聚1,4-二氨基蒽醌/多壁碳纳米管复合物的制备及其电化学性质研究

以多壁碳纳米管为基板,运用简单磁力搅拌方法,通过π-π堆积作用,使1,4-二氨基蒽醌负载于多壁碳纳米管材料上,获得了聚氨基蒽醌/多壁碳纳米管复合物(PDAAQ/MWCNTs)。采用傅立叶红外光谱(FTIR)、透射电子显微镜(TEM)、循环伏安(CV)和恒流充放电(GCD)等方法对PDAAQ/MWCNTs的结构和性能进行表征。结果发现3~4 nm厚的聚氨基蒽醌层原位生长在多壁碳纳米管上,这种独特的结构极大地增加了复合物的比表面积和聚氨基蒽醌的利用率。分散性能好的PDAAQ/MWCNTs复合物具有高的赝容性能。     

Enhanced Electrochemical Detection of DNA Hybridization Based on Au/MWCNTs Nanocomposites

Abstract

The nanocomposites of gold nanoparticles and multi‐walled carbon nanotubes (MWCNTs) have been applied in the enhanced electrochemical detection of DNA hybridization. Gold nanoparticles coated on MWCNTs uniformly were synthesized by simply one step reaction. Target DNA was detected by the peak current difference of differential pulse voltammetry (DPV) signals of the electroactive indicator methylene blue (MB) before and after hybridization on the Au/MWCNTs modified glass carbon electrode (GCE). Due to the excellent electrical conductivity of the novel matrix, the biosensor revealed high sensitivity with the detection level down to 1.0 pM. Excellently selectivity and reproducibility were also discussed.     

Synthesis,characterization and heterogeneous catalytic application of a nickel(II) Schiff base complex immobilized on MWCNTs for the Hantzsch four-component condensation

A nickel(II) Schiff base complex immobilized on multi-wall carbon nanotubes (MWCNTs) surface as a highly efficient heterogeneous catalyst was synthesized and characterized by IR, X-ray diffraction patterns, scanning electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma, elemental analysis, and thermal gravimetric analysis. Then a facile and environmentally benign procedure was developed for synthesis of polyhydroquinoline derivatives via Hantzsch one-pot condensation reaction of aromatic aldehydes, 1,3-diones, ethyl acetoacetate, and ammonium acetate in the presence of above synthesized catalyst under solvent-free conditions. This protocol has the advantages of stability, easy availability, recyclability and eco-friendly nature of catalyst, simple experimental and work-up procedure, and also high to excellent yields. Considering the solvent-free condition and also temperature, time, and yield of the model reaction, the nanocatalyst reported here is among the best catalysts reported so far for synthesis of polyhydroquinolines.     

Electrochemical Behaviour of Microwave‐assisted Oxidized MWCNTs Based Disposable Electrodes: Proposal of a NADH Electrochemical Sensor

The effect of the oxidation degree of multiwalled carbon nanotubes (MWCNTs) for the detection of NADH was evaluated in this paper. MWCNTs were oxidized by microwave‐assisted sulfonitic treatment at different times (5, 10, 15, and 30 min) and deposited onto a graphite screen printed electrodes. Oxidized MWCNTs were characterized and the electrochemical performance evaluated. The best sensor in terms of sensitivity and stability was obtained after 15 minutes of oxidation (SPE/CNT15). A significant reduction of the NADH oxidation potential was recorded for oxidized MWCNTs compared with unmodified MWCNTs (0.270 V and 0.500 V, respectively vs. Ag/AgCl pseudo reference electrode), increasing the selectivity of the system. Chronoamperometric calibration curves carried out applying a potential of 0.3 V for 1 min were linear in the 4–35 μM range of NADH. A limit of detection of 1 μM was achieved with negligible surface fouling (three consecutive calibration curves, 30 total measurements: slope decrease 5.9 %). Inter electrode reproducibility (n=13) was good resulting in RSD of 15.2 % and 5.0 % for the peak intensity and the oxidation potential, respectively. Quantification of glucose in white wine samples was carried out to demonstrate the ability of the NADH sensor to work in real samples. A good correlation with a spectrophotometric kit for the glucose quantification was achieved.     

