, Huiling; He, Peilei; Wang, Xun

    2015-06-10

    A preliminary study of the growth of 0D, 1D, and 2D nanostructures of uranium oxides with feature sizes from several nanometers down to 1 nm are presented. Cerium is successfully doped into these oxides and its influence on the growth dynamics and electrochemical performance investigated. PMID:25627103

  12. Isolation and Characterization of Electrochemically Active Subsurface Delftia and Azonexus Species

    PubMed Central

    Jangir, Yamini; French, Sarah; Momper, Lily M.; Moser, Duane P.; Amend, Jan P.; El-Naggar, Mohamed Y.

    2016-01-01

    Continental subsurface environments can present significant energetic challenges to the resident microorganisms. While these environments are geologically diverse, potentially allowing energy harvesting by microorganisms that catalyze redox reactions, many of the abundant electron donors and acceptors are insoluble and therefore not directly bioavailable. Extracellular electron transfer (EET) is a metabolic strategy that microorganisms can deploy to meet the challenges of interacting with redox-active surfaces. Though mechanistically characterized in a few metal-reducing bacteria, the role, extent, and diversity of EET in subsurface ecosystems remains unclear. Since this process can be mimicked on electrode surfaces, it opens the door to electrochemical techniques to enrich for and quantify the activities of environmental microorganisms in situ. Here, we report the electrochemical enrichment of microorganisms from a deep fractured-rock aquifer in Death Valley, CA, USA. In experiments performed in mesocosms containing a synthetic medium based on aquifer chemistry, four working electrodes (WEs) were poised at different redox potentials (272, 373, 472, 572 mV vs. SHE) to serve as electron acceptors, resulting in anodic currents coupled to the oxidation of acetate during enrichment. The anodes were dominated by Betaproteobacteria from the families Comamonadaceae and Rhodocyclaceae. A representative of each dominant family was subsequently isolated from electrode-associated biomass. The EET abilities of the isolated Delftia strain (designated WE1-13) and Azonexus strain (designated WE2-4) were confirmed in electrochemical reactors using WEs poised at 522 mV vs. SHE. The rise in anodic current upon inoculation was correlated with a modest increase in total protein content. Both genera have been previously observed in mixed communities of microbial fuel cell enrichments, but this is the first direct measurement of their electrochemical activity. While alternate

  13. Isolation and Characterization of Electrochemically Active Subsurface Delftia and Azonexus Species.

    PubMed

    Jangir, Yamini; French, Sarah; Momper, Lily M; Moser, Duane P; Amend, Jan P; El-Naggar, Mohamed Y

    2016-01-01

    Continental subsurface environments can present significant energetic challenges to the resident microorganisms. While these environments are geologically diverse, potentially allowing energy harvesting by microorganisms that catalyze redox reactions, many of the abundant electron donors and acceptors are insoluble and therefore not directly bioavailable. Extracellular electron transfer (EET) is a metabolic strategy that microorganisms can deploy to meet the challenges of interacting with redox-active surfaces. Though mechanistically characterized in a few metal-reducing bacteria, the role, extent, and diversity of EET in subsurface ecosystems remains unclear. Since this process can be mimicked on electrode surfaces, it opens the door to electrochemical techniques to enrich for and quantify the activities of environmental microorganisms in situ. Here, we report the electrochemical enrichment of microorganisms from a deep fractured-rock aquifer in Death Valley, CA, USA. In experiments performed in mesocosms containing a synthetic medium based on aquifer chemistry, four working electrodes (WEs) were poised at different redox potentials (272, 373, 472, 572 mV vs. SHE) to serve as electron acceptors, resulting in anodic currents coupled to the oxidation of acetate during enrichment. The anodes were dominated by Betaproteobacteria from the families Comamonadaceae and Rhodocyclaceae. A representative of each dominant family was subsequently isolated from electrode-associated biomass. The EET abilities of the isolated Delftia strain (designated WE1-13) and Azonexus strain (designated WE2-4) were confirmed in electrochemical reactors using WEs poised at 522 mV vs. SHE. The rise in anodic current upon inoculation was correlated with a modest increase in total protein content. Both genera have been previously observed in mixed communities of microbial fuel cell enrichments, but this is the first direct measurement of their electrochemical activity. While alternate

  14. Electrochemical DNA sensor for anthrax toxin activator gene atxA-detection of PCR amplicons.

    PubMed

    Das, Ritu; Goel, Ajay K; Sharma, Mukesh K; Upadhyay, Sanjay

    2015-12-15

    We report the DNA probe functionalized electrochemical genosensor for the detection of Bacillus anthracis, specific towards the regulatory gene atxA. The DNA sensor is fabricated on electrochemically deposited gold nanoparticle on self assembled layer of (3-Mercaptopropyl) trimethoxysilane (MPTS) on GC electrode. DNA hybridization is monitored by differential pulse voltammogram (DPV). The modified GC electrode is characterized by atomic force microscopy (AFM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) method. We also quantified the DNA probe density on electrode surface by the chronocoulometric method. The detection is specific and selective for atxA gene by DNA probe on the electrode surface. No report is available for the detection of B. anthracis by using atxA an anthrax toxin activator gene. In the light of real and complex sample, we have studied the PCR amplicons of 303, 361 and 568 base pairs by using symmetric and asymmetric PCR approaches. The DNA probe of atxA gene efficiently hybridizes with different base pairs of PCR amplicons. The detection limit is found to be 1.0 pM (S/N ratio=3). The results indicate that the DNA sensor is able to detect synthetic target as well as PCR amplicons of different base pairs. PMID:26257186

  15. Microfluidic Electrochemical Sensor for On-line Monitoring of Aerosol Oxidative Activity

    PubMed Central

    Sameenoi, Yupaporn; Koehler, Kirsten; Shapiro, Jeff; Boonsong, Kanokporn; Sun, Yele; Collett, Jeffrey; Volckens, John; Henry, Charles S.

    2012-01-01

    Particulate matter (PM) air pollution has a significant impact on human morbidity and mortality; however, the mechanisms of PM-induced toxicity are poorly defined. A leading hypothesis states that airborne PM induces harm by generating reactive oxygen species (ROS) in and around human tissues, leading to oxidative stress. We report here, a system employing a microfluidic electrochemical sensor coupled directly to a Particle-into-Liquid-Sampler (PILS) system to measure aerosol oxidative activity in an on-line format. The oxidative activity measurement is based on the dithiothreitol assay (DTT assay) where after oxidized by PM, the remaining reduced DTT was analyzed by the microfluidic sensor. The sensor consists of an array of working, reference, and auxiliary electrodes fabricated in a poly(dimethylsiloxane) (PDMS)-based microfluidic device. Cobalt (II) phthalocyanine (CoPC)-modified carbon paste was used as the working electrode material allowing selective detection of reduced DTT. The electrochemical sensor was validated off-line against the traditional DTT assay using filter samples taken from urban environments and biomass burning events. After off-line characterization, the sensor was coupled to a PILS to enable on-line sampling/analysis of aerosol oxidative activity. Urban dust and industrial incinerator ash samples were aerosolized in an aerosol chamber and analyzed for their oxidative activity. The on-line sensor reported DTT consumption rates (oxidative activity) in good correlation with aerosol concentration (R2 from 0.86–.97) with a time-resolution of approximately 3 minutes. PMID:22651886

  16. Polyvalent effect enhances diglycosidic antiplasmodial activity.

    PubMed

    Zhang, Wen-Qiang; He, Yun; Yu, Qun; Liu, Hai-Peng; Wang, De-Min; Li, Xiao-Bin; Luo, Jian; Meng, Xin; Qin, Hai-Juan; Lucchi, Naomi W; Udhayakumar, Venkatachalam; Iyer, Suri S; Yang, Yang; Yu, Peng

    2016-10-01

    An efficient and facile total synthesis of diglycoside Matayoside D isolated from the root bark of Matayba guianensis with antiplasmodial activity have been accomplished in 11 steps with 5% overall yields starting from commercially available glucose and rhamnose. Furthermore, a class of the diglycosidic derivatives with different lengths of the linker and valences were also prepared and evaluated for their antiplasmodial activities against chloroquine-susceptible (3D7) and chloroquine-resistant (W2) strains of Plasmodium falciparum. Low valent and short linker attached diglycoside show no enhancement of the antiplasmodial activity while polyvalent conjugates showed enhanced antiplasmodial activity with IC50 value at least 20 fold better than that of the corresponding diglycosidic monomer. The polyvalent diglycoside were non-cytotoxic against normal mammalian cells under 50,000 μg/L. PMID:27318984

  17. Direct electrochemical detection of kanamycin based on peroxidase-like activity of gold nanoparticles.

    PubMed

    Wang, Chunshuai; Liu, Chang; Luo, Jibao; Tian, Yaping; Zhou, Nandi

    2016-09-14

    An enzyme-free, ultrasensitive electrochemical detection of kanamycin residue was achieved based on mimetic peroxidase activity of gold nanoparticles (AuNPs) and target-induced replacement of the aptamer. AuNPs which were synthesized using tyrosine as a reducing and capping agent, exhibited mimetic peroxidase activity. In the presence of kanamycin-specific aptamer, however, the single-stranded DNA (ssDNA) adsorbed on the surface of AuNPs via the interaction between the bases of ssDNA and AuNPs, and therefore blocked the catalytic site of AuNPs, and inhibited their peroxidase activity. While in the presence of target kanamycin, it bound with the adsorbed aptamer on AuNPs with high affinity, exposed the surface of AuNPs and recovered the peroxidase activity. Then AuNPs catalyzed the reaction between H2O2 and reduced thionine to produce oxidized thionine. The latter exhibited a distinct reduction peak on gold electrode in differential pulse voltammetry (DPV), and could be utilized to quantify the concentration of kanamycin. Under the optimized conditions, the proposed electrochemical assay showed an extremely high sensitivity towards kanamycin, with a linear relationship between the peak current and the concentration of kanamycin in the range of 0.1-60 nM, and a detection limit of 0.06 nM. Moreover, the established approach was successfully applied in the detection of kanamycin in honey samples. Therefore, the proposed electrochemical assay has great potential in the fields of food quality control and environmental monitoring. PMID:27566341

