Hydrogen peroxide biosensor based on gold nanoparticles/thionine/gold nanoparticles/multi-walled carbon nanotubes-chitosans composite film-modified electrode

In this paper, an amperometric electrochemical biosensor for the detection of hydrogen peroxide (H₂O₂), based on gold nanoparticles (GNPs)/thionine (Thi)/GNPs/multi-walled carbon nanotubes (MWCNTs)-chitosans (Chits) composite film was developed. MWCNTs-Chits homogeneous composite was first dispersed in acetic acid solution and then the GNPs were in situ synthesized at the composite. The mixture was dripped on the glassy carbon electrode (GCE) and then the Thi was deposited by electropolymerization by Au-S or Au-N covalent bond effect and electrostatic adsorption effect as an electron transfer mediator. Finally, the mixture of GNPs and horseradish peroxidase (HRP) was assembled onto the modified electrode by covalent bond. The electrochemical behavior of the modified electrode was investigated by scanning electron microscope, cyclic voltammetry and chronoamperometry. This study introduces the in situ-synthesized GNPs on the other surface of the modified materials in H₂O₂ detection. The linear response range of the biosensor to H₂O₂ concentration was from 5 × 10⁻⁷ mol L⁻¹ to 1.5 × 10⁻³ mol L⁻¹ with a detection limit of 3.75 × 10⁻⁸ mol L⁻¹ (based on S/N = 3).     

Complex and new modification techniques of thiocholine detection electrodes with carbon nanotubes

A new and complex modification technique of glassy carbon electrode (GCE) with multi-walled carbon nanotubes (MWNTs) was developed. Firstly, MWNTs were electro-deposited on GCE at 1.70 V for 2 h. Secondly, by layer-by-layer (LBL) self-assembly technique, a functional membrane of {PDDA/MWNTs}_n were fabricated by alternative immersion in 1% PDDA solution and 1 mg L⁻¹ MWNTs dispersion either. As a result, the modified membrane with five {PDDA/MWNTs} bilayers have good sensitivity, stability, anti-fouling ability and catalytic activity for thiocholine (TCh) detection, the oxidation potential on the modified GCE was decreased almost by 50% while the peak current was increased almost by 100% compared with that on bare GCE. Meanwhile, it showed a low detection limit of less than 7.500 × 10⁻⁷ mol L⁻¹ TCh.     

An atomic force microscopy study of DNA hairpin probes monolabelled with gold nanoparticle: Grafting and hybridization on oxide thin films

First and original results are reported regarding the surface evolution of two kinds of oxide film after covalent grafting and hybridization of hairpin oligonucleotide probes. These hairpin probes were monolabelled with a 1.4 nm gold nanoparticle. One kind of oxide film was rough Sb doped SnO₂ oxide film and the other kind was smooth SiO₂ film. Same process of covalent grafting, involving a silanization step, was performed on both oxide surfaces. Atomic force microscopy (AFM) was used to study the evolution of each oxide surface after different steps of the process: functionalization, probe grafting and hybridization. In the case of rough SnO₂ films, a slight decrease of the roughness was observed after each step whereas in the case of smooth SiO₂ films, a maximum of roughness was obtained after probe grafting. Step height measurements of grafted probes could be performed on SiO₂ leading to an apparent thickness of around 3.7 ± 1.0 nm. After hybridization, on the granular surface of SnO₂, by coupling AFM with SEM FEG analyses, dispersed and well-resolved groups of gold nanoparticles linked to DNA duplexes could be observed. Their density varied from 6.6 ± 0.3 × 10¹⁰ to 2.3 ± 0.3 × 10¹¹ dots cm⁻². On the contrary, on smooth SiO₂ surface, the DNA duplexes behave like a dense carpet of globular structures with a density of 2.9 ± 0.5 × 10¹¹ globular structures cm⁻².     