Electrochemical synthesis and characterization of polydiphenylamine

Electrochemical oxidation of diphenylamine(DPA)in acetonitrile solution producedan adhesive conducting polydiphenylamine(PDPA)film on the electrode,which exhibited multiplecolour variation in a wide range of potential.The polymer was characterized by cyclic voltam-merry,FTIR and ESR.The results indicate that the electropolymerization of diphenylamine per-forms via the 4,4＇C—C phenyl-phenyl coupling mechanism.FTIR,ESR and conductivity mea-surements for the different states of PDPA show that polydiphenylamine can be reversibly dopedand dedoped either chemically or electrochemically.It is evidenced also that there are paramagneticspecies—polarons in PDPA supposed to be the current carrier.     

Electrochemical behavior of dihydroxybenzene isomers at MWCNTs modified electrode and simultaneous determination in neutral condition

Simultaneous determination of dihydroxybenzene isomers in neutral condition was successfully realized by a simple and easy prepared modified electrode without previous chemical or physical separations. The multi-walled carbon nanotubes modified glassy carbon electrode (MWCNTs/GCE), which was prepared by the drop-coating method, was characterized by FE-SEM and TEM. Then, the electrochemical behavior of dihydroxybenzene isomers at MWCNTs/GCE was systematically studied at different temperature and pH conditions. The oxidation peak potentials were separated in neutral condition with 105 mV to hydroquinone (HQ) and catechol (CC) and 390 mV to CC and resorcinol (RS). And in neutral condition, the amperometric current were found to be linear with concentration of HQ, CC, and RS (20–140 μM) with the presence of 100 μM other isomers. Furthermore, excellent anti-interference, stability, and reproducibility were also presented by this modified electrode.     

Electrochemical characterization and analytical application of arsenopyrite mineral in non-aqueous solutions by voltammetry and potentiometry

Based on the cyclic voltammetric method, in the present study we have employed carbon paste for arsenopyrite mineral characterization in non-aqueous solution. Arsenopyrite yields well-defined cyclic voltammetric responses with well-defined oxidation (in the potential region from −0.7 to 0.7 V, versus Ag/AgCl) and reduction (from −1.0 to 0.8 V) peaks using this electrode. In addition, arsenopyrite mineral was studied as a new indicator electrode for the potentiometric titrations of acids (benzoic, anthranilic and salicylic acids) and bases (N,N′-diphenylguanidine, tributylamine and collidine) in acetonitrile and propionitrile. Potassium hydroxide, tetrabutylammonium hydroxide (TBAH) and perchloric acid proved to be very suitable titrating agents for these titrations.The investigated electrode showed a linear dynamic response for p-toluenesulfonic acid concentrations in the range 0.1-0.001 M, with a Nernstian slope of 38.5 mV in acetonitrile and 44.6 mV in propionitrile. The electrode showed a relatively fast response time and can be used without any time limit or without considerable divergence in potentials. The response time of the electrode was less than 10 s in both solvents. The standard deviation of the determination of the investigated acids and bases was less than 0.6% from those obtained with a glass electrode.The advantages of the electrodes are long-term stability, fast response and reproducibility, while the sensors are easy to prepare and are of low cost.     

Electrochemical determination of bisphenol A based on PHD/MWCNTs modified glassy carbon electrode

A novel electrochemical sensor for the determination of bisphenol A (BPA) was fabricated by block polyelectrolyte composite films, which composed of diblock polyelectrolyte poly (2-hydroxyethyl methacrylate)-b-poly (2-(dimethylamino) ethyl methacrylate) (PHEMA-b-PDMAEMA, noted as PHD in the later content) and multi-walled carbon nanotubes (MWCNTs). The tertiary amino groups of PDMAEMA can be protonated at physiological pH. The protonated PDMAEMA can thus interact with the negatively charged BPA through electrostatic attraction to increase the BPA sorption capacity and enhance the ability for highly sensitive detection of BPA. The PHD/MWCNTs composite films combine the electrocatalytic property of MWCNTs and the electrostatic attraction of protonated PHD. Because of the above-mentioned excellent property of the composite films, the PHD/MWCNTs/glassy carbon electrode exhibited good electrocatalytic activity to electrooxidation of BPA. The wide linear response range of the BPA sensor was from 4.56 × 10^?5 g L^?1 to 2.28 × 10^?2 g L^?1 with a lower detection limit of 2.28 × 10^?6 g L^?1 (S/N = 3) and high sensitivity 2442.86 μA L g^?1 cm^?2. The current reached the steady-state current with a shorter response time less than 4 s. The proposed method was successfully applied to determine BPA in real samples (PVC food package, milk, tap water and pond water) and satisfactory results were obtained. These results indicated that the block polyelectrolyte composite have potential applicability of the BPA sensor.     