  18. Electrochemical characterization of electrospun activated carbon nanofibres as an electrode in supercapacitors

    NASA Astrophysics Data System (ADS)

    Kim, Chan

    A new form of nanofibre web electrode has been fabricated for a supercapacitor using electrospun polybenzimidazol (PBI)-based activated carbon nanofibres. A PBI solution in dimethyl acetamide (DMAc) is electrospun to a fibre web that consists of 250 nm ultra-fine fibres. The web is successfully activated by steam of 30 vol.% and the specific surface area of the activated web is in the range of 500-1220 m 2 g -1. The electrochemical properties of electrodes and the capacitive behaviour of the resulting capacitors are systematically studied using cyclic voltammetry, ac impedance and constant-current discharge tests. The specific capacitance ranges from 35 to 202 F g -1, depending on the activation temperature. The nanofibre web activated at 800 °C exhibits the largest specific surface area and results in the highest capacitance. The capacitance of the electrical double-layer capacitor is strongly dependent on the specific surface area, pore volume, and resistivity of the samples.

  19. Isolating the effect of pore size distribution on electrochemical double-layer capacitance using activated fluid coke

    NASA Astrophysics Data System (ADS)

    Zuliani, Jocelyn E.; Tong, Shitang; Kirk, Donald W.; Jia, Charles Q.

    2015-12-01

    Electrochemical double-layer capacitors (EDLCs) use physical ion adsorption in the capacitive electrical double layer of high specific surface area (SSA) materials to store electrical energy. Previous work shows that the SSA-normalized capacitance increases when pore diameters are less than 1 nm. However, there still remains uncertainty about the charge storage mechanism since the enhanced SSA-normalized capacitance is not observed in all microporous materials. In previous studies, the total specific surface area and the chemical composition of the electrode materials were not controlled. The current work is the first reported study that systematically compares the performance of activated carbon prepared from the same raw material, with similar chemical composition and specific surface area, but different pore size distributions. Preparing samples with similar SSAs, but different pores sizes is not straightforward since increasing pore diameters results in decreasing the SSA. This study observes that the microporous activated carbon has a higher SSA-normalized capacitance, 14.1 μF cm-2, compared to the mesoporous material, 12.4 μF cm-2. However, this enhanced SSA-normalized capacitance is only observed above a threshold operating voltage. Therefore, it can be concluded that a minimum applied voltage is required to induce ion adsorption in these sub-nanometer micropores, which increases the capacitance.

  20. Morphology-dependent Electrochemical Enhancements of Porous Carbon as Sensitive Determination Platform for Ascorbic Acid, Dopamine and Uric Acid

    NASA Astrophysics Data System (ADS)

    Cheng, Qin; Ji, Liudi; Wu, Kangbing; Zhang, Weikang

    2016-02-01

    Using starch as the carbon precursor and different-sized ZnO naoparticles as the hard template, a series of porous carbon materials for electrochemical sensing were prepared. Experiments of scanning electron microscopy, transmission electron microscopy and Nitrogen adsorption-desorption isotherms reveal that the particle size of ZnO has big impacts on the porous morphology and surface area of the resulting carbon materials. Through ultrasonic dispersion of porous carbon and subsequent solvent evaporation, different sensing interfaces were constructed on the surface of glassy carbon electrode (GCE). The electrochemical behaviors of ascorbic acid (AA), dopamine (DA) and uric acid (UA) were studied. On the surface of porous carbon materials, the accumulation efficiency and electron transfer ability of AA, DA and UA are improved, and consequently their oxidation signals enhance greatly. Moreover, the interface enhancement effects of porous carbon are also controlled by the particle size of hard template. The constructed porous carbon interface displays strong signal amplification ability and holds great promise in constructing a sensitive platform for the simultaneous determination of AA, DA and UA.

  1. Morphology-dependent Electrochemical Enhancements of Porous Carbon as Sensitive Determination Platform for Ascorbic Acid, Dopamine and Uric Acid

    PubMed Central

    Cheng, Qin; Ji, Liudi; Wu, Kangbing; Zhang, Weikang

    2016-01-01

    Using starch as the carbon precursor and different-sized ZnO naoparticles as the hard template, a series of porous carbon materials for electrochemical sensing were prepared. Experiments of scanning electron microscopy, transmission electron microscopy and Nitrogen adsorption-desorption isotherms reveal that the particle size of ZnO has big impacts on the porous morphology and surface area of the resulting carbon materials. Through ultrasonic dispersion of porous carbon and subsequent solvent evaporation, different sensing interfaces were constructed on the surface of glassy carbon electrode (GCE). The electrochemical behaviors of ascorbic acid (AA), dopamine (DA) and uric acid (UA) were studied. On the surface of porous carbon materials, the accumulation efficiency and electron transfer ability of AA, DA and UA are improved, and consequently their oxidation signals enhance greatly. Moreover, the interface enhancement effects of porous carbon are also controlled by the particle size of hard template. The constructed porous carbon interface displays strong signal amplification ability and holds great promise in constructing a sensitive platform for the simultaneous determination of AA, DA and UA. PMID:26924080

  2. Morphology-dependent Electrochemical Enhancements of Porous Carbon as Sensitive Determination Platform for Ascorbic Acid, Dopamine and Uric Acid.

    PubMed

    Cheng, Qin; Ji, Liudi; Wu, Kangbing; Zhang, Weikang

    2016-01-01

    Using starch as the carbon precursor and different-sized ZnO naoparticles as the hard template, a series of porous carbon materials for electrochemical sensing were prepared. Experiments of scanning electron microscopy, transmission electron microscopy and Nitrogen adsorption-desorption isotherms reveal that the particle size of ZnO has big impacts on the porous morphology and surface area of the resulting carbon materials. Through ultrasonic dispersion of porous carbon and subsequent solvent evaporation, different sensing interfaces were constructed on the surface of glassy carbon electrode (GCE). The electrochemical behaviors of ascorbic acid (AA), dopamine (DA) and uric acid (UA) were studied. On the surface of porous carbon materials, the accumulation efficiency and electron transfer ability of AA, DA and UA are improved, and consequently their oxidation signals enhance greatly. Moreover, the interface enhancement effects of porous carbon are also controlled by the particle size of hard template. The constructed porous carbon interface displays strong signal amplification ability and holds great promise in constructing a sensitive platform for the simultaneous determination of AA, DA and UA. PMID:26924080

  3. Enhanced electrochemical properties of Al2O3-coated LiV3O8 cathode materials for high-power lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Huang, S.; Tu, J. P.; Jian, X. M.; Lu, Y.; Shi, S. J.; Zhao, X. Y.; Wang, T. Q.; Wang, X. L.; Gu, C. D.

    2014-01-01

    Surface modified-LiV3O8 cathode materials with Al2O3 are successfully synthesized via a facile thermolysis process. The 0.5 wt.% Al2O3-coated LiV3O8 exhibits an enhanced cyclic stability at various charge-discharge current densities. At a current density of 100 mA g-1, it delivers an initial specific discharge capacity of 283.1 mAh g-1 between 2.0 and 4.0 V. Moreover, high capacities of 139.4 and 118.5 mAh g-1 are obtained at the 100th cycle at current densities of 2000 and 3000 mA g-1, respectively. The improved electrochemical performance is attributed to the Al2O3 coating, which can hinder the irreversible phase transformation and act as a protective layer to prevent the active material from direct contact with electrolyte. Furthermore, the formation of a Li-V-Al-O solid solution at the LiV3O8/Al2O3 interface provides a fast Li+ diffusion path which is of benefit to the electrochemical behaviors.

  4. Electrochemical determination of Sudan I in food samples at graphene modified glassy carbon electrode based on the enhancement effect of sodium dodecyl sulphonate.

    PubMed

    Ma, Xinying; Chao, Mingyong; Wang, Zhaoxia

    2013-06-01

    This paper describes a novel electrochemical method for the determination of Sudan I in food samples based on the electrochemical catalytic activity of graphene modified glassy carbon electrode (GMGCE) and the enhancement effect of an anionic surfactant: sodium dodecyl sulphonate (SDS). Using pH 6.0 phosphate buffer solution (PBS) as supporting electrolyte and in the presence of 1.5 × 10(-4)mol L(-1) SDS, Sudan I yielded a well-defined and sensitive oxidation peak at a GMGCE. The oxidation peak current of Sudan I remarkably increased in the presence of SDS. The experimental parameters, such as supporting electrolyte, concentration of SDS, and accumulation time, were optimised for Sudan I determination. The oxidation peak current showed a linear relationship with the concentrations of Sudan I in the range of 7.50 × 10(-8)-7.50 × 10(-6)mol L(-1), with the detection limit of 4.0 × 10(-8)mol L(-1). This new voltammetric method was successfully used to determine Sudan I in food products such as ketchup and chili sauce with satisfactory results. PMID:23411169

  5. Gold nanoparticles-induced enhancement of the analytical response of an electrochemical biosensor based on an organic-inorganic hybrid composite material.

