Layer-by-layer electrostatic self-assembly of anionic and cationic carbon nanotubes

<正>The layer-by-layer(LBL) self assembly of anionic and cationic multi-walled carbon nanotubes(MWNTs) through electrostatic interaction has been carried out to fabricate all-MWNT multilayer films.The alternate uniform assembly of anionic and cationic MWNTs was investigated by UV-vis spectroscopy.Scanning electron microscopy(SEM) images displayed the growth of the MWNT films.     

Nanostructured films from phthalocyanine and carbon nanotubes: surface morphology and electrical characterization

We report on the investigation of the surface morphology and DC conductivity of nanostructured layer-by-layer (LbL) films from nickel tetrasulfonated phthalocyanine (NiTsPc) alternated with either multi-walled carbon nanotubes (MWNTs/NiTsPc) or multi-walled carbon nanotubes dispersed in chitosan (MWNTs+Ch/NiTsPc). We have explored the surface morphology of the films by using fractal concepts and dynamic scale laws. The MWNTs/NiTsPc LbL films were found to have a fractal dimension of ca. 2, indicating a quasi Euclidean surface. MWNTs+Ch/NiTsPc LbL films are described by the Lai-Das Sarma-Villain (LDV) model, which predicts the deposition of particles and their subsequent relaxation. An increase in the wetting contact angle of MWNTs+Ch/NiTsPc LbL films was observed, as compared with MWNTs/NiTsPc LbL films, which presented an increase in the fractal dimension of the first system. Room temperature conductivities were found be ca. 0.45 S/cm for MWNTs/NiTsPc and 1.35 S/cm for MWNTs+Ch/NiTsPc.     

Ultradisperse catalytic layers supported by nanotubes and poly(diallyldimethylammonium)chloride polymer

A catalytic system consisting of carbon nanotubes, poly(diallyldimethylammonium)chloride, and a very thin layer of platinum or platinum-ruthenium is assembled layer-by-layer (LbL) on a glassy carbon (GC) electrode. Deposits of platinum metals are studied by electrochemical methods, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). Such catalyst layers are shown to exhibit much higher activity in the methanol oxidation reaction as compared with commercial and electroplated catalysts. The currents compared are calculated per the surface area of deposited metals determined with respect to hydrogen adsorption.     

A general electrochemical approach to deposition of metal hydroxide/oxide nanostructures onto carbon nanotubes

This communication describes a new and relatively general electrochemical approach to the deposition of transition metal hydroxide/oxide nanostructures onto multi-walled carbon nanotubes (MWNTs) based on the precipitation of metal hydroxide/oxide nanostructures onto MWNTs by increasing the local pH values at the electrode/electrolyte interface induced by the proton-consuming electrochemical reduction of hydrogen peroxide (H₂O₂). The results obtained with cyclic voltammetry, scanning electron microscopy, and X-ray photoelectron spectroscopy of the synthetic nanocomposites substantially suggest the deposition of the metal hydroxides/oxides onto MWNTs induced by the electrochemical reduction of H₂O₂. This study essentially offers a facile but effective and relatively general electrochemical approach to the synthesis of the nanocomposites consisting of metal hydroxides/oxides and MWNTs.     

Amperometric Biosensors for Glucose Based on Layer‐by‐Layer Assembled Functionalized Carbon Nanotube and Poly (Neutral Red) Multilayer Film

Abstract

Multiwalled carbon nanotubes (MWNTs) were treated with a mixture of concentrated sulfuric and nitric acid to introduce carboxylic acid groups to the nanotubes. Conducting polymer film was prepared by electrochemical polymerization of neutral red (NR). By using a layer‐by‐layer method, homogeneous and stable MWNTs and poly (neutral red) (PNR) multilayer films were alternately assembled on glassy carbon (GC) electrodes. With the introduction of PNR, the MWNTs/PNR multilayer film system showed synergy between the MWNTs and PNR, with a significant improvement of redox activity due to the excellent electron‐transfer ability of carbon nanotubes (CNTs) and PNR. The electropolymerization is advantageous, providing both prolonged long‐term stability and improved catalytic activity of the resulting modified electrodes. The MWNTs/PNR multilayer film modified glassy carbon electrode allows low potential detection of hydrogen peroxide with high sensitivity and fast response time. As compared to MWNTs and PNR‐modified GC electrodes, the magnitude of the amperometric response of the MWNTs/PNR composite‐modified GC electrode is more than three‐fold greater than that of the MWNTs modified GC electrode, and nine‐fold greater than that of the PNR‐modified GC electrode. With the immobilization of glucose oxidase onto the electrode surface using glutaric dialdehyde, a biosensor that responds sensitively to glucose has been constructed. In pH 6.98 phosphate buffer, nearly interference‐free determination of glucose has been realized at ?0.2 V vs. SCE with a linear range from 50 µM to 10 mM and response time <10s. The detection limit was 10 µM glucose (S/N=3).     

