Fabrication and electrocatalysis of self-assembly directed gold nanoparticles anchored carbon nanotubes modified electrode

A self-assembly directed approach was adopted to modify glassy carbon electrode (GC) with gold nanoparticles incorporation and the electrocatalytic performance of self-assembly modified electrode, GC/SA-Au-ME was critically evaluated for the oxidation of ascorbic acid (AA). The modification involves the dispersion of multi-wall carbon nanotube (MWNT) and an inclusion complex, beta-cyclodextrin-4-aminothiophenol on the surface of GC electrode in the presence of cetyltrimethylammonium bromide (CTAB). Gold nanoparticles were deposited into the self-assembled sites to fabricate the modified electrode, GC/SA-Au-ME. Another electrode (GC-Au-ME) was fabricated under similar conditions in the absence of CTAB. The electrocatalytic activity of the modified electrodes (GC/SA-Au-ME and GC-Au-ME) towards the oxidation of AA was critically compared. Cyclic voltammetry, chronoamperometry, and double potential chronoamperometry were used to evaluate the characteristics of the modified electrodes. The self-assembled electrode (GC/SA-Au-ME) shows excellent electrocatalytic activity over the other electrode, GC-Au-ME. Augmented current response, faster electron transfer kinetics (with a rate constant for electron transfer process as 3.25 x 10(4) cm3 mol(-1) s(-1)), linear range of response for the analyte (1-50 mM with an extended detection limit to 1 microM), better sensitivity, and selectivity were witnessed for the self-assembly directed modified electrode.     

Assembly of individual TiO2-C60/porphyrin hybrid nanoparticles for enhancement of photoconversion efficiency

Rational organization of porphyrin and C60 on the electrode surface in photovoltaic structures is essential to yield high quantum efficiency. In the present work, individual TiO2 nanoparticles were modified by introducing C60 and porphyrin units on the surface, and then electrophoretically deposited on an ITO/SnO2 electrode. The morphology of the photoactive layer on the electrode was significantly different from that of the layer produced as a result of separate deposition of C60 and porphyrin. The maximum incident photon to current efficiency of the resulting electrode approached 88% at 410 nm, which is the highest value among molecule-based photovoltaic cells reported to date. This indicates that molecular assembly of the C60 and porphyrin units on the individual nanoparticles through strong chemical attachment is a key factor in improving effective electron transfer between the photoactive units and the electrodes.     

Electrochemical biosensing platforms using platinum nanoparticles and carbon nanotubes

Platinum nanoparticles with a diameter of 2-3 nm were prepared and used in combination with single-wall carbon nanotubes (SWCNTs) for fabricating electrochemical sensors with remarkably improved sensitivity toward hydrogen peroxide. Nafion, a perfluorosulfonated polymer, was used to solubilize SWCNTs and also displayed strong interactions with Pt nanoparticles to form a network that connected Pt nanoparticles to the electrode surface. TEM and AFM micrographs illustrated the deposition of Pt nanoparticles on carbon nanotubes whereas cyclic voltammetry confirmed an electrical contact through SWCNTs between Pt nanoparticles and the glassy carbon (GC) or carbon fiber backing. With glucose oxidase (GOx) as an enzyme model, we constructed a GC or carbon fiber microelectrode-based biosensor that responds even more sensitively to glucose than the GC/GOx electrode modified by Pt nanoparticles or CNTs alone. The response time and detection limit (S/N = 3) of this biosensor was determined to be 3 s and 0.5 microM, respectively.     

Determination of serotonin on a glassy carbon electrode modified by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin and single walled carbon nanotubes

A chemically modified electrode [poly(TAPP)-SWNT/GCE] was prepared by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin (TAPP)-single walled carbon nanotubes (SWNT) on the surface of a glassy carbon electrode (GCE). This modified electrode was employed as an electrochemical biosensor for the determination of serotonin concentration and exhibited a typical enhance effect on the current response of serotonin and lower oxidation overpotential. The biosensor was very effective to determined 5-HT in a mixture. The linear response was in the range 2.0 x 10(-7) to 1.0 x 10(-5) M, with a correlation coefficient of 0.999 [i(p)(microA) = 3.406 C (microM)+0.132] on the anodic current, with a detection limit of 1 x 10(-9) M. Due to the relatively low currents and different potentials in the electrochemical responses to ascorbic acid and dopamine, the modified electrode is a useful and effective sensing device for the selective and sensitive serotonin determination in the presence of ascorbic acid and dopamine.     