    PubMed

    Barbadillo, M; Casero, E; Petit-Domínguez, M D; Vázquez, L; Pariente, F; Lorenzo, E

    2009-12-15

    The design and characterization of a new organic-inorganic hybrid composite material for glucose electrochemical sensing are described. This material is based on the entrapment of both gold nanoparticles (AuNPs) and glucose oxidase, which was chosen as a model, into a sol-gel matrix. The addition of spectroscopic grade graphite to this system, which confers conductivity, leads to the development of a material particularly attractive for electrochemical biosensor fabrication. The characterization of the hybrid composite material was performed using atomic force microscopy and scanning electron microscopy techniques. This composite material was applied to the determination of glucose in presence of hydroxymethylferrocene as a redox mediator. The system exhibits a clear electrocatalytic activity towards glucose, allowing its determination at 250 mV vs Ag/AgCl. The performance of the resulting enzyme biosensor was evaluated in terms of sensitivity, detection limit, linear response range, stability and accuracy. Finally, the enhancement of the analytical response of the resulting biosensor induced by the presence of gold nanoparticles was evaluated by comparison with a similar organic-inorganic hybrid composite material without AuNPs. PMID:19836554

  6. Impact of redox-active polymer molecular weight on the electrochemical properties and transport across porous separators in nonaqueous solvents.

    PubMed

    Nagarjuna, Gavvalapalli; Hui, Jingshu; Cheng, Kevin J; Lichtenstein, Timothy; Shen, Mei; Moore, Jeffrey S; Rodríguez-López, Joaquín

    2014-11-19

    Enhancing the ionic conductivity across the electrolyte separator in nonaqueous redox flow batteries (NRFBs) is essential for improving their performance and enabling their widespread utilization. Separating redox-active species by size exclusion without greatly impeding the transport of supporting electrolyte is a potentially powerful alternative to the use of poorly performing ion-exchange membranes. However, this strategy has not been explored possibly due to the lack of suitable redox-active species that are easily varied in size, remain highly soluble, and exhibit good electrochemical properties. Here we report the synthesis, electrochemical characterization, and transport properties of redox-active poly(vinylbenzyl ethylviologen) (RAPs) with molecular weights between 21 and 318 kDa. The RAPs reported here show very good solubility (up to at least 2.0 M) in acetonitrile and propylene carbonate. Ultramicroelectrode voltammetry reveals facile electron transfer with E1/2 ∼ -0.7 V vs Ag/Ag(+)(0.1 M) for the viologen 2+/+ reduction at concentrations as high as 1.0 M in acetonitrile. Controlled potential bulk electrolysis indicates that 94-99% of the nominal charge on different RAPs is accessible and that the electrolysis products are stable upon cycling. The dependence of the diffusion coefficient on molecular weight suggests the adequacy of the Stokes-Einstein formalism to describe RAPs. The size-selective transport properties of LiBF4 and RAPs across commercial off-the-shelf (COTS) separators such as Celgard 2400 and Celgard 2325 were tested. COTS porous separators show ca. 70 times higher selectivity for charge balancing ions (Li(+)BF4(-)) compared to high molecular weight RAPs. RAPs rejection across these separators showed a strong dependence on polymer molecular weight as well as the pore size; the rejection increased with both increasing polymer molecular weight and reduction in pore size. Significant rejection was observed even for rpoly/rpore (polymer

  7. Enhanced photo-electrochemical performances of graphene-based composite functionalized by Zn2+ tetraphenylporphyrin

    NASA Astrophysics Data System (ADS)

    Zhang, Zhongqiang; Zhu, Junwu; Han, Qiaofeng; Cui, Hao; Bi, Huiping; Wang, Xin

    2014-12-01

    Inspired by the role of electron transport chain in chlorophyll, graphene (G) complexation with zinc 5, 10, 15, 20-tetraphenylporphyrin (ZnTPP) is expected to have excellent photo-electrochemical performances. Here, we design a facile strategy to synthesize the functionalized graphene/zinc tetraphenylporphyrin (G/ZnTPP) composite. In which, all characterizations indicate synergistic effect does exist between graphene sheets and ZnTPP. The synergistic effect enables such composite to possess improved photo-electrochemical behaviors that are key features for photoelectric conversion device. On the basis of this, attempts to modify the absorption range, improve specific capacitance and lower resistance to acquire effective photo-current responses have been successfully demonstrated in this research.

  8. Reduced graphene oxide-yttria nanocomposite modified electrode for enhancing the sensitivity of electrochemical genosensor.

    PubMed

    Rasheed, P Abdul; Radhakrishnan, Thulasi; Shihabudeen, P K; Sandhyarani, N

    2016-09-15

    Reduced graphene oxide-yttria nanocomposite (rGO:Y) is applied as electrochemical genosensor platform for ultrahigh sensitive detection of breast cancer 1 (BRCA1) gene for the first time. The sensor is based on the sandwich assay in which gold nanoparticle cluster labeled reporter DNA hybridize to the target DNA. Glassy carbon electrode modified with rGO-yttria serves as the immobilization platform for capture probe DNA. The sensor exhibited a fine capability of sensing BRCA1 gene with linear range of 10attomolar (aM) to 1nanomolar (nM) and a detection limit of 5.95attomolar. The minimum distinguishable response concentration is down to the attomolar level with a high sensitivity and selectivity. We demonstrated that the use of rGO:Y modified electrode along with gold nanoparticle cluster (AuNPC) label leads to the highly sensitive electrochemical detection of BRCA1 gene. PMID:27153526

  9. Preparation of Nickel Cobalt Sulfide Hollow Nanocolloids with Enhanced Electrochemical Property for Supercapacitors Application

    NASA Astrophysics Data System (ADS)

    Chen, Zhenhua; Wan, Zhanghui; Yang, Tiezhu; Zhao, Mengen; Lv, Xinyan; Wang, Hao; Ren, Xiuli; Mei, Xifan

    2016-04-01

    Nanostructured functional materials with hollow interiors are considered to be good candidates for a variety of advanced applications. However, synthesis of uniform hollow nanocolloids with porous texture via wet chemistry method is still challenging. In this work, nickel cobalt precursors (NCP) in sub-micron sized spheres have been synthesized by a facile solvothermal method. The subsequent sulfurization process in hydrothermal system has changed the NCP to nickel cobalt sulfide (NCS) with porous texture. Importantly, the hollow interiors can be tuned through the sulfurization process by employing different dosage of sulfur source. The derived NCS products have been fabricated into supercapacitor electrodes and their electrochemical performances are measured and compared, where promising results were found for the next-generation high-performance electrochemical capacitors.

  10. Method of enhancing the wettability of boron nitride for use as an electrochemical cell separator

    DOEpatents

    McCoy, L.R.

    1981-01-23

    A felt or other fabric of boron nitride suitable for use as an interelectrode separator within an electrochemical cell is wetted with a solution containing a thermally decomposable organic salt of an alkaline earth metal. An aqueous solution of magnesium acetate is the preferred solution for this purpose. After wetting the boron nitride, the solution is dried by heating at a sufficiently low temperature to prevent rapid boiling and the creation of voids within the separator. The dried material is then calcined at an elevated temperature in excess of 400/sup 0/C to provide a coating of an oxide of magnesium on the surface of the boron nitride fibers. A fabric or felt of boron nitride treated in this manner is easily wetted by molten electrolytic salts, such as the alkali metal halides or alkaline earth metal halides, that are used in high temperature, secondary electrochemical cells.

  11. Method of enhancing the wettability of boron nitride for use as an electrochemical cell separator

    DOEpatents

    McCoy, Lowell R.

    1982-01-01

    A felt or other fabric of boron nitride suitable for use as an interelecte separator within an electrochemical cell is wetted with a solution containing a thermally decomposable organic salt of an alkaline earth metal. An aqueous solution of magnesium acetate is the preferred solution for this purpose. After wetting the boron nitride, the solution is dried by heating at a sufficiently low temperature to prevent rapid boiling and the creation of voids within the separator. The dried material is then calcined at an elevated temperature in excess of 400.degree. C. to provide a coating of an oxide of magnesium on the surface of the boron nitride fibers. A fabric or felt of boron nitride treated in this manner is easily wetted by molten electrolytic salts, such as the alkali metal halides or alkaline earth metal halides, that are used in high temperature, secondary electrochemical cells.

