Immobilization of glucose oxidase and platinum on mesoporous silica nanoparticles for the fabrication of glucose biosensor

In this study, amino group modified mesoporous silica nanoparticles (MSN) were prepared and used to immobilize both platinum nanoparticles (PtNP) and glucose oxidase (GOx). The prepared MSN–PtNP demonstrated high stability and reactivity for catalyzing H₂O₂ electro-reduction, mainly due to the large amount of PtNP immobilized, the high surface area of these catalysts and the unique nanostructures formed through the synthetic route. Working at −0.2 V, the linear range in response to H₂O₂ by the prepared MSN–PtNP can be 5 × 10⁻⁷ to 6 × 10⁻² mol L⁻¹. After immobilizing GOx onto MSN–PtNP, the resulting MSN–PtNP–GOx was capable of interference-free determination of glucose with the linear range as wide as 1 × 10⁻⁶ to 2.6 × 10⁻² mol L⁻¹. Furthermore, the fabricated glucose biosensor can offer significant advantages compared with its conventional counterparts, typically like the high sensitivity, good reproducibility and stability, and rapid response ability as well. The fabricated glucose biosensor demonstrated its potential in clinical applications, so as to enable the determination of glucose in real serum samples.     

Unusual electrochemical response of ZnO nanowires-decorated multiwalled carbon nanotubes

A novel type of ZnO nanowires-modified multiwalled carbon nanotubes (MWCNTs) nanocomposite (ZnO-NWs/MWCNTs) has been prepared by a hydrothermal process. The ZnO-NWs/MWCNTs nanocomposite has a uniform surface distribution and large coverage of ZnO nanowires onto MWCNTs with 3D configuration, which was characterized by scanning electron microscopy. Cyclic voltammetry and electrochemical impedance spectroscopy methods were applied to investigate the electrochemical properties of ZnO-NWs/MWCNTs nanocomposite. Surprisingly, unlike the conventional n-type semiconducting ZnO nanowires grown on Ta substrate, the ZnO-NWs/MWCNTs nanocomposite exhibits excellent electron transfer capability and gives a pair of well-defined symmetric redox peaks towards ferricyanide probe. What's more, the ZnO-NWs/MWCNTs nanocomposite shows remarkable electrocatalytic activity (current response increased 4 folds at 0.3 V) towards H₂O₂ by comparing with bare MWCNTs. The ZnO-NWs/MWCNTs nanocomposite could find applications in novel biosensors and other electronic devices.     

In situ growth of copper nanoparticles on multiwalled carbon nanotubes and their application as non-enzymatic glucose sensor materials

Cu-nanoparticles were coated on the sidewall of multiwalled carbon nanotubes (MWCNTs) by a facile and effective in situ approach via the template of a polyelectrolyte (polyethylenimine or poly(sodium 4-styrene sulfonate)) noncovalently functionalized on MWCNTs. Extensive characterizations of the fabricated nanocomposites have been studied using X-ray diffraction, transmission electron microscopy, selected area electron diffraction, X-ray photoelectron spectroscopy, thermal gravimetric analysis and inductively coupled plasma. The results demonstrate that Cu-nanoparticles were well distributed on the surface of MWCNTs. The nanocomposites can be easily modified on the glassy carbon electrodes due to the presence of polyelectrolyte. The electrocatalytic activity of the modified electrodes towards glucose oxidation was investigated by cyclic voltammetry and chronoamperometry. The nanocomposites showed good non-enzymatic electrocatalytic responses to glucose in alkaline media, and can be used for the development of enzyme-free glucose sensors.     