芦丁在铂纳米/碳纳米管修饰电极上电化学行为研究

通过电沉积的方式在多壁碳纳米管(MWCNTs)修饰玻碳电极表面上沉积铂(pt)纳米粒子,并运用循环伏安法(CV)、示差脉冲伏安法(DPV)探讨了芦丁在铂纳米/碳纳米管/玻碳电极上的电化学行为.实验结果表明,芦丁在该修饰电极上呈现一对良好氧化还原峰,其氧化峰电流与浓度在3.2×10(-8)～1.2×10(-5)mol/L...     

Electrochemical Determination of Phenylethanolamine A Based on Nafion/MWCNTs/AuNPs Modified Carbon Electrode

Phenylethanolamine A (PEA), a β‐agonist, was found to be illegally used as a growth promoter in pigs last year, causing Chinese government's great attention. Here, a sensitive electrochemical method was developed for detecting PEA by immobilization of gold nanoparticles (AuNPs), multiwalled carbon nanotubes (MWCNTs) and Nafion on the surface of a glassy carbon electrode (GCE). The Nafion/MWCNTs/AuNPs film was characterized by scanning electronic micrographs (SEM) and electrochemical impedance spectroscopy (EIS). The electrochemical behaviors of PEA at the modified GCE were investigated in detail. The synergetic effects of AuNPs, MWCNTs and Nafion amplify the electrochemical reduction signal of PEA, and result in high sensitivity for PEA determination. Under the optimal conditions, the electrochemical sensor shows a wide linear range of 0.01 to 10 (mol/L with a detection limit of 0.005 µmol/L. Moreover, the fabricated sensor presents high selectivity and long‐term stability, which paves a new way for simple, rapid, sensitive detection of PEA.     

Electrochemical and structural characterization of sulfonated polysulfone

We describe the synthesis, as well as the electrochemical and structural characterization, of sulfonated polysulfone intended for use in PEM fuel cells. Starting from a commercial polysulfone, we assessed the performance of these prepared ionomers using synthesis protocols compatible with industrial production. The efficiency of the trimethylsilyl chlorosulfonate and chlorosulfonic acid reagents in the sulfonation process was confirmed by ¹H NMR, FTIR, elemental analysis, chemical titration and thermal analysis (DSC and TGA). Chlorosulfonic acid was the most effective sulfonation reagent. However, based on SEC-MALLS, this reagent induced degradation of the backbone that is detrimental to the thermomechanical stability and lifespan of the membranes. The electrical characterization of the membranes was undertaken using impedance spectroscopy in contact with different HCl aqueous solutions at various temperatures. The activation energies, which ranged from 8.2 to 11 kJ/mol, were in agreement with the prevailing proton vehicular mechanism.     

Synthesis,characterization, and application of helical polymers

This review mainly describes the asymmetric synthesis of optically active polymers with helical conformation. Bulky methacrylates such as triphenylmethyl methacrylate and 1-phenyldibenzosuberyl methacrylate give one-handed helical and optically active polymers with almost perfectly isotactic main chain conformation by polymerization with chiral anionic initiators. The radical polymerization and copolymerization of these monomers under chiral conditions also afford optically active polymers with prevailing one-handed helicity. N, N-Disubstituted acrylamides also give optically active, helical polymers in the asymmetric anionic polymerization. Optically active polyisocyanates with a prevailing one-handed helical structure have been prepared in the copolymerization of an achiral isocyanate with a small amount of an optically active isocyanate and also in the polymerization of alkyl and aromatic isocyanates with optically active lithium alkoxide or amide compounds. The existence of a stable helical structure for polychloral has been successfully proved with the helical oligomers of chloral. One-handed helical polyisocyanides have been prepared by helix-sense-selective polymerization of bulky isocyanides and also by the cyclopolymerization of a 1, 2-diisocyanobenzene derivative with the Pd complex of a one-handed helical oligomer.     

Electrochemical hydrogen production from biomass

Thermodynamic data indicate that the oxidation of oxygenated organic species originating from biomass instead of water at the anode of an electrolysis cell should allow decreasing the cell voltage below 1.23 V. Biosourced alcohols, polyols, sugars, lignocellulosic compounds, and their derivatives are then electroreformed to produce clean hydrogen at the cathode and compounds at the anode of electrolysis cells. The reported studies highlight the main challenges to make electroreforming a future industrial process: higher reaction kinetics and hydrogen evolution rate; better selectivity of anode catalysts toward the formation of CO₂ or added-value compounds; and utilization of nonstrategical metals. An attractive solution to decrease hydrogen production costs and to make bankable other economic activities consists in directly valuing wastes from agriculture/forestry (lignocellulosic raw materials) and/or wastes from biofuel industries.     