Surface modification of indium tin oxide films by amino ion implantation for the attachment of multi-wall carbon nanotubes

Amino ion implantation was carried out at the energy of 80 keV with fluence of 5 × 10¹⁵ ions cm⁻² for indium tin oxide film (ITO) coated glass, and the existence of amino group on the ITO surface was verified by X-ray photoelectron spectroscopy analysis and Fourier transform infrared spectra. Scanning electron microscopy images show that multi-wall carbon nanotubes (MWCNTs) directly attached to the amino ion implanted ITO (NH₂/ITO) surface homogeneously and stably. The resulting MWCNTs-attached NH₂/ITO (MWCNTs/NH₂/ITO) substrate can be used as electrode material. Cyclic voltammetry results indicate that the MWCNTs/NH₂/ITO electrode shows excellent electrochemical properties and obvious electrocatalytic activity towards uric acid, thus this material is expected to have potential in electrochemical analysis and biosensors.     

Poly(3-methylthiophene)-based porous silicon substrates as a urea-sensitive electrode

Poly(3-methylthiophene) (P3MT)-based porous silicon (PS) substrates were fabricated and characterized by cyclic voltammetry, scanning electron microscopy, and auger electron spectroscopy. After doping urease (Urs) into the polymeric matrix, sensitivity and physicochemical properties of the P3MT-based PS substrate was investigated compared to planar silicon (PLS) and bulk Pt substrates. PS substrate was formed by electrochemical anodization in an etching solution composed of HF, H₂O, and ethanol. Subsequently, Ti and Pt thin-films were sputtered on the PS substrate. Effective working electrode area (A_eff) of the Pt-deposited PS substrate was determined from a redox reaction of Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ redox couple in which nearly reversible cyclic voltammograms were obtained. The i_p versus v^1/2 plots showed that A_eff of the PS-based Pt thin-film electrode was 1.62 times larger than that of the PLS-based electrode.Electropolymerization of P3MT on both types of electrodes were carried out by the anodic potential scanning under the given potential range. And then, urease molecules were doped to the P3MT film by the chronoamperometry. Direct electrochemistry of a Urs/P3MT/Pt/Ti/PS electrode in an acetonitrile solution containing 0.1 mol/L NaClO₄ was introduced compared to a P3MT/Pt/Ti/PS electrode at scan rates of 10 mV s⁻¹, 50 mV s⁻¹, and 100 mV s⁻¹.Amperometric sensitivity of the Urs/P3MT/Pt/Ti/PS electrode was ca. 1.67 μA mM⁻¹ per projected unit square centimeter, and that of the Urs/P3MT/Pt/Ti/PLS electrode was ca. 1.02 μA mM⁻¹ per projected unit square centimeter in a linear range of 1-100 mM urea concentrations. 1.6 times of sensitivity increase was coincident with the results from cyclic voltammetrc analysis.Surface morphology from scanning electron microscopy (SEM) images of Pt-deposited PS electrodes before and after the coating of Urs-doped P3MT films showed that pore diameter and depth were 2 μm and 10 μm, respectively. Multilayered-film structures composed of metals and organics for both electrodes were also confirmed by auger electron spectroscopy (AES) depth profiles.     

Stabilization of a very high-k crystalline ZrO2 phase by post deposition annealing of atomic layer deposited ZrO2/La2O3 dielectrics on germanium

The impact of the ZrO₂/La₂O₃ film thickness ratio and the post deposition annealing in the temperature range between 400 °C and 600 °C on the electrical properties of ultrathin ZrO₂/La₂O₃ high-k dielectrics grown by atomic layer deposition on (1 0 0) germanium is investigated. As-deposited stacks have a relative dielectric constant of 24 which is increased to a value of 35 after annealing at 500 °C due to the stabilization of tetragonal/cubic ZrO₂ phases. This effect depends on the absolute thickness of ZrO₂ within the dielectric stack and is limited due to possible interfacial reactions at the oxide/Ge interface. We show that adequate processing leads to very high-k dielectrics with EOT values below 1 nm, leakage current densities in the range of 0.01 A/cm², and interface trap densities in the range of 2-5 × 10¹² eV⁻¹ cm⁻².     