Selectively attaching Pt-nano-clusters to the open ends and defect sites on carbon nanotubes for electrochemical catalysis

Pt nano-clusters (nano-Pt) have been selectively attached to the open ends and defect sites of mildly oxidized multi-wall carbon nanotubes (MWCNTs) on a glassy carbon electrode (GCE) by a cyclic voltammetry (CV) electrodeposition method. The nano-Pt functionalized MWCNTs were characterized by XPS, XRD, FE-SEM and electrochemical techniques. The catalytic activity of the nano-Pt functionalized MWCNTs were tested by an oxygen reduction reaction (ORR) and a methanol oxidation reaction (MOR). Taking the ORR as an example, we found that the electrocatalytic activity of the nano-Pt functionalized MWCNTs can be well tuned by varying the cycle number and the PtCl₆²⁻ concentration of the deposition conditions. The average size of the nano-Pt was 123 nm, and it was constituted of nano-crystallite of an average size of 10.8 nm. Though the large nano-Pt particles (100-150 nm) were only attached on the open ends and defect sites of the MWCNTs, which were very different from the highly dispersed small Pt nanoparticles (<10 nm) on carbon nanotubes reported by other research groups. In our method, excellent electrocatalytic activity of the nano-Pt functionalized MWCNTs for ORR and MOR can be obtained. The mechanisms for nano-Pt deposition are proposed.     

Preparation of hollow platinum nanospheres/carbon nanotubes nanohybrids and their improved stability for electro-oxidation of methanol

We report a facile method for the synthesis of hollow platinum nanospheres/carbon nanotubes nanohybrids (CNTs-G-PtHNs). Silver nanoparticles were used as sacrificial templates and uniformly deposited on the functionalized carbon nanotubes (CNTs). By galvanic replacement reaction between CNTs-supported silver and PtCl₆²⁻, well-dispersed hollow platinum nanospheres (PtHNs) were “grown” on CNTs. The morphology and electrochemical properties of the CNTs-G-PtHNs nanohybrids have been investigated by transmission electron microscopy and cyclic voltammetry, respectively. PtHNs in the CNTs-G-PtHNs nanohybrids have an average diameter of about 8 nm and the CNTs-G-PtHNs nanohybrids have higher electrochemical surface area and better electrocatalytic performance towards methanol oxidation than CNTs-A-PtHNs nanohybrids which were obtained by adsorbing the pre-synthesized PtHNs onto CNTs. Most importantly, the long-term stability of CNTs-G-PtHNs nanohybrids for methanol electro-oxidation has obviously improved compared with that of the CNTs-A-PtHNs nanohybrids.     

Three-dimensional heterostructure of metallic nanoparticles and carbon nanotubes as potential nanofiller

ABSTRACT: The effect of the dimensionality of metallic nanoparticle-and carbon nanotube-based fillers on the mechanical properties of an acrylonitrile butadiene styrene (ABS) polymer matrix was examined. ABS composite films, reinforced with low dimensional metallic nanoparticles (MNPs, 0-D) and carbon nanotubes (CNTs, 1-D) as nanofillers, were fabricated by a combination of wet phase inversion and hot pressing. The tensile strength and elongation of the ABS composite were increased by 39% and 6%, respectively, by adding a mixture of MNPs and CNTs with a total concentration of 2 wt%. However, the tensile strength and elongation of the ABS composite were found to be significantly increased by 62% and 55%, respectively, upon addition of 3-D heterostructures with a total concentration of 2 wt%. The 3-D heterostructures were composed of multiple CNTs grown radially on the surface of MNP cores, resembling a sea urchin. The mechanical properties of the ABS/3-D heterostructured nanofiller composite films were much improved compared to those of an ABS/mixture of 0-D and 1-D nanofillers composite films at various filler concentrations. This suggests that the 3-D heterostructure of the MNPs and CNTs plays a key role as a strong reinforcing agent in supporting the polymer matrix and simultaneously serves as a discrete force-transfer medium to transfer the loaded tension throughout the polymer matrix.     

Synthesis of Pt nanocatalyst with micelle-encapsulated multi-walled carbon nanotubes as support for proton exchange membrane fuel cells

Micelle-encapsulated multi-walled carbon nanotubes (MWCNTs) with sodium dodecyl sulfate (SDS) were used as catalyst support to deposit platinum nanoparticles. High resolution transmission electron microscopy (HRTEM) images reveal the crystalline nature of Pt nanoparticles with a diameter of ∼4 nm on the surface of MWCNTs. A single proton exchange membrane fuel cell (PEMFC) with total catalyst loading of 0.2 mg Pt cm⁻² (anode 0.1 and cathode 0.1 mg Pt cm⁻², respectively) has been evaluated at 80 °C with H₂ and O₂ gases using Nafion-212 electrolyte. Pt/MWCNTs synthesized by using modified SDS-MWCNTs with high temperature treatment (250 °C) showed a peak power density of 950 mW cm⁻². Accelerated durability evaluation was carried out by conducting 1500 potential cycles between 0.1 and 1.2 V with 50 mV s⁻¹ scan rate, H₂/N₂ at 80 °C. The membrane electrode assembly (MEA) with Pt/MWCNTs showed superior performance stability with a power density degradation of only ∼30% compared to commercial Pt/C (70%) after potential cycles.     