Electrochemical characteristics of the immobilization of calf thymus DNA molecules on multi-walled carbon nanotubes

Immobilization of DNA on carbon nanotubes plays an important role in the development of new types of miniature DNA biosensors. Electrochemical characteristics of the immobilization of calf thymus DNA molecules on the surfaces of multi-walled carbon nanotubes (MWNTs) have been investigated by cyclic voltammetry and electrochemical impedance analysis. The peak currents for Fe(CN)(6)(3-)/Fe(CN)(6)(4-) redox couple observed in the cyclic voltammograms decrease and the electron-transfer resistance (R(et)) obtained from the Nyquist plots increase due to the immobilization of DNA molecules (dsDNA or ssDNA) on the surfaces of MWNTs. Most of calf thymus DNA are covalently immobilized on MWNTs via diimide-activated amidation between the carboxylic acid groups on the carbon nanotubes and the amino groups on DNA bases, though the direct adsorption of the DNA molecules on MWNTs can be observed. Additionally, the interaction between DNA molecules immobilized on MWNTs and small biomolecules (ethidium bromide) can be observed obviously by cyclic voltammetry and electrochemical impedance analysis. This implies that the DNA molecules immobilized at the surface of MWNTs, with little structure change, still has the ability to interact with small biomolecules.     

Flow Field Induced Steady Alignment of Oxidized Multi-walled Carbon Nanotubes

The steady ordered micro-ribbons of oxidized multi-walled carbon nanotubes (MWNTs) were obtained through micro-aperture PTFE membrane by vacuum filtration. After treatment by mixture of concentrated nitric acid and sulfuric acid, the surface functional groups modified MWNTs can be easily dispersed to form a homogeneous suspension. It is found that the steady micro-ribbons existed in the films obtained by vacuum filtration of the suspension. The filtration formed steady flow field and induced steady alignment of oxidized MWNTs. The chemical treatment of MWNTs forming strong interaction between MWNTs is necessity to keep steady of the micro-ribbons microstructure.     

Electrostatic synthesis and electrochemical properties of a composition comprising ultrathin layers of silicododecamolybdate anions and poly(allyl ammonium) cations

A layer-by-layer (LbL) composition comprising ultrathin anionic layers of silicododecamolybdate and cationic layers of poly(allyl ammonium) is synthesized. The synthesis is realized by means of successive immersion of a glassy-carbon rod into aqueous sulfuric acid solutions of silicododecamolybdic acid and poly(allyl ammonium) hydrochloride. Cyclic voltammetry shows that the silicododecamolybdate anion in the composition undergoes three steps of reversible reduction with formal potentials of 0.34, 0.22, and 0.02 V (SCE). It is established that in the course of synthesis one can obtain a sixfold increase in the currents of redox conversions as compared with currents of a monolayer of the anion chemisorbed on glassy carbon. The LbL composition exhibits catalytic activity during electrochemical reduction of NO ₂ ^? : the cathodic current of the third redox transition considerably increases and the peak in the reverse run of a cyclic voltammogram disappears. The calculated Michaelis constant of 5 × 10^?2 M speaks of a high catalytic activity of the electrode.     

Covalent assembly and micropatterning of functionalized multiwalled carbon nanotubes to monolayer-modified Si(111) surfaces

Multiwalled carbon nanotubes (MWNTs) covalently bound to monocrystalline p-type Si(111) surfaces have been prepared by attaching soluble amine-functionalized MWNTs onto a preassembled undecanoic acid monolayer using carbodiimide coupling. SEM analysis of these functionalized surfaces shows that the bound MWNTs are parallel to the surface rather than perpendicular. The voltammetric and electrochemical impedance spectroscopy measurements reveal that the electron transfer at the MWNT-modified surface is faster than that observed at a MWNT-free alkyl monolayer. We have also demonstrated that it is possible to prepare MWNT micropatterns using this surface amidation reaction and a "reagentless" UV photolithography technique. Following this approach, MWNT patterns surrounded by n-dodecyl areas have been produced and the local electrochemical properties of these micropatterned surfaces have been examined by scanning electrochemical microscopy. In particular, it is demonstrated that the MWNT patterns allow a faster charge transfer which is consistent with the results obtained for the uniformly modified surfaces.     