Selective MOCVD of titanium oxide and zirconium oxide thin films using single molecular precursors on Si(1 0 0) substrates

Titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films have been deposited on modified Si(1 0 0) substrates selectively by metal-organic chemical vapor deposition (MOCVD) method using new single molecular precursor of [M(OⁱPr)₂(tbaoac)₂] (M=Ti, Zr; tbaoac=tertiarybutyl-acetoacetate). For changing the characteristic of the Si(1 0 0) surface, micro-contact printing (μCP) method was adapted to make self-assembled monolayers (SAMs) using an octadecyltrichlorosilane (OTS) organic molecule which has -CH₃ terminal group. The single molecular precursors were prepared using metal (Ti, Zr) isopropoxide and tert-butylacetoacetate (tbaoacH) by modifying standard synthetic procedures. Selective depositions of TiO₂ and ZrO₂ were achieved in a home-built horizontal MOCVD reactor in the temperature range of 300-500 °C and deposition pressure of 1×10⁻³-3×10⁻² Torr. N₂ gas (5 sccm) was used as a carrier gas during film depositions. TiO₂ and ZrO₂ thin films were able to deposit on the hydrophilic area selectively. The difference in surface characteristics (hydrophobic/hydrophilic) between the OTS SAMs area and the SiO₂ or Si-OH layer on the Si(1 0 0) substrate led to the site-selectivity of oxide thin film growth.     

Electrochemical and surface characterisation of carbon-film-coated piezoelectric quartz crystals

The electrochemical properties of carbon films, of thickness between 200 and 500 nm, sputter-coated on gold- and platinum-coated 6 MHz piezoelectric quartz crystal oscillators, as new electrode materials have been investigated. Comparative studies under the same experimental conditions were performed on bulk electrodes. Cyclic voltammetry was carried out in 0.1 M KCl electrolyte solution, and kinetic parameters of the model redox systems Fe(CN)₆^3−/4− and [Ru(NH₃)₆]^3+/2+ as well as the electroactive area of the electrodes were obtained. Atomic force microscopy was used in order to examine the surface morphology of the films, and the properties of the carbon films and the electrode-solution interface were studied by electrochemical impedance spectroscopy. The results obtained demonstrate the feasibility of the preparation and development of nanometer thick carbon film modified quartz crystals. Such modified crystals should open up new opportunities for the investigation of electrode processes at carbon electrodes and for the application of electrochemical sensing associated with the EQCM.     

Electrochemical synthesis of Ag nanoparticles supported on glassy carbon electrode by means of p-isopropyl calix[6]arene matrix and its application for electrocatalytic reduction of H2O2

The silver nanoparticles were prepared on the glassy carbon (GC) electrode, modified with p-iso propyl calix[6]arene, by preconcentration of silver ions in open circuit potential and followed by electrochemical reduction of silver ions. The stepwise fabrication process of Ag nanoparticles was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. The prepared Ag nanoparticles were deposited with an average size of 70 nm and a homogeneous distribution on the surface of electrode. The observed results indicated that the presence of calixarene layer on the electrode surface can control the particle size and prevent the agglomeratione and electrochemical deposition is a promising technique for preparation of nanoparticles due to its easy-to-use procedure and low cost of implementation. Cyclic voltammetry experiments showed that Ag nanoparticles had a good catalytic ability for the reduction of hydrogen peroxide (H₂O₂). The effects of p-isopropyl calix[6]arene concentration, applied potential for reduction of Ag⁺, number of calixarene layers and pH value on the electrocatalytic ability of Ag nanoparticles were investigated. The present modified electrode exhibited a linear range from 5.0 × 10⁻⁵ to 6.5 × 10⁻³ M and a detection limit 2.7 × 10⁻⁵ M of H₂O₂ (S/N = 3) using amperometric method.     