Metallic nanoparticle-carbon nanotube composites for electrochemical determination of explosive nitroaromatic compounds

Metal nanoparticles (Pt, Au, or Cu) together with multiwalled and single-walled carbon nanotubes (MWCNT and SWCNT) solubilized in Nafion have been used to form nanocomposites for electrochemical detection of trinitrotoluene (TNT) and several other nitroaromatics. Electrochemical and surface characterization by cyclic voltammetry, AFM, TEM, SEM, and Raman spectroscopy confirmed the presence of metal nanoparticles on CNTs. Among various combinations tested, the most synergistic signal effect was observed for the nanocomposite modified glassy carbon electrode (GC) containing Cu nanoparticles and SWCNT solubilized in Nafion. This combination provided the best sensitivity for detecting TNT and other nitroaromatic compounds. Adsorptive stripping voltammetry for TNT resulted in a detection limit of 1 ppb, with linearity up to 3 orders of magnitude. Selectivity toward the number and position of the nitro groups in different nitroaromatics was very reproducible and distinct. Reproducibility of the TNT signal was within 7% (n = 8) from one electrode preparation to another, and the response signal was stable (+/-3.8% at 95% confidence interval) for 40 repeated analyses with 10 min of preconditioning. The Cu-SWCNT-modified GC electrode was demonstrated for analysis of TNT in tap water, river water, and contaminated soil.     

Poly-cobalt[tetrakis(o-aminophenyl)porphyrin] nanowire and single-walled carbon nanotube for the analysis of hydrogen peroxide

Nanowires of poly-cobalt[tetrakis(o-aminophenyl)porphyrin] (PCoTAPPNW) were fabricated by electrochemical polymerization by the cyclic voltammetric method in anodic aluminum oxide membranes. A glassy carbon electrode (GCE) modified by PCoTAPPNW and single-walled carbon nanotubes (SWNT) without any binder was investigated with voltammetric methods in phosphate buffer saline (PBS) at pH 7.4. The PCoTAPPNW + SWNT/GCE exhibited strongly enhanced voltammetric and amperometric sensitivity towards hydrogen peroxide (H2O2), which shortened the response time (< 5 seconds), showed detection limit of 1.0 microM and enhanced the sensitivity for H2O2 detection with 194 microA mM(-1) cm(-2). The PCoTAPPNW + SWNT/GCE can be used to monitor H2O2 at very low concentration in physiological pH as an efficient electrochemical H2O2 sensor.     

Fabrication of Ni nanoparticles on ordered mesoporous carbon using an immersion-electrodeposition method

Ni nanoparticles have been fabricated on the surface of CMK-3 mesoporous carbon through an immersion-electrodeposition (IE) technique. Transmission electron microscopy analysis indicated that it was a facile approach to electrochemically prepare nano-sized Ni clusters. The electrocatalytic properties of Ni/CMK-3 nanocomposites electrode for hydrogen evolution reaction have been investigated by liner scanning voltammetry in alkaline solution, and high electrocatalytic activity was observed. Therefore, for the first time, we report this IE method as a new route to prepare metal/CMK-3 nanocomposites which have potential applications in the catalytic field.     

Enhanced electrochemical detection of DNA hybridization with carbon nanotube modified paste electrode

A novel electrochemical genesensor using twice hybridization enhancement of gold nanoparticles based on carbon paste modified electrode is described. The carbon nanotube modified carbon paste electrode (CNTPE) and mesoporous molecular sieve SBA-15 modified carbon paste electrode (MSCPE) were investigated. The assay relies on the immobilization of streptavidin-biotin labeled target oligonucleotides onto the electrode surface and its hybridization to the gold nanoparticle-labeled DNA probe. After twice hybridization enhanced connection of gold nanoparticles to the hybridized system, the differential pulse voltammetry (DPV) signal of total gold nanoparticles was monitored. It was found that the adsorption of oligonucleotide and hybridized DPV signal on CNTPE were both enhanced in comparison with that of pure carbon paste electrode (CPE). But this trend was reverse on MSCPE. The DPV detection of twice hybridized gold nanoparticles indicated that the sensitivity of the genesensor enhanced about one order of magnitude compared with one-layer hybridization. One-base mismatched DNA and complementary DNA could be distinguished clearly. However, no distinct advantage of MSCPE over CPE was found.     