Electrochemical characterization of some ferrocenylcarboxylic acids

Summary Several carboxy-substituted ferrocene compounds are prepared and investigated by cyclic voltammetry in acetonitrile solution. The half-wave potentials of most of the acids studied (E _1/2=0.34–0.58 V versus s.c.e.) are more positive than that of ferrocene (0.33 V), reflecting a diminished susceptibility to oxidation of these compounds relative to the parent metallocene. Only -ferrocenylpropionic acid (0.32₅ V) is effectively identical with the latter in its oxidation behaviour, and -ferrocenylbutyric acid (0.31 V) tends to be more readily oxidized. The results are of interest for subsequent chemical oxidation studies of ferrocenylcarboxylic acids.     

Electrochemical characterization of Prussian Blue nanoparticles

Mixing of FeCl₃ solution with the excess of K₄Fe(CN)₆ solution results in well-dispersed Prussian Blue (PB) nanoparticles that are stable over at least one month. Polyaniline was deposited onto the PB-nanoparticle-modified electrode to provide its stability. Promising results of the enhanced detection of H₂O₂ with these PB nanoparticles are described. The text was submitted by the authors in English.     

Electrochemical and structural characterization of lithium titanate electrodes

Lithium titanate (LTO) materials of different particle size, surface area, and morphology were characterized by constant current cycling and cyclic voltammetry. By examining the particles and electrodes with scanning electron microscopy, we show that particle morphology, in addition to particle size, has important implications for high-rate performance. Large agglomerates, even when porous and made of small crystallites, cannot effectively form homogenous electrodes with the polymer binder and carbon conducting diluents; hence, low power performance results. Another nanostructured LTO of very high surface area was found to have poor electrochemical performance most likely due to its high concentration of structural defects. We recommend further development in nanoparticles of LTO of optimal crystallinity as well as improved electrode homogeneity through the use of more compatible binders and conducting diluents and better electrode processing techniques. Simultaneous realization of these imperatives should facilitate the development of LTO-based high-power batteries for automotive applications.     

Electrochemical deposition and characterization of SnS thin films

Thin films of SnS were cathodically deposited onto stainless steel substrates from bath containing 0.025 M SnSO₄, 0.25 M KSCN and 0.25 M Na₂SO₄. The mechanism of electrochemical co-deposition of tin and sulphur was investigated by cyclic voltammetry. Analysis of the chronoamperometric current–time transients suggested that, in the potential range −560 to −590 mV vs saturated calomel electrode, the electrodeposition of SnS involved progressive nucleation model. However, at a potential −600 mV, the electrodeposition involved instantaneous nucleation model. The deposits have been characterized by scanning electron microscopy, X-ray diffraction and optical measurements. SnS films were found to be polycrystalline with an optical energy gap of 1.38 eV.     

Electrochemical deposition and structural characterization of Au-Sn alloys

In the present work the electrochemical deposition of Au-Sn alloys is addressed and a cyanide-free process is presented. The electrolyte is an acidic thiourea solution containing gold as a Au[CS(NH₂)₂]⁺ complex and tin as stannous ions. Results concerning the plating process development and deposit characterization are reported. Au-Sn alloy films with a Sn content up to 50 at% and a single-phase structure can be obtained from the acidic thiourea–Au(I) solution under pulsed current plating conditions. Alloy deposits show three main crystal structures: a face centred cubic (fcc) Au(Sn) solid solution, extending up to 7 at% Sn; a hexagonal close-packed structure, of the same type as the metallurgical phase, up to about 18 at% Sn; and a NiAs-type structure, corresponding to the phase of the equilibrium diagram, with an enlarged homogeneity range. Mechanical properties of thin layers of Au-Sn alloys derived from micro-indentation measurements follow the structural modification with the alloy composition. The ordered intermetallic phases occurring in the equilibrium binary system, in particular the and phases at 8 at% and 16 at% Sn, respectively, are not detected in the electrodeposited alloys. The main factors controlling electrochemical phase formation are pointed out, considering the differences between the phase structure of the electrodeposited alloys and the equilibrium phase diagram.Presented at the 3rd International Symposium on Electrochemical Processing of Tailored Materials held at the 53rd Annual Meeting of the International Society of Electrochemistry, 15–20 September 2002, Düsseldorf, Germany