Structural and optical studies of CdS and CdS:Ag nano needles prepared by a SILAR method

Nano-crystalline CdS and Ag-doped CdS films are deposited on glass substrate by a SILAR technique at room temperature with cationic precursors of cadmium nitrate and silver nitrate, and anionic precursor of sodium sulfide with different S:Cd ratio in starting solutions. In order to fabricate samples, substrates were taken in the solutions with determined duration and immersion cycles. To investigate the structural and morphological characteristics of the samples XRD analysis and SEM were used. The X-ray diffraction patterns show that the CdS samples have cubic crystal structure with preferential orientation along the (111) plane and CdS:Ag samples have hexagonal crystal structure with preferential orientation along the (002) plane. Also the peak intensity of XRD patterns of CdS increases with increasing the number of immersion cycles. Optical reflection of the layers is measured with a spectrophotometer and their optical absorption coefficient and band gaps are calculated. The band gap energy of Ag-doped samples decreases respect to CdS samples. It seems that silver doping creates intermediate levels in the energy gap and this causes decreasing of energy gap. Making samples with different S:Cd ratio demonstrates that the sample with 3:1 ratio has highest peak intensity in the XRD pattern and best stoichiometry. It is also observed that with increasing S:Cd ratio, the band gap energy of the samples decreases.     

金纳米粒子修饰玻碳电极的电化学行为研究

利用层层自组装技术,通过有机偶联层胱胺将金纳米粒子修饰在玻碳电极上,得到金纳米粒子/胱胺/玻碳电极,并通过循环伏安法和电化学阻抗谱对修饰电极的电化学行为进行研究,结果表明该修饰电极具有优于裸玻碳电极的良好的电化学性能,可用于进一步的应用。     

Gold nanoparticle/carbon nanotube hybrids as an enhanced material for sensitive amperometric determination of tryptophan

In this work, a highly sensitive electrochemical sensor for the determination of tryptophan (Trp) was fabricate by electrodeposition of gold nanoparticles (AuNPs) onto carbon nanotube (CNT) films pre-cast on a glassy carbon electrode (GCE), forming an AuNP-CNT composite-modified GCE (AuNP-CNT/GCE). Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used for the surface analysis of the electrode. The results indicate that the hybrid nanomaterials induced a substantial decrease in the overpotential of the Trp oxidation reaction and exhibited a remarkable synergistic effect on the electrocatalytic activity toward the oxidation of Trp. In phosphate buffer solution (pH 7.4), the modified electrode showed excellent analytical performance for the amperometric determination of Trp. The peak currents possess a linear relationship with the concentration of Trp in the range of 30 nM to 2.5 μM, and the detection limit is 10 nM (S/N = 3). In addition, the modified electrode was used to determine Trp concentration in pharmaceutical samples with satisfactory results.     

Bi-component MnO/ZnO hollow microspheres embedded in reduced graphene oxide as electrode materials for enhanced lithium storage

Novel composite of bi-component MnO/ZnO (denoted as MZO) hollow microspheres embedded in reduced graphene oxide (RGO) as a high performance electrode material for Lithium ion batteries (LIBs) is prepared via one-pot hydrothermal method and subsequent annealing. The structures and morphologies of as-prepared hybrid materials are characterized by X-ray diffraction, scanning electron microscopy, Raman spectra, FTIR and transmission electron microscopy. The results reveal that the MZO hollow microspheres with nanometer-sized building blocks are well dispersed in the RGO support. The electrochemical tests show that the hybrid material has a reversible capacity of 660 mAh/g at a current density of 100 mA/g with a coulombic efficiency of 98% after 100 cycles. Besides, a specific capacity of about 207 mAh/g is retained even at a current density as high as 1600 mA/g, exhibiting high reversibility and good capacity retention. Our results suggest that the composite of bi-component MZO hollow microspheres embedded in RGO will be promising electrode materials for low-cost, environmentally friendly and high-performance LIBs.     

Decoration of multiwall nanotubes with cadmium sulfide nanoparticles

This study focuses on in situ synthesis of CdS nanoparticles on the surfaces of multiwalled carbon nanotubes. By chemical reaction of cadmium chloride and thioacetamide in the solution with carbon nanotubes, which were pretreated by air oxidization and acid modification, cadmium sulfide nanoparticles densely supported on carbon nanotubes with 10 nm size and homogeneous distribution were prepared. The composite material with the composite structure of CdS decorating the nanotube surfaces was characterized using scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction and electron diffraction pattern. The CdS nanoparticles are of cubic crystal structure, show good adhesion to the nanotubes. This method can be extended to prepare other inorganic nanoparticle-carbon nanotube composites.     