  12. Enhanced Electrochemical Performance of Heterogeneous Si/MoSi2 Anodes Prepared by a Magnesiothermic Reduction.

    PubMed

    Wu, Lili; Yang, Juan; Zhou, Xiangyang; Tang, Jingjing; Ren, Yongpeng; Nie, Yang

    2016-07-01

    This work explores facile synthesis of heterogeneous Si/MoSi2 nanocomposites via a one-step magnesiothermic reduction. MoSi2 serves as a highly electrically conductive nanoparticle that has several advantages of electrochemical properties, which is formed through the absorption of local heat accumulation generated by magnesiothermic reduction. As a result, the Si/MoSi2 nanocomposites exhibit excellent electrochemical performance, showing initial charge capacity of 1933.9 mA h g(-1) at a rate of 0.2 C and retaining 85.2% after 150 cycles. This work using local heat accumulation generated by magnesiothermic reduction demonstrates a large-scale method for producing high-performance Si-based anode materials, which could provide referential significances for other materials. PMID:27300698

  13. Preparation of Nickel Cobalt Sulfide Hollow Nanocolloids with Enhanced Electrochemical Property for Supercapacitors Application

    PubMed Central

    Chen, Zhenhua; Wan, Zhanghui; Yang, Tiezhu; Zhao, Mengen; Lv, Xinyan; Wang, Hao; Ren, Xiuli; Mei, Xifan

    2016-01-01

    Nanostructured functional materials with hollow interiors are considered to be good candidates for a variety of advanced applications. However, synthesis of uniform hollow nanocolloids with porous texture via wet chemistry method is still challenging. In this work, nickel cobalt precursors (NCP) in sub-micron sized spheres have been synthesized by a facile solvothermal method. The subsequent sulfurization process in hydrothermal system has changed the NCP to nickel cobalt sulfide (NCS) with porous texture. Importantly, the hollow interiors can be tuned through the sulfurization process by employing different dosage of sulfur source. The derived NCS products have been fabricated into supercapacitor electrodes and their electrochemical performances are measured and compared, where promising results were found for the next-generation high-performance electrochemical capacitors. PMID:27114165

  14. Preparation of Nickel Cobalt Sulfide Hollow Nanocolloids with Enhanced Electrochemical Property for Supercapacitors Application.

    PubMed

    Chen, Zhenhua; Wan, Zhanghui; Yang, Tiezhu; Zhao, Mengen; Lv, Xinyan; Wang, Hao; Ren, Xiuli; Mei, Xifan

    2016-01-01

    Nanostructured functional materials with hollow interiors are considered to be good candidates for a variety of advanced applications. However, synthesis of uniform hollow nanocolloids with porous texture via wet chemistry method is still challenging. In this work, nickel cobalt precursors (NCP) in sub-micron sized spheres have been synthesized by a facile solvothermal method. The subsequent sulfurization process in hydrothermal system has changed the NCP to nickel cobalt sulfide (NCS) with porous texture. Importantly, the hollow interiors can be tuned through the sulfurization process by employing different dosage of sulfur source. The derived NCS products have been fabricated into supercapacitor electrodes and their electrochemical performances are measured and compared, where promising results were found for the next-generation high-performance electrochemical capacitors. PMID:27114165

  15. Electrochemical DNA sensor-based strategy for sensitive detection of DNA demethylation and DNA demethylase activity.

    PubMed

    Shen, Qingming; Fan, Mengxing; Yang, Yin; Zhang, Hui

    2016-08-31

    DNA demethylation and demethylase activity play important roles in DNA self-repair, and their detection is key to early diagnosis of fatal diseases. Herein, a facile electrochemical DNA (E-DNA) sensor was developed for the sensitive detection of DNA demethylation and demethylase activity based on an enzyme cleavage strategy. The thiol modified hemi-methylated hairpin probe DNA (pDNA) was self-assembled on a Au electrode surface through the formation of AuS bonds. The hemi-methylated pDNA served as the substrate of DNA demethylase (using methyl-CpG-binding domain protein 2 (MBD2) as an example). Following demethylation, the hairpin stem was then recognized and cleaved by BstUI endonuclease. The ferrocene carboxylic acid (FcA)-tagged pDNA strands were released into the buffer solution from the electrode surface, resulting in a significant decrease of electrochemical signal and providing a means to observe DNA demethylation. The activity of DNA demethylase was analyzed in the concentration ranging from 0.5 to 500 ng mL(-1) with a limit of detection as low as 0.17 ng mL(-1). With high specificity and sensitivity, rapid response, and low cost, this simple E-DNA sensor provides a unique platform for the sensitive detection of DNA demethylation, DNA demethylase activity, and related molecular diagnostics and drug screening. PMID:27506345

  16. Electrochemical biosensor modified with dsDNA monolayer for restriction enzyme activity determination.

    PubMed

    Zajda, Joanna; Górski, Łukasz; Malinowska, Elżbieta

    2016-06-01

    A simple and cost effective method for the determination of restriction endonuclease activity is presented. dsDNA immobilized at a gold electrode surface is used as the enzymatic substrate, and an external cationic redox probe is employed in voltammetric measurements for analytical signal generation. The assessment of enzyme activity is based on a decrease of a current signal derived from reduction of methylene blue which is present in the sample solution. For this reason, the covalent attachment of the label molecule is not required which significantly reduces costs of the analysis and simplifies the entire determination procedure. The influence of buffer components on utilized dsDNA/MCH monolayer stability and integrity is also verified. Electrochemical impedance spectroscopy measurements reveal that due to pinhole formation during enzyme activity measurement the presence of any surfactants should be avoided. Additionally, it is shown that the sensitivity of the electrochemical biosensor can be tuned by changing the restriction site location along the DNA length. Under optimal conditions the proposed biosensor exhibits a linear response toward PvuII activity within a range from 0.25 to 1.50 U/μL. PMID:26859430

  17. Vertically aligned carbon nanofiber nanoelectrode arrays: electrochemical etching and electrode reusability

    PubMed Central

    Gupta, Rakesh K.; Meyyappan, M.; Koehne, Jessica E.

    2014-01-01

    Vertically aligned carbon nanofibers in the form of nanoelectrode arrays were grown on nine individual electrodes, arranged in a 3 × 3 array geometry, in a 2.5 cm2 chip. Electrochemical etching of the carbon nanofibers was employed for electrode activation and enhancing the electrode kinetics. Here, we report the effects of electrochemical etching on the fiber height and electrochemical properties. Electrode regeneration by amide hydrolysis and electrochemical etching is also investigated for electrode reusability. PMID:25089188

  18. Turning the Halide Switch in the Synthesis of Au-Pd Alloy and Core-Shell Nanoicosahedra with Terraced Shells: Performance in Electrochemical and Plasmon-Enhanced Catalysis.

    PubMed

    Hsu, Shih-Cheng; Chuang, Yu-Chun; Sneed, Brian T; Cullen, David A; Chiu, Te-Wei; Kuo, Chun-Hong

    2016-09-14

    Au-Pd nanocrystals are an intriguing system to study the integrated functions of localized surface plasmon resonance (LSPR) and heterogeneous catalysis. Gold is both durable and can harness incident light energy to enhance the catalytic activity of another metal, such as Pd, via the SPR effect in bimetallic nanocrystals. Despite the superior catalytic performance of icosahedral (IH) nanocrystals compared to alternate morphologies, the controlled synthesis of alloy and core-shell IH is still greatly challenged by the disparate reduction rates of metal precursors and lack of continuous epigrowth on multiply twinned boundaries of such surfaces. Herein, we demonstrate a one-step strategy for the controlled growth of monodisperse Au-Pd alloy and core-shell IH with terraced shells by turning an ionic switch between [Br(-)]/[Cl(-)] in the coreduction process. The core-shell IH nanocrystals contain AuPd alloy cores and ultrathin Pd shells (<2 nm). They not only display more than double the activity of the commercial Pd catalysts in ethanol electrooxidation attributed to monatomic step terraces but also show SPR-enhanced conversion of 4-nitrophenol. This strategy holds promise toward the development of alternate bimetallic IH nanocrystals for electrochemical and plasmon-enhanced catalysis. PMID:27575057

  19. Electrochemical oxidation of the poultry manure anaerobic digested effluents for enhancing pollutants removal by Chlorella vulgaris.

    PubMed

    Wang, Mengzi; Cao, Wei; Wu, Yu; Lu, Haifeng; Li, Baoming

    2016-01-01

    The mechanisms and pseudo-kinetics of the electrochemical oxidation for wastewater treatment and the synergistic effect of combining algal biological treatment were investigated. NaCl, Na2SO4 and HCl were applied to compare the effect of electrolyte species on nutrients removal. NaCl was proved to be more efficient in removing ammonia ([Formula: see text]), total phosphorus (TP), total organic carbon (TOC) and inorganic carbon (IC). [Formula: see text] oxidation by using Ti/Pt-IrO2 electrodes was modelled, which indicates that the [Formula: see text] removal followed the zero-order kinetic with sufficient Cl(-) and the first-order kinetic with insufficient Cl(-), respectively. The feasibility of combining electrochemical oxidation with microalgae cultivation for wastewater treatment was also determined. A 2 h electrochemical pretreatment reduced 57% [Formula: see text], 76% TP, 72% TOC and 77% IC from the digested effluent, which is applied as feedstock for algae cultivation, and resulted in increasing both the biomass production and pollutants removal efficiencies of the algal biological process. PMID:26853507

  20. Mediator-free electrochemical biosensor based on buckypaper with enhanced stability and sensitivity for glucose detection.