Removal of anionic and cationic dyes from wastewater by adsorption using multiwall carbon nanotubes

This paper evaluated the efficiency and reusability of multiwall carbon nanotubes (MWNTs) on removal of cationic and anionic dyes under effect of pH, dose of MWNTs and concentration of dyes. The characterization of MWNTs is characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), Raman spectra and BET (Brunauer, Emmett and Teller) surface area. SEM and TEM analyses showed that MWNTs had size within nano scale range of 10–50 nm. The experimental results indicated that the efficiency of removal of MWNTs increase under condition of normal pH, at contact time 60 min with agitation speed 240 rpm and initial concentration of dyes 10 mg/l. Under these optimal conditions, the removal reached 98.7% and 97.2% for anionic dyes and cationic dyes, respectively. For economic use, MWNTs can be used more than one time where the same experiments with the already used MWNTs was repeated and it was found that the percent removal is almost the same.     

Preparation of polypyrrole/multi-walled carbon nanotube hybrids by electropolymerization combined with a coating method for counter electrodes in dye-sensitized solar cells

In this work, multi-wall carbon nanotubes coated with polypyrrole (PPy/MWCNT) have been used as counter electrode (CE) materials for dye-sensitized solar cells (DSSCs). PPy was deposited onto fluorine-doped tin-oxide-coated glass by electrochemical polymerization of pyrrole. Three surfactants were used in the preparation of the hybrids: cationic cetyltrimethylammonium bromide, anionic sodium dodecylbenzenesulfonate (DBSNa), and non-ionic polyoxyethylene sorbitan monolaurate (Tween20). The morphologies of the PPy and PPy/MWCNT hybrids were investigated using scanning electron spectroscopy. Chemical composition of the prepared CEs was determined by X-ray photoelectron spectroscopy and Fourier-transformed infrared spectroscopy. The catalytic activity of the PPy and PPy/MWCNT layers was evaluated using cyclic voltammetry, and the photovoltaic properties of DSSCs with PPy and PPy/MWCNT CEs were characterized using I–V measurements. PPy/MWCNT samples that were prepared by electrochemical polymerization showed the best results when the anionic surfactant DBSNa was used during polymerization. The photoelectric conversion efficiency of PPy/MWCNT prepared by electrochemical polymerization was 2.9%, which was 59% of that of Pt CE (4.9%).     

Structural and characteristic analysis of carbon nanotubes-ionic liquid gel biosensor

The structure and characteristic of carbon nanotubes-ionic liquid gel biosensor were studied by voltammetry, microscopy and spectroscopy. Various biomolecules were electrochemically detected with this gel biosensor such as glucose oxidase and NADH. The excellent electrochemical behavior of this gel biosensor might be due to the following three main factors: (1) the inherently perfect electrochemical characteristic of multi-wall carbon nanotubes (MWNTs); (2) the better solvent effect and conductivity of ionic liquid as well as the proper interactions between MWNTs and ionic liquid; (3) the proper mixing ratio of MWNTs to ionic liquid. Meanwhile, the interactions between MWNTs and ionic liquid were carefully studied as well. It can be concluded that the non-covalent (π–π) interaction between the imidazole loop of ionic liquid and MWNTs side wall should play an important role. This work gives a further understanding of what results in the high sensitivity and selectivity of such a biosensor to some biomolecules, and provides a simple and easy approach to design new biosensors with various nano-particles and versatile ionic liquid.     