Electrochemical properties of thin TiO2 electrode on Li1 + xAlxGe2 − x(PO4)3 solid electrolyte

A fabrication of all-solid-state thin-film rechargeable lithium ion batteries by sol-gel method is expected to achieve both the simplification and cost reduction for fabrication process. TiO₂ thin film electrode was prepared by PVP (polyvinylpyrrolidone) sol-gel method combined with spin-coating on Li_1 + xAl_xGe_2 − x(PO₄)₃ (LAGP) solid electrolyte which has wide electrochemical window. The thin film was composed of anatase TiO₂ that is the most active phase for Li insertion and extraction and contacted well with LAGP substrate. In the cyclic voltammogram, a redox couple was observed at 1.8 V vs. Li/Li⁺ assigned to Li insertion/extraction into/from anatase TiO₂, indicating that the thin film worked as electrode for lithium battery. The charge and discharge test in various charge and discharge rates revealed that the discharge process (delithiation) is thought to be faster than charge process (lithiation). It is attested that the sol-gel process, which derives both simplification and cost reduction for fabrication process, can be applied to thin film battery using LAGP solid electrolyte.     

Synthesis of spherical LiFePO4/C via Ni doping

Spherical LiFePO₄/C powders were synthesized by the conventional solid-state reaction method via Ni doping. Low-cost asphalt was used as both the reduction agent and the carbon source. An Ni-doped spherical LiFePO₄/C composite exhibited better electrochemical performances compared to an un-doped one. It presented an initial discharge capacity of 161 mAhg⁻¹ at 0.1 C rate (the theoretical capacity of LiFePO₄ with 5 wt% carbon is about 161 mAhg⁻¹). After 50 cycles at 0.5 C rate, its capacity remained 137 mAhg⁻¹ (100% of the initial capacity) compared to 115 mAhg⁻¹ (92% of the initial capacity) for an un-doped one. The electrochemical impedance spectroscopy analysis and cyclic voltammograms results revealed that Ni doping could decrease the resistance of LiFePO₄/C composite electrode drastically and improve its reversibility.     

Intercalation of lithium ions into bulk and powder highly oriented pyrolytic graphite

The electrochemical reactions of highly oriented pyrolytic graphite (HOPG) bulk and powder electrodes in 1 M LiPF₆ 1:1 EC/DMC solution were investigated and the results show that the intercalation reaction of lithium ion into HOPG electrode occurs only at the edge plane and SEI formation reaction on the basal plane is negligible in comparison with that on the edge plane. The active surface area of HOPG powder electrode could be deduced by comparing the peak area (consumed charge for SEI formation) at potential of 0.5 V on voltammograms with that of bulk HOPG edge electrode. The diffusion coefficients of lithium ion in HOPG bulk layers and in HOPG powder was for the first time measured by use of electrochemical impedance spectra and potential step chronamperameter methods. It was found that the diffusion coefficients of lithium in HOPG were in the range of 10⁻¹¹-10⁻¹² cm² s⁻¹ for the lithium-HOPG intercalation compounds at potentials from 0.2 (vs. Li/Li⁺) to 0.02 V, decreasing with the increase of lithium intercalation degree. A good agreement was obtained between the results from bulk and powder HOPG electrodes by electrochemical impedance spectra method.     

Metallo-organic decomposition derived (Ca, Sr)ZrO3 dielectric thin films on Pt coated Si substrate

Metallo-organic decomposition derived dielectric thin films of calcium zirconate doped with various concentrations of strontium ((Ca, Sr)ZrO₃) were prepared on Pt coated silicon substrate. Mainly in this paper, we present the investigations of their structural developments and present their electric and dielectric properties as well. The structural developments show that the CaZrO₃ film has amorphous structure with carbonate existing when annealed at 600 °C, while annealed at 650 °C and above, the carbonate is decomposed and those films crystallize into perovskite phase without preferred orientation. In addition, the prepared (Ca, Sr)ZrO₃ films with their Zr-O bonds affected by strontium doping are homogenous and stable as solid solutions in any concentration of strontium and all Bragg diffraction characteristics for the films shift downward with the increase in the concentration of strontium. Moreover, the electric properties show that the (Ca, Sr)ZrO₃ films have very low leakage current density and high breakdown strength; typically, the CaZrO₃ film annealed at 650 °C has the leakage current density approximately 9.5 × 10⁻⁸ A cm⁻² in the field strength of 2.6 MV cm⁻¹. Furthermore, the dielectric properties show that their dielectric constants are higher than 12.8 with very little dispersion in the frequency range from 100 Hz to 1 MHz and are independent of applied dc bias as well. The dielectric properties, in combination with the electric properties, make the materials promising candidates for high-voltage and high-reliability capacitor applications.     