    PubMed

    Ahmadalinezhad, Asieh; Wu, Guosheng; Chen, Aicheng

    2011-12-15

    Here we report on a novel platform based on buckypaper for the design of high-performance electrochemical biosensors. Using glucose oxidase as a model enzyme, we constructed a biocompatible mediator-free biosensor and studied the potential effect of the buckypaper on the stability of the biosensor with both amperometry and FTIR spectroscopy. The results showed that the biosensor responses sensitively and selectively to glucose with a considerable functional lifetime of over 80 days. The fabricated enzymatic sensor detects glucose with a dynamic linear range of over 9 mM and a detection limit of 0.01 mM. To examine the efficiency of enzyme immobilization, the Michaelis-Menten constant (K(M)(app)) was calculated to be 4.67 mM. In addition, the fabricated electrochemical biosensor shows high selectivity; no amperometric response to the common interference species such as ascorbic acid, uric acid and acetamidophenol was observed. The facile and robust buckypaper-based platform proposed in this study opens the door for the design of high-performance electrochemical biosensors for medical diagnostics and environmental monitoring. PMID:22014621

  1. Potential amoebicidal activity of hydrazone derivatives: synthesis, characterization, electrochemical behavior, theoretical study and evaluation of the biological activity.

    PubMed

    Toledano-Magaña, Yanis; García-Ramos, Juan Carlos; Navarro-Olivarria, Marisol; Flores-Alamo, Marcos; Manzanera-Estrada, Mayra; Ortiz-Frade, Luis; Galindo-Murillo, Rodrigo; Ruiz-Azuara, Lena; Meléndrez-Luevano, Ruth Ma; Cabrera-Vivas, Blanca M

    2015-01-01

    Four new hydrazones were synthesized by the condensation of the selected hydrazine and the appropriate nitrobenzaldehyde. A complete characterization was done employing 1H- and 13C-NMR, electrochemical techniques and theoretical studies. After the characterization and electrochemical analysis of each compound, amoebicidal activity was tested in vitro against the HM1:IMSS strain of Entamoeba histolytica. The results showed the influence of the nitrobenzene group and the hydrazone linkage on the amoebicidal activity. meta-Nitro substituted compound 2 presents a promising amoebicidal activity with an IC50 = 0.84 μM, which represents a 7-fold increase in cell growth inhibition potency with respect to metronidazole (IC50 = 6.3 μM). Compounds 1, 3, and 4 show decreased amoebicidal activity, with IC50 values of 7, 75 and 23 µM, respectively, as a function of the nitro group position on the aromatic ring. The observed differences in the biological activity could be explained not only by the redox potential of the molecules, but also by their capacity to participate in the formation of intra- and intermolecular hydrogen bonds. Redox potentials as well as the amoebicidal activity can be described with parameters obtained from the DFT analysis. PMID:26035095

  2. Electrochemical and fluorescence properties of SnO2 thin films and its antibacterial activity.

    PubMed

    Henry, J; Mohanraj, K; Sivakumar, G; Umamaheswari, S

    2015-05-15

    Nanocrystalline SnO2 thin films were deposited by a simple and inexpensive sol-gel spin coating technique and the films were annealed at two different temperatures (350°C and 450°C). Structural, vibrational, optical and electrochemical properties of the films were analyzed using XRD, FTIR, UV-Visible, fluorescence and cyclic voltammetry techniques respectively and their results are discussed in detail. The antimicrobial properties of SnO2 thin films were investigated by agar agar method and the results confirm the antibacterial activity of SnO2 against Escherichiacoli and Bacillus. PMID:25727293

  3. Enhanced photoelectrochemical activity of vertically aligned ZnO-coated TiO{sub 2} nanotubes

    SciTech Connect

    Cai, Hua; Yang, Qin; You, Qinghu; Sun, Jian; Xu, Ning; Wu, Jiada; Hu, Zhigao; Duan, Zhihua

    2014-02-03

    Vertically aligned ZnO-TiO{sub 2} hetero-nanostructures constructed of anatase TiO{sub 2} nanotubes (NTs) and wurtzite ZnO coatings are fabricated by atomic layer deposition of ZnO coatings on electrochemical anodization formed TiO{sub 2} NTs, and their photoelectrochemical activities are studied through photoelectrochemical and electrochemical characterization. Compared with bare TiO{sub 2} NTs, the transient photocurrent increases to over 1.5-fold for the annealed ZnO-coated TiO{sub 2} NTs under visible illumination. The ZnO-coated TiO{sub 2} NTs also show a longer electron lifetime, a lower charge-transfer resistance and a more negative flat-band potential than the bare TiO{sub 2} NTs, confirming the improved photoelectrochemical activity due to the enhanced charge separation.

  4. Chromatin remodeling effects on enhancer activity.

    PubMed

    García-González, Estela; Escamilla-Del-Arenal, Martín; Arzate-Mejía, Rodrigo; Recillas-Targa, Félix

    2016-08-01

    During organism development, a diversity of cell types emerges with disparate, yet stable profiles of gene expression with distinctive cellular functions. In addition to gene promoters, the genome contains enhancer regulatory sequences, which are implicated in cellular specialization by facilitating cell-type and tissue-specific gene expression. Enhancers are DNA binding elements characterized by highly sophisticated and various mechanisms of action allowing for the specific interaction of general and tissue-specific transcription factors (TFs). However, eukaryotic organisms package their genetic material into chromatin, generating a physical barrier for TFs to interact with their cognate sequences. The ability of TFs to bind DNA regulatory elements is also modulated by changes in the chromatin structure, including histone modifications, histone variants, ATP-dependent chromatin remodeling, and the methylation status of DNA. Furthermore, it has recently been revealed that enhancer sequences are also transcribed into a set of enhancer RNAs with regulatory potential. These interdependent processes act in the context of a complex network of chromatin interactions, which together contributes to a renewed vision of how gene activation is coordinated in a cell-type-dependent manner. In this review, we describe the interplay between genetic and epigenetic aspects associated with enhancers and discuss their possible roles on enhancer function. PMID:27026300

  5. Electrochemical Assay for the Signal-on Detection of Human DNA Methyltransferase Activity

    PubMed Central

    Muren, Natalie B.; Barton, Jacqueline K.

    2013-01-01

    Strategies to detect human DNA methyltransferases are needed, given that aberrant methylation by these enzymes is associated with cancer initiation and progression. Here we describe a non-radioactive, antibody-free, electrochemical assay in which methyltransferase activity on DNA-modified electrodes confers protection from restriction for signal-on detection. We implement this assay with a multiplexed chip platform and show robust detection of both bacterial (SssI) and human (Dnmt1) methyltransferase activity. Essential to work with human methyltransferases, our unique assay design allows activity measurements on both unmethylated and hemimethylated DNA substrates. We validate this assay by comparison with a conventional radioactive method. The advantages of electrochemistry over radioactivity and fluorescence make this assay an accessible and promising new approach for the sensitive, label-free detection of human methyltransferase activity. PMID:24164112

  6. Platinum nanoparticles encapsulated metal-organic frameworks for the electrochemical detection of telomerase activity.

    PubMed

    Ling, Pinghua; Lei, Jianping; Jia, Li; Ju, Huangxian

    2016-01-21

    A simple and rapid electrochemical sensor is constructed for the detection of telomerase activity based on the electrocatalysis of platinum nanoparticle (Pt NP) encapsulated metal-organic frameworks (MOFs), which are synthesized by one-pot encapsulation of Pt NPs into prototypal MOFs, UiO-66-NH2. Integrating with the efficient electrocatalysis of Pt@MOFs towards NaBH4 oxidation, this biosensor shows the wide dynamic correlation of telomerase activity from 5 × 10(2) to 10(7) HeLa cells mL(-1) and the telomerase activity in a single HeLa cell was calculated to be 2.0 × 10(-11) IU, providing a powerful platform for detecting telomerase activity. PMID:26612011

  7. Electrochemical activation of commercial polyacrylonitrile-based carbon fiber for the oxygen reduction reaction.

    PubMed

    Xu, Haibo; Xia, Guangsen; Liu, Haining; Xia, Shuwei; Lu, Yonghong

    2015-03-28

    Nitrogen (N)-doped carbon and its non-noble metal composite replacing platinum-based oxygen reduction reaction (ORR) electrocatalysts still have some fundamental problems that remain. Here the micron-sized commercial polyacrylonitrile-based carbon fiber (PAN-CF) electrode was modified using an electrochemical method, converting its inherent pyridinic-N into 2-pyridone (or 2-hydroxyl pyridine) functional group existing in three-dimensional active layers with remarkable ORR catalytic activity and stability. The carbon atom adjacent to the nitrogen and oxygen atoms is prone to act as an active site to efficiently catalyze a two-electron ORR process. However, after coordinating pyridone to the Cu(2+) ion, together with the electrochemical reaction, the chemical redox between Cu(+) and ORR intermediates synergistically tends towards a four-electron pathway in alkaline solution. In different medium, the complexation and dissociation can induce the charge transfer and reconstruction among proton, metal ion and pyridone functionalities, eventually leading to the changes of ORR performance. PMID:25712410

  8. Electrochemically activated solutions: evidence for antimicrobial efficacy and applications in healthcare environments.

    PubMed

    Thorn, R M S; Lee, S W H; Robinson, G M; Greenman, J; Reynolds, D M

    2012-05-01

    Due to the limitations associated with the use of existing biocidal agents, there is a need to explore new methods of disinfection to help maintain effective bioburden control, especially within the healthcare environment. The transformation of low mineral salt solutions into an activated metastable state, by electrochemical unipolar action, produces a solution containing a variety of oxidants, including hypochlorous acid, free chlorine and free radicals, known to possess antimicrobial properties. Electrochemically activated solutions (ECAS) have been shown to have broad-spectrum antimicrobial activity, and have the potential to be widely adopted within the healthcare environment due to low-cost raw material requirements and ease of production (either remotely or in situ). Numerous studies have found ECAS to be highly efficacious, as both a novel environmental decontaminant and a topical treatment agent (with low accompanying toxicity), but they are still not in widespread use, particularly within the healthcare environment. This review provides an overview of the scientific evidence for the mode of action, antimicrobial spectrum and potential healthcare-related applications of ECAS, providing an insight into these novel yet seldom utilised biocides. PMID:21809085

  9. Specific Surface versus Electrochemically Active Area of the Carbon/Polypyrrole Capacitor: Correlation of Ion Dynamics Studied by an Electrochemical Quartz Crystal Microbalance with BET Surface.