Impedimetric Aptasensors Based on Carbon Nanotubes – Poly(methylene blue) Composite

The effect of aptamer structure and immobilization platform on the efficiency of thrombin binding and its detection using electrochemical impedance spectroscopy (EIS) characteristics was investigated with aptasensors based on glassy carbon electrodes covered with multiwalled carbon nanotubes (MWNTs). Aptamers with one or two binding sequences GGTTGGTGTGGTTGG specific for thrombin and poly(dA) and poly(dT) tags able to form dimeric products (aptabodies) were used to establish significance of steric and electrostatic factors in aptasensor performance. We have shown that electropolymerization of methylene blue onto MWNTs significantly improved electrochemical characteristics and sensitivity of thrombin detection against bare MWNTs. Charge transfer resistance and capacitance of the surface layer were measured in the presence of redox probe [Fe(CN)₆]^3?/4?. Aptasensors make it possible to detect thrombin in the concentration range 1 nM–1 µM with the limit of detection of 0.7 nM (monitoring resistance changes) and 0.5 nM (capacitance changes), respectively.     

Temperature-responsive polymer/carbon nanotube hybrids: smart conductive nanocomposite films for modulating the bioelectrocatalysis of NADH

A temperature-sensitive polymer/carbon nanotube interface with switchable bioelectrocatalytic capability was fabricated by self-assembly of poly(N-isopropylacrylamide)-grafted multiwalled carbon nanotubes (MWNT-g-PNIPAm) onto the PNIPAm-modified substrate. Electron microscopy and electrochemical measurements revealed that these fairly thick (>6?μm) and highly porous nanocomposite films exhibited high conductivity and electrocatalytic activity. The morphological transitions in both the tethered PNIPAm chains on a substrate and those polymers wrapping around the MWNT surface resulted in the opening, closing, or tuning of its permeability, and simultaneously an electron-transfer process took place through the channels formed in the nanostructure in response to temperature change. By combining the good electron-transfer and electrochemical catalysis capabilities, the large surface area, and good biocompatibility of MWNTs with the responsive features of PNIPAm, reversible temperature-controlled bioelectrocatalysis of 1,4-dihydro-β-nicotinamide adenine dinucleotide with improved sensitivity has been demonstrated by cyclic voltammetry and electrochemical impedance spectroscopy measurements. The mechanism behind this approach was studied by Raman spectroscopy, in situ attenuated total reflection FTIR spectroscopy, and contact angle measurements. The results also suggested that the synergetic or cooperative interactions of PNIPAm with MWNTs gave rise not only to an increase in surface wettability, but also to the enhancement of the interfacial thermoresponsive behavior. This bioelectrocatalytic "smart" system has potential applications in the design of biosensors and biofuel cells with externally controlled activity. Furthermore, this concept might be proposed for biomimetics, interfacial engineering, bioelectronic devices, and so forth.     

Electro-deposition of platinum nanoparticles on 4-mercaptobenzene-functionalized multi-walled carbon nanotubes

A new method to electro-deposit platinum nanoparticles on the surface of multi-walled carbon nanotubes (MWNTs) functionalized with 4-mercaptobenzene has been described. X-ray photoelectron spectroscopy results reveal that 4-mercaptobenzene was attached to the surface of MWNTs. Transmission electron microscope and X-ray diffraction analysis confirm that platinum nanoparticles were highly dispersed on the surface of MWNTs, and the average size of the platinum particle is 4.2 nm. The electrocatalytic properties of the Pt/MWNT composite electrode for methanol oxidation were investigated by cyclic voltammetry, and the results show that the fabricated composites exhibit high catalytic activity and good long-term stability. The study provides a feasible approach to fabricate Pt/MWNT composite electrode for direct methanol fuel cell.     

Preparation of cobalt hexacyanoferrate nanowires using carbon nanotubes as templates

A simple and convenient method for preparation of cobalt hexacyanoferrate (CoHCF) nanowires by electrodeposition was reported. Multiwall carbon nanotubes (MWNTs) were used as templates to fabricate CoHCF nanowires. MWNTs could affect the size of CoHCF nanoparticles and made them grow on the sidewalls of carbon nanotubes during the process of electrodeposition. Thus CoHCF nanowires could be obtained by this method. Field-emission scanning electron microscopy, UV-vis spectroscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy were used to characterize these nanowires. These results showed the CoHCF nanowires could be easily and successfully obtained and it gave a novel approach to prepare inorganic nanowires.     