NbTi0.5Ni0.5O4 as anode compound material for SOFCs

NbTi_0.5Ni_0.5O₄ (NTNO) has been prepared using solid state synthesis and investigated as a potential anode material. The oxide form of NTNO has single phase rutile-type structure with tetragonal (P42/mnm) space group. The reduced form is a composite of nano-scaled particles of metallic Ni and Nb_1.33Ti_0.67O₄ phase. Reduced NTNO showed high electronic conductivity up to 280 S.cm^− 1 at 900 °C in reducing atmosphere, but suffers from low CTE equal to 3.78 10^− 6 K^− 1. Studies of NTNO as anode material were carried out in a three electrode - electrochemical half cell configuration under pure humidified H₂ at 900 °C using a 2 mm thick zirconia electrolyte and without any additional current collector material. The results show a reasonable series resistance (R_s) equal to 2.7 Ωcm² (about 50% higher than for metallic gold layers) indicating a good current collection performance for a 10 μm layer of material. The polarization resistance (R_p) was equal to 33 Ωcm² and is attributed to a poor density of three phase boundaries (TPB) and shortage of oxide ion conduction in the anode layer. The results show the potential of NTNO as an anode material, especially after optimization of the microstructure towards the increase of TPB length.     

Electrochemical study and electrodeposition of copper in the hydrophobic tri-n-octylmethylammonium chloride ionic liquid media

The electrodeposition of metallic Copper in binary mixture ionic liquid/organic solvent (tri-n-octylmethylammonium chloride (TOMAC))/chloroform (CHCl₃) was investigated. The electrochemical behavior of Cu(II) in TOMAC/CHCl₃ at glassy carbon working electrode at room temperature was studied by cyclic voltammetry and spectroscopy impedance. The results from the cyclic voltammetry showed that the electrodeposition of metallic Cu in the binary mixture ionic liquid/organic solvent was an irreversible process and was controlled by the diffusion of Cu(II) on a glassy carbon working electrode. The average value of αn_α was found to be 0.23 at 25 °C and the diffusion coefficient (D₀) of Cu(II) was calculated to be 7.12 10^− 9 cm²/s at room temperature. The performance of TOMAC ionic liquid such as internal resistance has been investigated with electrochemical impedance spectroscopy (EIS). The scanning electron microscopy (SEM) micrographs was used to observe that the copper plating was moderately dense and contains fine crystallites with average sizes of about 1 μm at room temperature. Energy dispersive X-ray analysis (EDAX) profile showed that the obtained film was copper.     

Characterization of single-crystalline In2O3 films deposited on Y-stabilized ZrO2 (1 0 0) substrates by MOCVD

Epitaxial In₂O₃ films have been deposited on Y-stabilized ZrO₂ (YSZ) (1 0 0) substrates by metalorganic chemical vapor deposition (MOCVD). The films were deposited at different substrate temperatures (450-750 °C). The film deposited at 650 °C has the best crystalline quality, and observation of the interface area shows a clear cube-on-cube epitaxial relationship of In₂O₃(1 0 0)||YSZ(1 0 0) with In₂O₃[0 0 1]||YSZ[0 0 1]. The Hall mobility of the single-crystalline In₂O₃ film deposited at 650 °C is as high as 66.5 cm² V⁻¹ s⁻¹ with carrier concentration of 1.5 × 10¹⁹ cm⁻³ and resistivity of 6.3 × 10⁻³ Ω cm. The absolute average transmittance of the obtained films in the visible range exceeds 95%.     