    PubMed

    Mosch, Heike L K S; Akintola, Oluseun; Plass, Winfried; Höppener, Stephanie; Schubert, Ulrich S; Ignaszak, Anna

    2016-05-10

    Carbon/polypyrrole (PPy) composites are promising electrode materials for energy storage applications such as lightweight capacitors. Although these materials are composed of relatively inexpensive components, there is a gap of knowledge regarding the correlation between surface, porosity, ion exchange dynamics, and the interplay of the double layer capacitance and pseudocapacitance. In this work we evaluate the specific surface area analyzed by the BET method and the area accessible for ions using electrochemical quartz-crystal microbalance (EQCM) for SWCNT/PPy and carbon black Vulcan XC72-R/PPy composites. The study revealed that the polymer has significant influence on the pore size of the composites. Although the BET surface is low for the polypyrrole, the electrode mass change and thus the electrochemical area are large for the polymer-containing electrodes. This indicates that multiple redox active centers in the charged polymer chain are good ion scavengers. Also, for the composite electrodes, the effective charge storage occurs at the polypyrrole-carbon junctions, which are easy to design/multiply by a proper carbon-to-polymer weight ratio. The specific BET surface and electrochemically accessible surface area are both important parameters in calculation of the electrode capacitance. SWCNTs/PPy showed the highest capacitances normalized to the BET and electrochemical surface as compared to the polymer-carbon black. TEM imaging revealed very homogeneous distribution of the nanosized polymer particles onto the CNTs, which facilitates the synergistic effect of the double layer capacitance (CNTs) and pseudocapacitance (polymer). The trend in the electrode mass change in correlation with the capacitance suggest additional effects such as a solvent co-insertion into the polymer and the contribution of the charge associated with the redox activity of oxygen-containing functional groups on the carbon surface. PMID:27082127

  10. Phase-Controlled Electrochemical Activity of Epitaxial Mg-Spinel Thin Films.

    PubMed

    Feng, Zhenxing; Chen, Xiao; Qiao, Liang; Lipson, Albert L; Fister, Timothy T; Zeng, Li; Kim, Chunjoong; Yi, Tanghong; Sa, Niya; Proffit, Danielle L; Burrell, Anthony K; Cabana, Jordi; Ingram, Brian J; Biegalski, Michael D; Bedzyk, Michael J; Fenter, Paul

    2015-12-30

    We report an approach to control the reversible electrochemical activity (i.e., extraction/insertion) of Mg(2+) in a cathode host through the use of phase-pure epitaxially stabilized thin film structures. The epitaxially stabilized MgMn2O4 (MMO) thin films in the distinct tetragonal and cubic phases are shown to exhibit dramatically different properties (in a nonaqueous electrolyte, Mg(TFSI)2 in propylene carbonate): tetragonal MMO shows negligible activity while the cubic MMO (normally found as polymorph at high temperature or high pressure) exhibits reversible Mg(2+) activity with associated changes in film structure and Mn oxidation state. These results demonstrate a novel strategy for identifying the factors that control multivalent cation mobility in next-generation battery materials. PMID:26641524

  11. Electrochemical impedance monitoring of immunochemical reactions using varying IDE geometries for signal enhancement

    NASA Astrophysics Data System (ADS)

    Page, Robin H.; McNeil, Calum

    2010-02-01

    Electrochemical Impedance Spectroscopy (EIS) has been applied to the detection of analytes for immunosensors [1-3]. The development of hand held devices based on this technique is a very promising prospect for point-of-care applications and is an attractive alternative to laboratory-based immunochemical analysis [1, 4]. The work in this paper will focus primarily on the development of an EIS method of transduction for immunoassay detection that could be potentially introduced into a hand held point-of-care device. Varying geometries of IDEs will be reported and discussed to improve the detection of antigen.

  12. Scanning Electrochemical Microscopy

    NASA Astrophysics Data System (ADS)

    Amemiya, Shigeru; Bard, Allen J.; Fan, Fu-Ren F.; Mirkin, Michael V.; Unwin, Patrick R.

    2008-07-01

    This review describes work done in scanning electrochemical microscopy (SECM) since 2000 with an emphasis on new applications and important trends, such as nanometer-sized tips. SECM has been adapted to investigate charge transport across liquid/liquid interfaces and to probe charge transport in thin films and membranes. It has been used in biological systems like single cells to study ion transport in channels, as well as cellular and enzyme activity. It is also a powerful and useful tool for the evaluation of the electrocatalytic activities of different materials for useful reactions, such as oxygen reduction and hydrogen oxidation. SECM has also been used as an electrochemical tool for studies of the local properties and reactivity of a wide variety of materials, including metals, insulators, and semiconductors. Finally, SECM has been combined with several other nonelectrochemical techniques, such as atomic force microscopy, to enhance and complement the information available from SECM alone.

  13. Activated carbon electrodes: electrochemical oxidation coupled with desalination for wastewater treatment.

    PubMed

    Duan, Feng; Li, Yuping; Cao, Hongbin; Wang, Yi; Crittenden, John C; Zhang, Yi

    2015-04-01

    The wastewater usually contains low-concentration organic pollutants and some inorganic salts after biological treatment. In the present work, the possibility of simultaneous removal of them by combining electrochemical oxidation and electrosorption was investigated. Phenol and sodium chloride were chosen as representative of organic pollutants and inorganic salts and a pair of activated carbon plate electrodes were used as anode and cathode. Some important working conditions such as oxygen concentration, applied potential and temperature were evaluated to reach both efficient phenol removal and desalination. Under optimized 2.0 V of applied potential, 38°C of temperature, and 500 mL min(-1) of oxygen flow, over 90% of phenol, 60% of TOC and 20% of salinity were removed during 300 min of electrolysis time. Phenol was removed by both adsorption and electrochemical oxidation, which may proceed directly or indirectly by chlorine and hypochlorite oxidation. Chlorophenols were detected as degradation intermediates, but they were finally transformed to carboxylic acids. Desalination was possibly attributed to electrosorption of ions in the pores of activated carbon electrodes. The charging/regeneration cycling experiment showed good stability of the electrodes. This provides a new strategy for wastewater treatment and recycling. PMID:25585871

  14. Production of bioelectricity, bio-hydrogen, high value chemicals and bioinspired nanomaterials by electrochemically active biofilms.

    PubMed

    Kalathil, Shafeer; Khan, Mohammad Mansoob; Lee, Jintae; Cho, Moo Hwan

    2013-11-01

    Microorganisms naturally form biofilms on solid surfaces for their mutual benefits including protection from environmental stresses caused by contaminants, nutritional depletion or imbalances. The biofilms are normally dangerous to human health due to their inherited robustness. On the other hand, a recent study suggested that electrochemically active biofilms (EABs) generated by electrically active microorganisms have properties that can be used to catalyze or control the electrochemical reactions in a range of fields, such as bioenergy production, bioremediation, chemical/biological synthesis, bio-corrosion mitigation and biosensor development. EABs have attracted considerable attraction in bioelectrochemical systems (BESs), such as microbial fuel cells and microbial electrolysis cells, where they act as living bioanode or biocathode catalysts. Recently, it was reported that EABs can be used to synthesize metal nanoparticles and metal nanocomposites. The EAB-mediated synthesis of metal and metal-semiconductor nanocomposites is expected to provide a new avenue for the greener synthesis of nanomaterials with high efficiency and speed than other synthetic methods. This review covers the general introduction of EABs, as well as the applications of EABs in BESs, and the production of bio-hydrogen, high value chemicals and bio-inspired nanomaterials. PMID:23680192

  15. Enhanced kappa-Cygnid activity 2014

    NASA Astrophysics Data System (ADS)

    Rendtel, Jürgen; Molau, Sirko

    2015-04-01

    The κ-Cygnid (012 KCG) meteor shower produced about 3-4 times the average visual rate and video flux in August 2014 for about four days. We are able to trace the increased activity to one component of the Cygnid complex proposed by Koseki recently. Video data indicate that the population index of all shower components is lower than that of the sporadic meteors, probably r≈ 2.6. Our analysis supports the suggested 7-year periodicity in activity enhancement of the κ-Cygnids

  16. Synthesis of Co3O4/NiO nanofilms and their enhanced electrochemical performance for supercapacitor application

    NASA Astrophysics Data System (ADS)

    Zuo, Yong; Ni, Jing-Jing; Song, Ji-Ming; Niu, He-Lin; Mao, Chang-Jie; Zhang, Sheng-Yi; Shen, Yu-Hua

    2016-05-01

    Transition metallic oxides have attracted considerable attention for supercapacitor applications because of their superior electrochemical performance at relatively low cost. Co3O4/NiO nanofilms were successfully prepared by calcination of precursor α-Co(OH)2/α-Ni(OH)2. XRD, XPS, SEM and TEM techniques were used to characterize the composition and morphology of as-prepared samples. The results demonstrated that Co3O4/NiO nanofilms presented graphene-like morphology with shrinkage and wrinkles. The Brunauer-Emmett-Teller (BET) measurement showed that specific surface area of Co3O4/NiO was 176.5 m2/g. Electrochemical properties tests indicated that the Co3O4/NiO nanofilms had a higher specific capacitance and better rate capability than that of precursor α-Co(OH)2/α-Ni(OH)2 at high current density. As to the cycling performance, the specific capacitance of Co3O4/NiO electrode would first increase from 556 F/g to 710 F/g quickly at 2 A/g after 80 cycles and then remained stable. Therefore, compared with that of precursor α-Co(OH)2/α-Ni(OH)2, the capacitance performance of as-prepared Co3O4/NiO nanofilms was improved after calcination. The possible reason for the enhancement of capacitance performance was discussed.