Characterization of platinum nanoparticle-embedded carbon film electrode and its detection of hydrogen peroxide

A method for the highly sensitive determination of acetylcholine (ACh) and choline (Ch) that employs a graphite-like carbon film electrode containing 6.5% platinum (Pt) nanoparticles was developed for use as a detector in microbore liquid chromatography (LC) with a postcolumn enzyme reactor. The film electrode was prepared by RF cosputtering carbon and Pt, which requires only a one-step formation process. This method can control the Pt content of the film at a relatively low deposition temperature (below 200 degrees C). The average size of the Pt nanoparticles was 2.5 nm. The film electrode showed excellent electrocatalytic activity, high sensitivity, and negligible baseline drift when detecting hydrogen peroxide. The electrode was modified with glucose oxidase and responded rapidly to glucose with a much more stable baseline current than at a Pt bulk electrode based sensor. Therefore, it is appropriate to employ the electrode to detect trace amounts of biomolecules, such as neurotransmitters and hormones combined with various oxidase enzymes. We used the electrode as a detector for microbore LC and observed a low detection limit of 2.5 and 2.3 fmol (10-microL injection) for ACh and Ch, respectively, which is approximately 1 order of magnitude lower than that of a Pt bulk electrode.     

Sonochemical synthesis of ordered SnO₂/CMK-3 nanocomposites and their lithium storage properties

In this study, we successfully prepare SnO(2) nanoparticles inside the pore channels of CMK-3 ordered mesoporous carbon via sonochemical method. The content of SnO(2) is 17 wt % calculated according to the energy-dispersive X-ray spectroscopy (EDS) result. CMK-3 with 17 wt % loading of SnO(2) nanoparticles has a large specific surface area and pore volume. Electrochemical performance demonstrates that the ordered SnO(2)/CMK-3 nanocomposites electrode possesses higher reversible capacity and cycling stability than that of original CMK-3 electrode. Moreover, the ordered SnO(2)/CMK-3 nanocomposites electrode also exhibits high capacity at higher charge/discharge rate. The improved electrochemical performance is attributed to the nanometer-sized SnO(2) formed inside CMK-3 and the large surface area of the mesopores (3.4 nm) in which the SnO(2) nanoparticles are formed.     

Well-defined core-shell carbon black/polypyrrole nanocomposites for electrochemical energy storage

The well-defined core-shell carbon black/polypyrrole (CB/PPy) nanocomposites were prepared via the in situ chemical oxidative polymerization of pyrrole from the surfaces of the carbon black (CB) nanoparticles, with poly(2-hydroxy-3-(methacryloyloxy) propane-1-sulfonate) (PHMAS) as both the surfactant and the dopant. The nanocomposites exhibited the high conductivity at room temperature and the weakly temperature dependence of conductivity from 283 to 423 K. When the core-shell CB/PPy nanocomposites were used as the electrode materials for the supercapacitors, the maximum discharge capacity of 366 F/g was achieved, after being corrected for the weight percentage of the PPy phase at the current density of 5 mA/cm(2) in 1.0 M NaNO(3) electrolyte solution.     

High-density assembly of gold nanoparticles to multiwalled carbon nanotubes using ionic liquid as interlinker

Gold nanoparticles were deposited onto the surface of carbon nanotubes through an interlinker of ionic liquid terminated with hydroxyethyl units at one end and exchangeable chloride counterions at the other end. The morphology, structure, and composition of the resulting hybrids were characterized by transmission electron microscopy and X-ray diffraction. A very high density of gold nanoparticles was homogeneously dispersed and well-separated from one another on the modified multi-walled carbon nanotubes. The optical absorption of the products was observed by UV-visible spectroscopy. The results imply that the obtained carbon nanotube-gold nanocomposites have a good application potential in catalysis, sensor, and fuel cells.     