Surfactant functionalization of carbon nanotubes (CNTs) for layer-by-layer assembling of CNT multi-layer films and fabrication of gold nanoparticle/CNT nanohybrid

This paper describes a new strategy through noncovalent functionalization of multi-walled carbon nanotube (MWNTs) with supramolecular surfactant for layer-by-layer (LbL) assembling MWNT multi-layer film onto indium tin oxide (ITO)-coated glass plate and for attaching gold nanoparticles (GNPs) onto the MWNTs to fabricate GNP/MWNT nanohybrid. Surfactant (i.e., sodium dodecyl sulfate, SDS) can interact with the MWNTs through hydrophobic interaction between the hydrophobic chain of SDS and the sidewall of the MWNTs. Such an interaction essentially leads to noncovalent adsorption of SDS onto the MWNTs, resulting in an enhanced solubilization of the MWNTs in distilled water and providing some negative charges on the tube surface. Both properties make it possible to assemble MWNT multi-layer films onto the ITO plate through an alternative adsorption of oppositely charged SDS-functionalized MWNTs and polyelectrolyte [i.e., poly(diallyldimethylammonium chloride), PDDA] as revealed by scanning electron microscopy (SEM), ultraviolet-visible-near-infrared spectroscopy (UV-vis-NIR), quartz crystal microbalance (QCM), and cyclic voltammetry (CV). The same properties of the SDS-functionalized MWNTs are demonstrated to be useful for mediating the attachment of GNPs onto the tube surfaces to form GNP/MWNT nanohybrid as verified with transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemistry.     

Electrodeposition of gold–platinum alloy nanoparticles on carbon nanotubes as electrochemical sensing interface for sensitive detection of tumor marker

A novel electrochemical sensing interface, electrodeposition of gold–platinum alloy nanoparticles (Au–PtNPs) on carbon nanotubes, was proposed and used to fabricate a label-free amperometric immunosensor. On the one hand, the multiwalled carbon nanotubes (MWCNTs) could increase active area of the electrode and enhance the electron transfer ability between the electrode and redox probe; on the other hand, the Au–PtNPs not only could be used to assemble biomolecules with bioactivity kept well, but also could further facilitate the shuttle of electrons. In the meanwhile, horseradish peroxidase (HRP) instead of bovine serum albumin (BSA) was employed to block the possible remaining active sites and avoid the nonspecific adsorption. With the synergetic catalysis effect of Au–PtNPs and HRP towards the reduction of hydrogen peroxide (H₂O₂), the signal could be amplified and the sensitivity could be enhanced. Using alpha-fetoprotein (AFP) as model analyte, the fabricated immunosensor exhibited two wide linear ranges in the concentration ranges of 0.5–20 ng mL⁻¹ and 20–200 ng mL⁻¹ with a detection limit of 0.17 ng mL⁻¹ at a signal-to-noise of 3. Moreover, the immunosensor exhibited good selectivity, stability and reproducibility. The developed protocol could be easily extended to other protein detection and provided a promising potential in clinical diagnosis application.     

Seed-mediated electrochemical growth of gold nanostructures on indium tin oxide thin films

Two-dimensional gold nanostructures (Au NSs) were fabricated on amine-terminated indium tin oxide (ITO) thin films using constant potential electrolysis. By controlling the deposition time and by choosing the appropriate ITO surface, Au NSs with different shapes were generated. When Au NSs were formed directly on aminosilane-modified ITO, the surface roughness of the interface was largely enhanced. Modification of such Au NSs with n-tetradecanethiol resulted in a highly hydrophobic interface with a water contact angle of 144°. Aminosilane-modified ITO films further modified with colloidal Au seeds before electrochemical Au NSs formation demonstrated interesting optical properties. Depending on the deposition time, surface colors ranging from pale pink to beatgold-like were observed. The optical properties and the chemical stability of the interfaces were characterized using UV-vis absorption spectroscopy. Well-defined localized surface plasmon resonance signals were recorded on Au-seeded interfaces with λ_max = 675 ± 2 nm (deposition time 180 s). The prepared interfaces exhibited long-term stability in various solvents and responded linearly to changes in the corresponding refractive indices.     