  17. Enhanced Yields of Iron-Oxidizing Bacteria by In Situ Electrochemical Reduction of Soluble Iron in the Growth Medium

    PubMed Central

    Blake, Robert C.; Howard, Gary T.; McGinness, Stephen

    1994-01-01

    An electrochemical apparatus for culturing chemolithotrophic bacteria that respire aerobically on ferrous ions is described. Enhanced yields of the bacteria were achieved by the in situ electrochemical reduction of soluble iron in the growth medium. When subjected to a direct current of 30 A for 60 days, a 45-liter culture of Thiobacillus ferrooxidans grew from 6 × 107 to 9.5 × 109 cells per ml. Growth of the bacterium within the electrolytic bioreactor was linear with time. A final cell density corresponding to 4.7 g of wet cell paste per liter was achieved, and a total of 320 g of wet cell paste was harvested from one culture. The apparatus was designed to deliver protons concomitantly with electrons; therefore, the pH of the culture remained stable at 1.6 ± 0.1 for the duration of growth. This laboratory-scale apparatus may be readily adapted to pilot or production scale. It is thus anticipated that abundant numbers of iron-oxidizing bacteria may be obtained for both fundamental and applied studies. PMID:16349344

  18. Three-dimensional mesoporous gold film to enhance the sensitivity of electrochemical detection

    NASA Astrophysics Data System (ADS)

    El-Said, Waleed Ahmed; Kim, Tae-Hyung; Kim, Hyuncheol; Choi, Jeong-Woo

    2010-11-01

    Cell-cell and cell-extracellular matrix (ECM) adhesion are fundamental and important in the development of a cell-based chip. In this study, a novel, simple, rapid, and one-step technique was developed for the fabrication of a uniform three-dimensional mesoporous gold thin film (MPGF) onto a gold (Au) coated glass plate based on an electrochemical deposition method. Scanning electron microscopy images demonstrated that the resulting MPGF electrode had uniformly distributed pores with diameters of about 20 nm. The cyclic voltammetric behavior of [Fe(CN)6]4 - /3 - coupled onto MPGF and Au electrodes demonstrated that the MPGF electrode had a higher electrocatalytic sensitivity and reversibility than the bare Au electrode. The Arg-Gly-Asp (RGD) sequence containing the peptide was immobilized on the MPGF and bare Au substrates. HeLa cancer cells were then cultured on the RGD peptide layer. The successful immobilization of the peptide and cells was confirmed by atomic force microscopy. The cell proliferation and viability were evaluated by cyclic voltammetry and Trypan blue dyeing assay. These results indicated that the RGD/MPGF modified electrodes showed an electrochemical sensitivity in the detection of cancer cells which is approximately three times higher, especially at low cell density, than RGD/Au electrodes. This much improved sensitivity of the MPGF modified electrode demonstrates the potential for the fabrication of a highly sensitive and low-cost cell-based chip for rapid cancer detection.

  19. Nanostructured rough gold electrodes as platforms to enhance the sensitivity of electrochemical genosensors.

    PubMed

    García-Mendiola, T; Gamero, M; Campuzano, S; Revenga-Parra, M; Alonso, C; Pedrero, M; Pariente, F; Pingarrón, J M; Lorenzo, E

    2013-07-25

    An electrochemical DNA genosensor constructed by using rough gold as electrode support is reported in this work. The electrode surface nanopatterning was accomplished by repetitive square-wave perturbing potential (RSWPP). A synthetic 25-mer DNA capture probe, modified at the 5' end with a hexaalkylthiol, able to hybridize with a specific sequence of lacZ gene from the Enterobacteriaceae bacterial family was assembled to the rough gold surface. A 25 bases synthetic sequence fully complementary to the thiolated DNA capture probe and a 326 bases fragment of lacZ containing a fully matched sequence with the capture probe, which was amplified by a specific asymmetric polymerase chain reaction (aPCR), were employed as target sequences. The hybridization event was electrochemically monitored by using two different indicators, hexaammineruthenium (III) chloride showing an electrostatic DNA binding mode, and pentaamineruthenium-[3-(2-phenanthren-9-yl-vinyl)-pyridine] (in brief RuL) which binds to double stranded DNA (dsDNA) following an intercalative mechanism. After optimization of the different variables involved in the hybridization and detection reactions, detection limits of 5.30 pg μL(-1) and 10 pg μL(-1) were obtained for the 25-mer synthetic target DNA and the aPCR amplicon, respectively. A RSD value of 6% was obtained for measurements carried out with 3 different genosensors prepared in the same manner. PMID:23845493

  20. Effects of CO{sub 2} activation on electrochemical performance of microporous carbons derived from poly(vinylidene fluoride)

    SciTech Connect

    Lee, Seul-Yi; Park, Soo-Jin

    2013-11-15

    In this work, we have prepared microporous carbons (MPCs) derived from poly(vinylidene fluoride) (PVDF), and the physical activation of MPCs using CO{sub 2} gas is subsequently carried out with various activation temperatures to investigate the electrochemical performance. PVDF is successfully converted into MPCs with a high specific surface area and well-developed micropores. After CO{sub 2} activation, the specific surface areas of MPCs (CA-MPCs) are enhanced by 12% compared with non-activated MPCs. With increasing activation temperature, the micropore size distributions of A-MPCs also become narrower and shift to larger pore size. It is also confirmed that the CO{sub 2} activation had developed the micropores and introduced the oxygen-containing groups to MPCs′ surfaces. From the results, the specific capacitances of the electrodes in electric double layer capacitors (EDLCs) based on CA-MPCs are distinctly improved through CO{sub 2} activation. The highest specific capacitance of the A-MPCs activated at 700 °C is about 125 F/g, an enhancement of 74% in comparison with NA-MPCs, at a discharge current of 2 A/g in a 6 M KOH electrolyte solution. We also found that micropore size of 0.67 nm has a specific impact on the capacitance behaviors, besides the specific surface area of the electrode samples. - Graphical abstract: The A-MPC samples with high specific surface area (ranging from 1030 to 1082 m{sup 2}/g), corresponding to micropore sizes of 0.67 and 0.72 nm, and with the amount of oxygen-containing groups ranging from 3.2% to 4.4% have been evaluated as electrodes for EDLC applications. . Display Omitted - Highlights: • Microporous carbons (MPCs) were synthesized without activation process. • Next, we carried out the CO{sub 2} activation of MPCs with activation temperatures. • It had developed the micropores and introduced the O-functional groups to MPCs. • The highest specific capacitance: 125 F/g, an increase of 74% compared to MPCs.

  1. Enhancement of polyether biodegradation in activated sludge

    SciTech Connect

    Christopher, L.J.

    1993-01-01

    Previous studies in this laboratory showed that pretreatment with Petroleum Chemical Extinguisher[reg sign] (PCE), a C[sub 18] unsaturated fatty acid diester of polyethylene glycol (PEG), enhanced the biodegradation of PEG 1,000 and PEG 1,450 in soil. In this study the ability of PCE and other PEG-fatty acid diesters to enhance biodegradation of PEGs in activated sludge was investigated. Additionally, polyether-fatty acid esters similar to PCE were synthesized and tested to determine how they affected biodegradation of PEGs and other polyethers. Attempts were made to understand the mechanism for enhancement of biodegradation. Carbon-dioxide evolution and thin-layer chromatographic analysis indicated degradation of PEG 1,000, PEG 1,450, and PEG 3,350 in sludge samples which were previously exposed to PCE. Those samples which were not pre-treated with PCE showed no detectable PEG degradation during the two-week study. Preexposure to PCE did not enhance subsequent degradation of PEG 8,000, nor polypropylene glycol (PPG) 1,025. However, pretreatment of sludge with a PPG 1,025-di oleic acid ester promoted PPG 1,205 degradation. Interestingly, microbial populations do not seem to be gaining much biomass or energy from the degradation of PEG-di fatty acid esters or PEGs. When PCE-pretreated sludge samples were given [sup 14]C-PEG 3,350 as substrate, evolution of [sup 14]CO[sub 2] occurred and little (<5%) of the [sup 14]C was assimilated by the microorganisms in the sludge. Futhermore, determinations of ATP content and esterase activity of sludge samples suggested that there was not a substantial increase in biomass as a result of degradation of either PCE or PEGs. PCE preexposure effected an increase in PEG dehydrogenase activity. This increase may be due to induction of enzymes responsible for PEG biodegradation or selection for organisms in the microbial population which are PEG degraders.