Picomolar detection of insulin at renewable nickel powder-doped carbon composite electrode

A sol-gel technique was used for fabrication of a renewable carbon composite electrode (CCE) modified with nickel powder. This modified electrode shows excellent catalytic activity for the oxidation of insulin in alkaline solutions. The nickel powder was then oxidized to form a nickel oxide film electrode, which was used as an amperometric detector for hydrodynamic amperometry and flow injection analysis of insulin. It was found that the calibration curve was linear up to 30 microM with a detection limit of 40 pM under the optimized conditions for hydrodynamic amperometry using a rotating disk modified CCE. Flow injection amperometric determination of insulin at this modified electrode yielded a calibration curve with the following characteristics; linear dynamic range of 15-1000 pM, sensitivity of 8659.23 pA pM-1 cm-2, and detection limit of 2 pM. This electrode shows many advantages as an insulin sensor such as simple preparation method without using any specific electron-transfer mediator or specific reagent, high sensitivity, excellent catalytic activity, short response time, long-term stability, and remarkable antifouling property toward insulin and its oxidation product. Sensitivity, detection limit, and antifouling properties of this insulin sensor are better than all of the reports in the literature. Additionally, it is promising for monitoring insulin in chromatographic effluents.     

Fabrication of a gold nanoparticles decorated carbon nanotubes based novel modified electrode for the electrochemical detection of glucose

A modified electrode based on gold nanoparticles decorated multiwall carbon nanotubes (MWNTs), MWNT-Au(nano)-ME is fabricated. MWNTs are functionalized with 4-aminothiophenol and coated over the glassy carbon electrode. Further, Au nanoparticles are deposited into MWNTs coated GC electrode by electrochemical reduction of HAuCl4. Field emission transmission electron microscope (FETEM) image shows the formation of approximately 5 nm sized Au nanoparticles without any agglomeration on the MWNTs surface. Further, the presence of Au nanoparticles is confirmed through X-ray photoelectron spectroscopic (XPS) studies. The electrocatalytic activity of the MWNT-Au(nano)-ME towards the detection of glucose is investigated. MWNT-Au(nano)-ME shows enhanced current response than pristine MWNT-ME over the entire (+0.05 to +0.80 V) potential range. The modified electrode shows linear response to current with the concentration of glucose between 1 and 20 mM. Larger current responses to glucose oxidation are witnessed at +0.60 V than at +0.05 V. However, a large interference signal, reflecting the accelerated oxidation of electroactive interference is observed at +0.60 V. No overlapping signal from the interferents such as ascorbic acid, acetaminophen, and dopamine are observed at the MWNT-Au(nano)-ME at +0.05 V. Further, the MWNT-Au(nano)-ME shows high resistance to the toxictiy of chloride ions.     

Preparation of multiwalled carbon nanotubes-platinum-Nafion-glucose oxidase nanobiocomposite and its application to glucose biosensor

Platinum (Pt) nanoparticles were electrodeposited within multiwalled carbon nanotubes-Nafion-glucose oxidase (MWNTs-Nafion-GOx) nanobiocomposite by a potentiostatic method. The morphology and nature of the resulting MWNTs-Pt-Nafion-GOx nanobiocomposite were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). The electrocatalytic properties of the MWNTs-Pt-Nafion-GOx nanobiocomposite film modified glassy carbon electrode were characterized by cyclic voltammetry and amperometry in the presence of hydrogen peroxide. The glucose biosensor sensitivity was strongly influenced by the deposits of Pt nanoparticles and amount of GOx concentration within the MWNTs-Pt-Nafion-GOx nanobiocomposite film. The optimized glucose biosensor displayed a sensitivity of 640 nA mM(-1), a linear range of up to 4 mM, a detection limit of 4 microM, and a response time of less than 4 s at an operating potential of +500 mV versus Ag/AgCl (3 M KCl).     

Antioxidant redox sensors based on DNA modified carbon screen-printed electrodes

Antioxidant redox sensors based on DNA modified carbon screen-printed electrodes were developed. The carbon ink was doped with TiO2 nanoparticles, onto which double-strand DNA was adsorbed. A redox mediator, namely, tris-2,2'-bipyridine ruthenium(II) [Ru(bpy)3(2+)] was electrooxidized on the electrode surface to subsequently oxidize both the adsorbed ds-DNA and the antioxidants in solution. The resulting oxidation damage of the adsorbed ds-DNA was then detected by square wave voltammetry in a second solution containing only Ru(bpy)3Cl2 at a low concentration (microM). A kinetic model was developed to study the protecting role of antioxidants in aqueous solutions. The electrochemical sensor has been applied to evaluate the redox antioxidant capacity of different molecules.     