Electrochemically fabricated polyaniline nanowire-modified electrode for voltammetric detection of DNA hybridization

A novel and sensitive electrochemical DNA biosensor based on electrochemically fabricated polyaniline nanowire and methylene blue for DNA hybridization detection is presented. Nanowires of conducting polymers were directly synthesized through a three-step electrochemical deposition procedure in an aniline-containing electrolyte solution, by using the glassy carbon electrode (GCE) as the working electrode. The morphology of the polyaniline films was examined using a field emission scanning electron microscope (SEM). The diameters of the nanowires range from 80 to 100 nm. The polyaniline nanowires-coated electrode exhibited very good electrochemical conductivity. Oligonucleotides with phosphate groups at the 5′ end were covalently linked onto the amino groups of polyaniline nanowires on the electrode. The hybridization events were monitored with differential pulse voltammetry (DPV) measurement using methylene blue (MB) as an indicator. The approach described here can effectively discriminate complementary from non-complementary DNA sequence, with a detection limit of 1.0 × 10⁻¹² mol l⁻¹ of complementary target, suggesting that the polyaniline nanowires hold great promises for sensitive electrochemical biosensor applications.     

The effect of electrolytic oxidation on the electrochemical properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWNTs) were electrochemically oxidized by a constant-potential electrolysis method and then investigated in detail using scanning electron microscope, transmission electron microscope, FT-IR, electrical impedance spectroscopy, and cyclic voltammetry. The FT-IR spectra showed that the amount of hydroxyl generated on the surface of MWNTs increased with increasing the electrochemical oxidation time of MWNTs. The CV results, being conducted in nitrobenzene solution, showed that the nitrobenzene reduction current increased with the increase in oxidation time of the MWNTs within the first 60 min of electrolysis. An electrical equivalent circuit model for electrical impedance spectroscopy was further established to analyze the surface capacitance and resistance of the MWNTs, and the model results showed that the capacitance of the oxidized MWNTs increased greatly while the charge transfer resistance decreased, suggesting electrochemical oxidized MWNTs modified pyrolytic carbon electrode being an effective electrochemical sensor for nitrobenzene determination.     

Simultaneous voltammetric determination of tramadol and acetaminophen using carbon nanoparticles modified glassy carbon electrode

A sensitive and selective electrochemical sensor was fabricated via the drop-casting of carbon nanoparticles (CNPs) suspension onto a glassy carbon electrode (GCE). The application of this sensor was investigated in simultaneous determination of acetaminophen (ACE) and tramadol (TRA) drugs in pharmaceutical dosage form and ACE determination in human plasma. In order to study the electrochemical behaviors of the drugs, cyclic and differential pulse voltammetric studies of ACE and TRA were carried out at the surfaces of the modified GCE (MGCE) and the bare GCE. The dependence of peak currents and potentials on pH, concentration and the potential scan rate were investigated for these compounds at the surface of MGCE. Atomic force microscopy (AFM) was used for the characterization of the film modifier and its morphology on the surface of GCE. The results of the electrochemical investigations showed that CNPs, via a thin layer model based on the diffusion within a porous layer, enhanced the electroactive surface area and caused a remarkable increase in the peak currents. The thin layer of the modifier showed a catalytic effect and accelerated the rate of the electron transfer process. Application of the MGCE resulted in a sensitivity enhancement and a considerable decrease in the anodic overpotential, leading to negative shifts in peak potentials. An optimum electrochemical response was obtained for the sensor in the buffered solution of pH 7.0 and using 2 μL CNPs suspension cast on the surface of GCE. Using differential pulse voltammetry, the prepared sensor showed good sensitivity and selectivity for the determination of ACE and TRA in wide linear ranges of 0.1-100 and 10-1000 μM, respectively. The resulted detection limits for ACE and TRA was 0.05 and 1 μM, respectively. The CNPs modified GCE was successfully applied for ACE and TRA determinations in pharmaceutical dosage forms and also for the determination of ACE in human plasma.     

Poly(indole-6-carboxylic acid) and tetracyanoquinodimethane-modified electrode for selective oxidation of dopamine

Poly(indole-6-carboxylic acid) (PICA) was synthesized electrochemically over glassy carbon electrode (GCE) through potentiodynamic mode of polymerization. The resulting polymer was soluble in Tris-HCl buffer (pH 7.0). The processable polymer was cast over desired electrode surface along with organic redox mediator tetracyanoquinodimethane (TCNQ) as an electron transfer relay using Nafion^®. Nafion^® was used to solubilize TCNQ as well as to introduce permselectivity to the blend of polymer and TCNQ. The above blend was cast over GCE and characterized by cyclic voltammetry followed by its application in electrochemical sensing of dopamine (DA) and ascorbic acid (AA). The modified electrode was found to be selective for DA analysis. The lowest detection limit of DA sensing was found to be 4 μМ with a sensitivity of 18 μA ± 6 nA/mM of DA.     