  2. Electrodes and electrochemical storage cells utilizing tin-modified active materials

    DOEpatents

    Anani, Anaba; Johnson, John; Lim, Hong S.; Reilly, James; Schwarz, Ricardo; Srinivasan, Supramaniam

    1995-01-01

    An electrode has a substrate and a finely divided active material on the substrate. The active material is ANi.sub.x-y-z Co.sub.y Sn.sub.z, wherein A is a mischmetal or La.sub.1-w M.sub.w, M is Ce, Nd, or Zr, w is from about 0.05 to about 1.0, x is from about 4.5 to about 5.5, y is from 0 to about 3.0, and z is from about 0.05 to about 0.5. An electrochemical storage cell utilizes such an electrode as the anode. The storage cell further has a cathode, a separator between the cathode and the anode, and an electrolyte.

  3. Enhanced removal of 8-quinolinecarboxylic acid in an activated carbon cloth by electroadsorption in aqueous solution.

    PubMed

    López-Bernabeu, S; Ruiz-Rosas, R; Quijada, C; Montilla, F; Morallón, E

    2016-02-01

    The effect of the electrochemical treatment (potentiostatic treatment in a filter-press electrochemical cell) on the adsorption capacity of an activated carbon cloth (ACC) was analyzed in relation with the removal of 8-quinolinecarboxylic acid pollutant from water. The adsorption capacity of an ACC is quantitatively improved in the presence of an electric field (electroadsorption process) reaching values of 96% in comparison to 55% in absence of applied potential. In addition, the cathodic treatment results in higher removal efficiencies than the anodic treatment. The enhanced adsorption capacity has been proved to be irreversible, since the removed compound remains adsorbed after switching the applied potential. The kinetics of the adsorption processes is also improved by the presence of an applied potential. PMID:26433936

  4. Enhancement of photoelectrochemical activity for water splitting by controlling hydrodynamic conditions on titanium anodization

    NASA Astrophysics Data System (ADS)

    Sánchez-Tovar, R.; Fernández-Domene, R. M.; García-García, D. M.; García-Antón, J.

    2015-07-01

    This work studies the electrochemical and photoelectrochemical properties of a new type of TiO2 nanostructure (nanosponge) obtained by means of anodization in a glycerol/water/NH4F electrolyte under controlled hydrodynamic conditions. For this purpose different techniques such as Scanning Electronic Microscopy (SEM), Raman Spectroscopy, Electrochemical Impedance Spectroscopy (EIS) measurements, Mott-Schottky (M-S) analysis and photoelectrochemical water splitting tests under standard AM 1.5 conditions are carried out. The obtained results show that electron-hole separation is facilitated in the TiO2 nanosponge if compared with highly ordered TiO2 nanotube arrays. As a result, nanosponges enhance the photoelectrochemical activity for water splitting.

  5. The effect of coal type and pyrolysis temperature on the electrochemical activity of coal at a solid carbon anode in molten carbonate media

    NASA Astrophysics Data System (ADS)

    Allen, J. A.; Glenn, M.; Donne, S. W.

    2015-04-01

    A systematic assessment of the electrochemical activity of two different parent coal types, pyrolysed at temperatures between 500 and 900 °C higher heating temperature (HHT), is presented in this work. Analysis shows that certain coal chars are catalytically activated in molten carbonate media at 600 °C, however activity does not appear to follow trends established for ashless carbon sources. It is seen here that it is not possible to predict activity based solely on electrical resistance, surface functionalization, or the BET surface area of pyrolysed coals. Instead, it is suggested that coal ash type, abundance and distribution plays a pivotal role in activating the coal char to allow fast electrochemical oxidation through a catalytically enhanced pathway. Activation from ash influence is discussed to result from wetting of the molten carbonate media with the carbon surface (change in polarity of electrode surface), through ash mediated oxide adsorption and transfer to carbon particles, or possibly through another catalytic pathway not yet able to be predicted from current results.

  6. Performance evaluation of poly 3-(phenylthiophene) derivatives as active materials for electrochemical capacitor applications

    SciTech Connect

    Ferraris, J.P.; Eissa, M.M.; Brotherston, I.D.; Loveday, D.C.

    1998-11-01

    Electroactive polymers from 3-(4-fluorophenyl)thiophene, 3-(4-cyanophenyl)thiophene, 3-(4-methylsulfonylphenyl)thiophene, and 3-(3,4-difluorophenyl)thiophene were electrochemically deposited onto carbon paper electrodes from tetramethylammonium trifluoromethane-sulfonate (Me{sub 4}NCF{sub 3}SO{sub 3})/acetonitrile and/or tetraethylammonium tetrafluoroborate/acetonitrile electrolyte solutions. The morphologies and electrochemical performance of the films were shown to depend on both the growth and cycling electrolytes. Constant current multicycle tests were performed on model single-cell devices using the type III capacitor configuration at high voltage (2.8--2.9 V). Active material energy and power densities of up to 50 Wh/kg and 5 kW/kg were achieved at discharge rates of 50 and 10 mA/cm{sup 2}, respectively. The long-term stabilities (up to 1000 cycles) of these polymers were investigated by repeated charging and discharging using cyclic voltammetry in both the p- and n-doping regimes.

  7. Preparation and electrochemical characterization of polyaniline/activated carbon composites as an electrode material for supercapacitors.

    PubMed

    Oh, Misoon; Kim, Seok

    2012-01-01

    Polyaniline (PANI)/activated carbon (AC) composites were prepared by a chemical oxidation polymerization. To find an optimum ratio between PANI and AC which shows superior electrochemical properties, the preparation was carried out in changing the amount of added aniline monomers. The morphology of prepared composites was investigated by scanning electron microscopy (SEM) and transmission electron microscope (TEM). The structural and thermal properties were investigated by Fourier transform infrared spectra (FT-IR) and thermal gravimetric analysis (TGA), respectively. The electrochemical properties were characterized by cyclic voltammetry (CV). Composites showed a summation of capacitances that consisted of two origins. One is double-layer capacitance by ACs and the other is faradic capacitance by redox reaction of PANI. Fiber-like PANIs are coated on the surface of ACs and they contribute to the large surface for redox reaction. The vacancy among fibers provided the better diffusion and accessibility of ion. High capacitances of composites were originated from the network structure having vacancy made by PANI fibers. It was found that the composite prepared with 5 ml of aniline monomer and 0.25 g of AC showed the highest capacitance. Capacitance of 771 F/g was obtained at a scan rate of 5 mV/s. PMID:22524013

  8. Micron dimensioned cavity array supported lipid bilayers for the electrochemical investigation of ionophore activity.

    PubMed

    Maher, Sean; Basit, Hajra; Forster, Robert J; Keyes, Tia E

    2016-12-01

    Microcavity supported lipid bilayers, MSLBs, were applied to an electrochemical investigation of ionophore mediated ion transport. The arrays comprise of a 1cm(2) gold electrode imprinted with an ordered array of uniform spherical-cap pores of 2.8μm diameter prepared by gold electrodeposition through polystyrene templating spheres. The pores were pre-filled with aqueous buffer prior to Langmuir-Blodgett assembly of a 1,2-dioleoyl-sn-glycero-3-phosphocholine bilayer. Fluorescence lifetime correlation spectroscopy enabled by the micron dimensions of the pores permitted study of lipid diffusion across single apertures, yielding a diffusion coefficient of 12.58±1.28μm(2)s(-1) and anomalous exponent of 1.03±0.02, consistent with Brownian motion. From FLCS, the MSLBs were stable over 3days and electrochemical impedance spectroscopy of the membrane with and without ionic gradient over experimental windows of 6h showed excellent stability. Two ionophores were studied at the MSLBs; Valinomycin, a K(+) uniporter and Nigericin, a K(+)/H(+) antiporter. Ionophore reconstituted into the DOPC bilayer resulted in a decrease and increase in membrane resistance and capacitance respectively. Significant increases in Valinomycin and Nigericin activity were observed, reflected in large decreases in membrane resistance when K(+) was present in the contacting buffer and in the presence of H(+) ionic gradient across the membrane respectively. PMID:27420132

  9. Electrochemical synthesis of fractal bimetallic Cu/Ag nanodendrites for efficient surface enhanced Raman spectroscopy.

    PubMed

    Li, Da; Liu, Jingquan; Wang, Hongbin; Barrow, Colin J; Yang, Wenrong

    2016-09-21

    Here, we for the first time synthesized bimetallic Cu/Ag dendrites on graphene paper (Cu/Ag@G) using a facile electrodeposition method to achieve efficient SERS enhancement. Cu/Ag@G combined the electromagnetic enhancement of Cu/Ag dendrites and the chemical enhancement of graphene. SERS was ascribed to the rough metal surface, the synergistic effect of copper and silver nanostructures and the charge transfer between graphene and the molecules. PMID:27522964

  10. Enhanced electrochemical properties of fluoride-coated LiCoO2 thin films.

    PubMed

    Lee, Hye Jin; Kim, Seuk Buom; Park, Yong Joon

    2012-01-01

    The electrochemical properties of fluoride-coated lithium cobalt oxide [LiCoO2] thin films were characterized. Aluminum fluoride [AlF3] and lanthanum fluoride [LaF3] coating layers were fabricated on a pristine LiCoO2 thin film by using a spin-coating process. The AlF3- and LaF3-coated films exhibited a higher rate capability, cyclic performance, and stability at high temperature than the pristine film. This indicates that the AlF3 and LaF3 layers effectively protected the surface of the pristine LiCoO2 film from the reactive electrolyte. PMID:22221488