Effects of fullerenes and single-wall carbon nanotubes on murine and human macrophages

The discovery in 1985 of C-fullerenes, a novel carbon allotrope with a polygonal structure made up solely by 60 carbon atoms, and in 1991 of C-nanotubes, thin carbon filaments (1-3 μm in length and 0.001 μm in diameter) with extraordinary mechanical properties, opened a wide field of activity in carbon research. While toxicity and biocompatibility of C-fullerenes have been widely investigated, literature data concerning the biological properties and biotoxicity of C-nanotubes are poor and contradictory. Here we test the ability of highly purified C-Single-Walled-Nanotubes (SWNTs) and C-fullerenes to elicit an inflammatory response by murine and human macrophage cells in vitro. In order to determine the potential of these C-derivatives as biological inducers of inflammatory reactions we evaluate the ability of C-single-walled nanotubes and C-fullerenes to induce the release of NO by murine macrophages cells, to stimulate the phagocytic activity of human macrophage cells and to be cytotoxic against these cells. We show that SWNTs-C-nanotubes, when highly purified, as well as C-fullerenes, do not stimulate the release of NO by murine macrophage cells in culture, their uptake by human macrophage cells is very low, and they possess a very low toxicity against human macrophage cells.     

Paper-structured fiber composites impregnated with platinum nanoparticles synthesized on a carbon fiber matrix for catalytic reduction of nitrogen oxides

Platinum nanoparticles (PtNPs) were synthesized on surface-activated carbon fibers with high thermal conductivity, and paper-structured composites were fabricated by a papermaking technique, using the PtNPs-supported carbon fibers and ceramic fibers as matrix materials. As-prepared materials, denoted paper-structured PtNPs catalyst, possessed a unique porous microstructure derived from entangled inorganic fiber networks on which PtNPs were well dispersed. In catalytic reduction of nitrogen oxides (NO_X) in the presence of methane (CH₄), both of which are model exhaust gas components of combustion engines, paper-structured PtNPs catalyst demonstrated excellent NO_X and CH₄ removal efficiency and rapid thermal responsiveness by comparison with the PtNPs-supported carbon fibers, commercial Pt catalyst powders and a monolithic Pt-loaded honeycomb. These features of the new catalyst material are thought to arise from synergistic effects of the highly active PtNPs in association with the unique paper-like microstructure, in promoting effective transfer of heat and reactants to the active sites of the Pt nanocatalysts. The paper-structured PtNPs catalyst with paper-like practical utility is expected to be a promising catalytic material for efficient NO_X gas purification.     

Synthesis of Pt and Pd nanosheaths on multi-walled carbon nanotubes as potential electrocatalysts of low temperature fuel cells

Pt and Pd nanosheaths are successfully synthesized on multi-walled carbon nanotubes (MWCNTs) using the non-covalent poly(diallyldimethylammonium chloride) (PDDA) functionalization and seed-mediated growth methods. In this method, negatively charged Pt or Pd metal precursors are self-assembled with positively charged PDDA-functionalized MWCNTs, forming uniformly distributed Pt or Pd nanoseeds on MWCNTs supports. The contiguous and highly porous Pt and Pd nanosheath structured catalysts are then formed by the seed-mediated growth in corresponding metal precursors using ascorbic acid as the reducing agent. The essential role of uniformly dispersed Pt and Pd nanoseeds on PDDA-MWCNTs is demonstrated. The results indicate that both Pt and Pd nanosheaths show an enhanced catalytic activity for the methanol and formic acid oxidation reaction in acid solution, respectively, as compared with conventional Pt/C and Pd/C catalysts. The enhanced activities are most likely due to the reduced oxophilicity, which results in a weakened chemisorption energy with oxygen-containing species such as CO_ad, and the increased reactive sites due to the large number of grain boundaries of the Pt and Pd nanosheath structured electrocatalysts.     