肌醇六磷酸钙膜固定辣根过氧化酶制备过氧化氢生物传感器

利用肌醇六磷酸钙(Ca-IP6)的磷酸酯键及Ca2+对HRP具有静电吸引和螯合作用,将其自组装于玻碳电极(GCE)表面,制备Nafion/HRP/Ca-IP6/GCE生物传感器。用紫外-可见吸收光谱、电化学阻抗光谱和循环伏安法对Nafion/HRP/Ca-IP6/GCE膜进行了表征。实验结果表明,吸附了HRP仍然能够保持原有的生物活性,实现了辣根过氧化物酶在电极表面的直接电子转移。该修饰电极对过氧化氢有很好的电催化活性,线性范围为2.67×10-7~1.067×10-6mol/L,最低检测限为1.3×10-7mol/L(信噪比S/N=3),米氏常数为0.259 mmol/L。该生物传感器拥有较低的检测限,较高的电催化效率和较好的稳定性及重现性。     

Detection of hydrazine based on Nano-Au deposited on Porous-TiO2 film

The fabrication of Nano-Au/Porous-TiO₂ composite modified glassy carbon electrode (GCE) and its application in the determination of hydrazine were proposed. The morphological characterization was examined by transmission electron microscope and scanning electron microscopy. The Nano-Au/Porous-TiO₂/GCE exhibited a wide linear range of hydrazine from 2.5 to 500 μM, with a detection limit of 0.5 μM at a signal-to-noise ratio of 3 and with a fast response time (within 3 s). Furthermore, the reaction mechanism of the hydrazine on the Nano-Au/Porous-TiO₂/GCE was explored. The ease of fabrication, high stability, and low cost of the modified electrode are the promising features of the proposed sensor.     

Trioctylphosphine as Both Solvent and Stabilizer to Synthesize CdS Nanorods

High quality CdS nanorods are synthesized reproducibly with cadmium acetate and sulfur as precursors in trioctylphosphine solution. The morphology, crystalline form and phase composition of CdS nanorods are characterized by transmission electron microscopy (TEM), high-resolution TEM and X-ray diffraction (XRD). CdS nanorods obtained are uniform with an aspect ratio of about 5:1 and in a wurtzite structure. The influence of reaction conditions on the growth of CdS nanorods demonstrates that low precursor concentration and high reaction temperature (260 °C) are favorable for the formation of uniform CdS nanorods with 85.3% of product yield.     

ZnS, CdS and HgS Nanoparticles via Alkyl-Phenyl Dithiocarbamate Complexes as Single Source Precursors

The synthesis of II-VI semiconductor nanoparticles obtained by the thermolysis of certain group 12 metal complexes as precursors is reported. Thermogravimetric analysis of the single source precursors showed sharp decomposition leading to their respective metal sulfides. The structural and optical properties of the prepared nanoparticles were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) UV-Vis and photoluminescence spectroscopy. The X-ray diffraction pattern showed that the prepared ZnS nanoparticles have a cubic sphalerite structure; the CdS indicates a hexagonal phase and the HgS show the presence of metacinnabar phase. The TEM image demonstrates that the ZnS nanoparticles are dot-shaped, the CdS and the HgS clearly showed a rice and spherical morphology respectively. The UV-Vis spectra exhibited a blue-shift with respect to that of the bulk samples which is attributed to the quantum size effect. The band gap of the samples have been calculated from absorption spectra and werefound to be about 4.33 eV (286 nm), 2.91 eV (426 nm) and 4.27 eV (290 nm) for the ZnS, CdS and HgS samples respectively.     

Studies of electrochemical reduction of dioxygen with RRDE

The electrochemical behaviors of dioxygen (O₂) were studied by using rotate ring-disk electrode (RRDE) and other electrochemical methods at bare glassy carbon electrode (GCE) and single-walled carbon nanotubes (SWNTs)-dihexadecyl hydrogen phosphate (DHP) film modified GCE. The results showed that the electrochemical reduction of dioxygen was considered to proceed by a two-step two-electron reduction pathway at both bare GCE and SWNTs-DHP film modified GCE in 0.1 mol/L air-saturated sodium hydroxide (NaOH). Maybe because each reaction rate for two cases was different the cyclic voltammograms measurements exhibited different behaviors. The detection of ring current confirmed the presence of middle product hydrogen peroxide (H₂O₂). Furthermore, larger current and more positive reduction potential indicated that SWNTs showed a catalytic effect towards the electrochemical reduction of dioxygen.     