Porphyrin-modified electrodes as biomimetic sensors for the determination of organohalide pollutants in aqueous samples

A preliminary examination of a simple and rapid screening method for quantifying a range of toxic organohalides directly in aqueous solution based on their electrocatalytic reduction with a metalloporphyrin catalyst is described. Homogenous catalysis is described as well as heterogeneous catalysis using precipitated cobalt(II) tetraphenylporphine ((TPP)Co) at a graphite foil electrode which permitted the sensitive detection of a wide range of different organohalides, including a number of chemically diverse industrial pollutants such as 1,2,3,4,5,6-hexachlorocyclohexane (lindane) and carbon tetrachloride, representative of haloalkane compounds, haloalkenes such as perchloroethylene, and aromatics, such as 2,4-dichlorophenoxyacetic acid, pentachlorophenol, and the insecticide DDT. The coordinating effect of solvent on the thermodynamics of the Co(II)/(I) electrode reaction is used to practical advantage to build an amperometric detector that is insensitive to interference from oxygen, a parameter that varies considerably in environmental samples. Devices also appear relatively insensitive to the ionic composition of the analyte sample. The work provides the basis for developing a prototype sensor for screening toxic organohalogen pollutants for use in environmental monitoring situations.     

Ionic liquid-assisted hydrothermal synthesis of TiO2 nanoparticles and its applications towards the photocatalytic activity and electrochemical sensor

This work reports the synthesis of TiO₂ nanoparticles via ionic liquid-assisted hydrothermal method at 130?°C for two days. The obtained product was characterised by various techniques. The X-ray diffraction data reveal the anatase phase TiO₂ nanoparticles with crystallite size 37 nm. The Fourier transform infrared spectrum shows a band at 400 cm^?1 due to Ti–O–Ti stretching vibration, in addition to the presence of ionic liquid. The UV–Vis spectrum of TiO₂ nanoparticles shows an absorption band at 314 nm which indicates a blueshift compared with that of bulk TiO_2. The transmission electron microscopy images show almost spherical-shaped nanoparticles with an average diameter of 40–80 nm. TiO₂ nanoparticles exhibit excellent photocatalytic activity for the degradation of trypan blue, and also help in the reduction of Cr⁺⁶ to Cr⁺³. TiO₂ nanoparticles modified glassy carbon electrode exhibits better electrocatalytic oxidation towards dopamine compared with bare glassy carbon electrode.     

Anodic stripping voltammetry of arsenic(III) using gold nanoparticle-modified electrodes

A novel method for the detection of arsenic(III) in 1 M HCl at a gold nanoparticle-modified glassy carbon electrode has been developed. The gold nanoparticles were electrodeposited onto the glassy carbon electrode via a potential step from +1.055 to -0.045 V vs SCE for 15 s from 0.5 M H2SO4 containing 0.1 mM HAuCl4. The resulting electrode surfaces were characterized with both AFM and cyclic voltammetry. Anodic stripping voltammetry of arsenic(III) on the modified electrode was performed. After optimization, a LOD of 0.0096 ppb was obtained with LSV.     

氮掺杂多孔碳负载铜钴纳米复合材料的制备及其电催化性能EI北大核心CSCD

先以ZIF-8作为前驱体采用简单的高温炭化法制备出氮掺杂多孔碳纳米多面体(NPC),再通过一步化学还原法将铜和钴颗粒负载到多孔碳上,成功制备出Cu@Co/NPC纳米复合材料。运用X射线粉末衍射仪、透射电子显微镜和X射线光电子能谱等手段对复合材料进行表征,将该复合材料修饰到玻碳电极表面上,研究其对肼的电化学响应。结果表明,Cu@Co/NPC纳米复合材料发挥出协同作用,从而对肼展现出比单一组分修饰电极更优异的电催化作用。在优化的实验条件下,复合材料修饰电极与肼的浓度在5~1850μmol/L范围内呈良好的线性关系,检测限达0.08μmol/L。此外,该复合材料修饰电极测定肼的稳定性、重现性以及选择性均较好,已被成功用于环境水样中肼的检测,结果令人满意。