Preparation and electrochemical properties of gold nanoparticles containing carbon nanotubes-polyelectrolyte multilayer thin films

Multi-walled carbon nanotubes (MWCNT)/polyelectrolyte (PE) hybrid thin films were fabricated by alternatively depositing negatively charged MWCNT and positively charged (diallyldimethylammonium chloride) (PDDA) via layer-by-layer (LbL) assembly technique. The stepwise growth of the multilayer films of MWCNT and PDDA was characterized by UV–vis spectroscopy. Scanning electron microscopy (SEM) images indicated that the MWCNT were uniformly embedded in the film to form a network and the coverage density of MWCNT increased with layer number. Au nanoparticles (NPs) could be further adsorbed onto the film to form PE/MWCNT/Au NPs composite films. The electron transfer behaviour of multilayer films with different compositions were studied by cyclic voltammetry using [Fe(CN)₆]^3−/4− as an electrochemical probe. The results indicated that the incorporation of MWCNT and Au NPs not only greatly improved the electronic conductivity of pure polyelectrolyte films, but also provided excellent electrocatalytic activity towards the oxidation of nitric oxide (NO).     

Nanocomposite electrodes based on pre-synthesized organically capped platinum nanoparticles and carbon nanotubes. Part I: Tuneable low platinum loadings, specific H upd feature and evidence for oxygen reduction

A bottom-up approach is used here to combine carbon nanotubes synthesized by CVD and organically capped platinum nanoparticles electrocatalyst exhibiting a direct electrochemical activity towards oxygen reduction. Both nano-objects are handled in liquid suspension and are associated together in a controlled way. The nanocomposite liquid dispersions can be precisely controlled in terms of platinum nanoparticles to carbon nanotubes weight ratios (NP/NT) which correspond to different coverages of nanotubes by nanoparticles. Electrodes with low to ultra-low platinum loadings can then be prepared on porous fuel cell carbon supports by filtration. The direct electrochemical activity towards aqueous oxygen reduction reaction (ORR) of electrodes with platinum loadings ranging from about 1 to 60 μg/cm² is reported without any activation step in order to keep the features of the nanoparticles intact. Before that, we studied the responses obtained when impregnating our hydrophobic electrodes by a voltamperometric gas consumption procedure. These responses are also dependent of the composition of our electrodes. Whereas our results are of particular interest with respect to the optimization of platinum loading in fuel cell electrodes, the specific behaviour of these capped platinum nanoparticles towards proton adsorption-desorption reveals the difficulty to determine reliable active surface area with related regard to the platinum loading and point to the necessity to determine other characteristic parameters for the electrodes.     

Investigation of the supercritical deposition of platinum nanoparticles into carbon aerogels

The preparation of platinum/carbon aerogel (CA) nanocomposites by the supercritical deposition method was investigated. CAs were impregnated with dimethyl(cyclooctadiene)platinum, CODPtMe₂, from supercritical carbon dioxide (scCO₂) solutions and the resulting CODPtMe₂/CA composites were converted to Pt/CA composites. The adsorption isotherms of CODPtMe₂ on CAs were measured and could be represented by the Langmuir model. The results indicated a strong interaction between CODPtMe₂ molecules and the CA surface and that a substantial fraction of the surface of the CAs was covered with CODPtMe₂ molecules at relatively low concentrations. Four different reduction methods were used to convert the CODPtMe₂ impregnated CAs which were: (1) thermal reduction at atmospheric pressure in an inert atmosphere; (2) thermal reduction in scCO₂; (3) chemical reduction in scCO₂ with hydrogen; and (4) chemical reduction at atmospheric pressure with hydrogen. Method 1 gave highly dispersed Pt nanoparticles (1–3 nm) at loadings ranging from 10 to 40 wt.%. The use of hydrogen in Method 4 increased the average particle size by a factor of 2 over Method 1 at the same Pt loading, but the particles still had a narrow unimodal size distribution. When the thermal reduction was carried out in scCO₂, loadings as high as 73% could be obtained. Method 3 generated a composite having a disordered columnar Pt coating and equiaxed particles ≈1 μm in diameter on the external surface of the monolith and dispersed Pt nanoparticles in the interior. The analysis of the reaction products in scCO₂ indicated an autocatalytic reaction. Increasing the Pt loading was found to decrease the surface area of the CA, primarily through blockage of the micropores.     