Characterization of nanocrystalline SnO2 thin film fabricated by electrodeposition method for dye-sensitized solar cell application

Nanocrystalline SnO₂ thin film was prepared by cathodic electrodeposition-anodic oxidation and its structure was characterized by X-ray diffraction, SEM, UV-visible absorption and nitrogen adsorption-desorption by BET method. The obtained film has a surface area of 137.9 m²/g with grain sized of 24 nm. Thus the prepared SnO₂ thin film can be applied as an electrode in dye-sensitized solar cell. The SnO₂ electrode was successfully sensitized by Erythrosin dye and photoelectrochemical measurements indicate that the cell present short-circuit photocurrent (J_sc) of 760 μA/cm², fill factor (FF = 0.4), photovoltage (V_oc = 0.21 V) and overall conversion efficiency (η) of 0.06% under direct sun light illumination. The relatively low fill factor and photovoltage are attributed to the reduction of triodiode by conduction band electrons and intrinsic properties of SnO₂.     

Optical and electrochemical properties of ordered macroporous gold array on the ITO surface

The electrochemical and optical properties of transparent, two-dimensional macroporous gold film were investigated. Colloidal crystal templates were assembled onto indium-doped tin oxide (ITO) glass surface through vertical depositing method. Following gold electrodeposition, they were removed by dissolution with tetrahydrofuran (THF). The highly ordered macroporous gold array was achieved. It was characterized by scanning electron microscope (SEM) and ultraviolet visible (UV-vis) spectrophotometry. The optical transparency of the gold film was near 25% and fairly constant between 300 and 900 nm. The macroporous gold film electrode was mounted into a thin-layer transmission cell. The electrochemical response was evaluated by thin-layer cyclic voltammograms (CV) of the Fe (CN)₆³⁻/Fe (CN)₆⁴⁻ couple. Thin-layer cell exhibits good shape of waves and nearly symmetric cathodic and anodic waves. E⁰′ value and n of TMPD⁺/TMPD (TMPD is acronyms for N,N,N′,N′-tetramethyl-p-phenylenediamine, and TMPD⁺ is its mono-cation radical) couple were determined. Furthermore, results demonstrated electrolytic equilibrium was faster reached in macroporous gold film than ITO electrode.     

Annealing induced microstructural evolution of electrodeposited electrochromic tungsten oxide films

A significant influence of microstructure on the electrochromic and electrochemical performance characteristics of tungsten oxide (WO₃) films potentiostatically electrodeposited from a peroxopolytungstic acid (PPTA) sol has been evaluated as a function of annealing temperature. Powerful probes like X-ray diffractometry (XRD), transmission electron microscopy (TEM), UV-vis spectrophotometry, multiple step chronoamperometry and cyclic voltammetry have been employed for the thin film characterization. The as-deposited and the film annealed at 60 °C are composed of nanosized grains with a dominant amorphous phase, as well as open structure which ensues from a nanoporous matrix. This ensures a greater number of electroactive sites and a higher reaction area thereby manifesting in electrochromic responses superior to that of the films annealed at higher temperatures. The films annealed at temperatures ≥250 °C are characterized by a prominent triclinic crystalline structure and a hexagonal phase co-exists at temperatures ≥400 °C. The deleterious effect on the electrochromic properties of the film with annealing is ascribed to the loss of porosity, densification and the increasing crystallinity and grain size. Amongst all films under investigation, the film annealed at 60 °C exhibits a high transmission modulation (ΔT ∼ 68%) and coloration efficiency (η ∼ 77.6 cm² C⁻¹) at λ = 632.8 nm, charge storage capacity (Q_ins ∼ 21 mC cm⁻²), diffusion coefficient (6.08 × 10⁻¹⁰ cm² s⁻¹), fast color-bleach kinetics (t_c ∼ 275 s and t_b ∼ 12.5 s) and good electrochemical activity, as well as reversibility for the lithium insertion-extraction process upon cycling. The remarkable potential, which the film annealed at 60 °C has, for practical “smart window” applications has been demonstrated.