Enhanced separation of Compound Xueshuantong capsule using functionalized carbon nanotubes with cationic surfactant solutions in MEEKC

A novel additive of multi‐walled carbon nanotubes (MWNTs) dispersed with cationic surfactants or mixed cationic/anionic surfactants was used for MEEKC separation of eight phenolic compounds, four glycosides, and one phenanthraquinone. In this context, several parameters affecting MEEKC separation were studied, including the dispersion agents of MWNTs, MWNTs content, oil type, SDS concentration, and the type and concentration of cosurfactant. Compared with conventional MEEKC, the addition of all types of MWNTs dispersions using single or mixed cationic surfactant solutions in running buffers was especially useful for improving the separation of solutes tested, as they influenced the partitioning between the oil droplets and aqueous phase due to the exceptional electrical properties and large surface areas of MWNTs. Use of cationic surfactant‐coated MWNTs (6.4 μg/mL) as the additive in a microemulsion buffer (0.5% octanol, 2.8% SDS, 5.8% isopropanol, and 5 mM borate buffer) yielded complete resolution of 13 analytes. The proposed method has been successfully applied for the detection and quantification of the studied compounds in a complex matrix sample (Compound Xueshuantong capsule).     

In situ PEI and formic acid directed formation of Pt NPs/MWNTs hybrid material with excellent electrocatalytic activity

A hybrid material based on Pt nanoparticles (Pt NPs) and multi-walled carbon nanotubes (MWNTs) was fabricated with the assistance of PEI and formic acid. The cationic polyelectrolyte PEI not only favored the homogenous dispersion of carbon nanotubes (CNTs) in water, but also provided sites for the adsorption of anionic ions PtCl₄²⁻ on the MWNTs’ sidewalls. Deposition of Pt NPs on the MWNTs’ sidewalls was realized by in situ chemical reduction of anionic ions PtCl₄²⁻ with formic acid. The hybrid material was characterized with TEM, XRD and XPS. Its excellent electrocatalytic activity towards both oxygen reduction in acid media and dopamine redox was also discussed.     

Temperature‐Responsive Polymer/Carbon Nanotube Hybrids: Smart Conductive Nanocomposite Films for Modulating the Bioelectrocatalysis of NADH

A temperature‐sensitive polymer/carbon nanotube interface with switchable bioelectrocatalytic capability was fabricated by self‐assembly of poly(N‐isopropylacrylamide)‐grafted multiwalled carbon nanotubes (MWNT‐g‐PNIPAm) onto the PNIPAm‐modified substrate. Electron microscopy and electrochemical measurements revealed that these fairly thick (>6 μm) and highly porous nanocomposite films exhibited high conductivity and electrocatalytic activity. The morphological transitions in both the tethered PNIPAm chains on a substrate and those polymers wrapping around the MWNT surface resulted in the opening, closing, or tuning of its permeability, and simultaneously an electron‐transfer process took place through the channels formed in the nanostructure in response to temperature change. By combining the good electron‐transfer and electrochemical catalysis capabilities, the large surface area, and good biocompatibility of MWNTs with the responsive features of PNIPAm, reversible temperature‐controlled bioelectrocatalysis of 1,4‐dihydro‐β‐nicotinamide adenine dinucleotide with improved sensitivity has been demonstrated by cyclic voltammetry and electrochemical impedance spectroscopy measurements. The mechanism behind this approach was studied by Raman spectroscopy, in situ attenuated total reflection FTIR spectroscopy, and contact angle measurements. The results also suggested that the synergetic or cooperative interactions of PNIPAm with MWNTs gave rise not only to an increase in surface wettability, but also to the enhancement of the interfacial thermoresponsive behavior. This bioelectrocatalytic “smart” system has potential applications in the design of biosensors and biofuel cells with externally controlled activity. Furthermore, this concept might be proposed for biomimetics, interfacial engineering, bioelectronic devices, and so forth.     

基于铁氰化镍的非标记型核酸适配体电化学传感器检测凝血酶

在玻碳电极（GCE）表面首先用增敏作用的多壁碳纳米管(MWCNTs)夹心于两层电沉积的铁氰化镍（NiHCF）氧化还原电化学探针之间,然后以金纳米粒子为固定核酸适配体的载体,构建了检测凝血酶的非标记型核酸适配体生物传感器。 利用扫描电子显微镜(SEM)对MWCNTs和NiHCF的形貌进行了表征。 利用电化学阻抗谱对传感器的组装过程进行了监测,用循环伏安法（CV）和差分脉冲伏安法（DPV）对传感器的电化学行为进行了研究。 以铁氰化镍为探针的传感器对凝血酶的检测在1.0 ng/L~1.0 mg/L范围内呈良好的线性关系,相关系数为0.998,检测限为0.2 ng/L(S/N=3)。