Multifunctional polymer foams with carbon nanoparticles

Increasingly demanding industry requirements in terms of developing polymer-based components with higher specific properties have recently aroused a great interest around the possibility of combining density reduction through foaming with the addition of small amounts of functional nanosized particles. Particular interest has been given to the creation of lightweight conductive polymers by incorporating conductive carbon-based nanoparticles, related to processing improvements in attaining homogeneous nanoparticle dispersion and distribution throughout the polymer as well as new processes that enable a higher control and throughput of highly pure carbon nanoparticles, which could overcome some of the common problems of conductive polymers, such as high cost and poor mechanical properties. This review article considers the use of carbon nanoparticles in polymer foams, initially focusing on the important aspects of foam preparation, the main results found in the literature about conductive polymer composites containing carbon nanoparticles, as well as the main polymer foaming processes and types of foams. The main section is dedicated to the properties of multifunctional polymer foams with carbon nanoparticles, with special focus being given to the electrical and transport properties of these materials.     

Enhancement of oxygen reduction by incorporation of heteropolytungstate into the electrocatalytic ink of carbon supported platinum nanoparticles

Nafion stabilized inks of Vulcan XC-72 supported platinum (20 wt.%) nanoparticles (Pt/XC-72) were utilized to produce electrocatalytic films on glassy carbon. The catalysts were modified (activated) with phosphododecatungstic acid H₃PW₁₂O₄₀ (PW₁₂). Comparison was made to bare (PW₁₂-free) electrocatalytic films. Electroreduction of dioxygen was studied at 25 °C in 0.5 mol dm⁻³ H₂SO₄ electrolyte using rotating disk voltammetry. For the same loading of platinum (≈95 μg cm⁻²) and for the approximately identical distribution of the catalyst, the reduction of oxygen at a glassy carbon electrode modified with the ink containing PW₁₂ proceeded at ca. 30-60 mV more positive potential (depending on the PW₁₂ content), and the system was characterized by a higher kinetic parameter (rate of heterogeneous electron transfer), when compared to the PW₁₂-free electrocatalyst. Gas diffusion electrodes with Pt/XC-72 supported on carbon paper (Pt loading 1 mg cm⁻²) were also tested. Under the same experimental conditions, while the exchange current density and the total resistance contribution to polarization components, computed from the galvanostatic polarization curves were found to be clearly higher and lower, respectively, for the ink modified with PW₁₂ relative to the unmodified system. The results demonstrate that addition of heteropolytungstatic acid (together with Nafion) enhances the electrocatalytic activity of platinum towards reduction of oxygen.     

Nanocomposite electrodes based on pre-synthesized organically capped platinum nanoparticles and carbon nanotubes. Part II: Determination of diffusion area for oxygen reduction reflects platinum accessibility

In this paper we report the determination of the diffusion area for oxygen reduction in porous electrode structure having a controlled platinum loading and based on capped platinum electrocatalysts and carbon nanotubes. Such a parameter is expected to be higher than the macroscopic geometrical area of the active porous layer. The oxygen diffusion area is determined by cyclic voltammetry after impregnation of the electrode structure by the electrolyte, and using the equations available for peak potential and peak current as a function of scan speed for irreversible redox couple. First it is found first that the oxygen diffusion area is dependent on the total amount of platinum in the electrode. Second, for a given platinum loading, the diffusion area is higher when the mass ratio of platinum to carbon nanotube decreases. This point indicates that the accessibility of platinum capped electrocatalyst is better in such cases. It is thus concluded that the oxygen diffusion area determination in porous electrode structures may be used to characterize the accessibility of the capped electrocatalysts for oxygen reduction. Even if this area is different in nature from the one calculated by Hydrogen Underpotential Deposition, we believe that its determination might be of interest for the characterization of porous electrodes structures in which the electrocatalyst is combined with a finely divided carbon support.