Bi2MoO6 hierarchical hollow microspheres with remarkable electrochemical performance

Hierarchical hollow architectures have demonstrated a remarkable electrochemical performance. In this contribution, Bi₂MoO₆ hierarchical hollow microspheres constructed by nanosheets are prepared by a facile hydrothermal method without any post-treatment, and investigated firstly as anode of lithium-ion batteries. The time-dependent experiments show the morphology evolution from solid microspheres to hierarchical hollow microspheres. Compared with the previous reports, the results manifest expectedly a superior lithium storage performance in terms of specific capacity, cycling stability, rate capability, active energy and Li⁺ diffusion kinetics.     

Phase Controlled Monodispersed CdS Nanocrystals Synthesized in Polymer Solution Using Microwave Irradiation

Cadmium sulfide (CdS) nanocrystals were synthesized in aqueous solution of polyvinyl pyrrolidone (PVP) via the simple and rapid microwave irradiation method. It is revealed that sulfur source is a key factor in controlling the phase formation of the resulting nanocrystals. The hexagonal and cubic structure of CdS nanocrystals could be obtained with varying sulfur sources of thioacetamide and sodium sulphide respectively. The interaction mechanism of PVP with precursor ions of cadmium and sulfur sources in the preparation process was proposed. It is found that PVP compounded the CdS nanoparticles and protected them from agglomerating. With increasing of PVP concentration, the average particle size of CdS nanocrystals increased and subsequently their optical band gap decreased. At the appropriate dosage of PVP, well isolated nanoparticles with relatively narrow size distribution were obtained for both sulfur sources. Moreover the stability of CdS nanoparticles enhanced after coating with polymer.     

铁掺杂二氧化钛空心球的制备及性能

以TiF₄为钛源、九水合硝酸铁为掺杂前体,采用水热法制备铁掺杂的TiO₂空心微球。采用SEM、TEM、XRD、BET、XPS等技术对样品的形貌、结构、晶型、比表面积、元素组成等进行表征,以亚甲基蓝（MB）的光催化降解为目标反应,评价其光催化活性。结果表明,160℃下水热反应生成的纳米TiO₂空心微球晶型为锐钛矿,少量掺铁并不影响微球的形貌及晶体结构。光催化实验表明,160℃下水热反应12 h生成的TiO₂空心微球样品均匀性好、光催化活性最佳;铁掺杂能显著提高TiO₂空心微球的催化活性,当铁钛比为1.5:100时,所得样品粒径最小,比表面积最大,光催化活性最高。     

Hybridization biosensor using sodium tanshinone IIA sulfonate as electrochemical indicator for detection of short DNA species of chronic myelogenous leukemia

Cyclic voltammetry (CV) was used to investigate electrochemical behavior of sodium tanshinone IIA sulfonate (STS) and the interaction between STS and salmon sperm DNA. STS had excellent electrochemical activity on the glassy carbon electrode (GCE) with a couple reversible redox peaks. In pH 4.0 phosphate buffer solution (PBS), the binding ratio between STS and salmon sperm DNA was calculated to be 1:1 and the binding constant was 1.67 × 10⁴ L/mol. A chronic myelogenous leukemia (CML, Type b3a2) DNA biosensor was developed by immobilizing covalently single-stranded CML DNA fragment to a modified GCE. The surface hybridization of the immobilized single-stranded CML DNA fragment with its complementary DNA fragment was evidenced by electrochemical methods using STS as a novel electrochemical indicator, with a detection limit of 6.7 × 10⁻⁹ M and a linear range from 2.0 × 10⁻⁸ M to 2.0 × 10⁻⁷ M. Selective determination of complementary ssDNA was achieved using differential pulse voltammetry (DPV).     

Synergizing hexagonal ferrite with transition metals in core-shell-shell nanostructures (SrFe@Dop@M) as dualistic probe for detoxification and electrochemical detection of pharmaceutical drugs

A novel hexagonal ferrite-based core-shell-shell nanostructures (SrFe@Dop@M, M = Cr, Mn, Fe, Co, Ni, Cu and Zn) were designed for dual application of simultaneous electrochemical detection and photocatalytic degradation of pharmaceutical drugs. The phase analysis and topographical investigations of synthesized nanostructures were examined via PXRD, FE-SEM and HR-TEM techniques. XPS was employed to investigate the elemental composition and their corresponding electronic states. The electron transfer rate of synthesized nanostructures was estimated by EIS and CV studies. The comparative photocatalytic evaluation of SrFe, SrFe@Dop and SrFe@Dop@M was performed towards degradation of levofloxacin and sulfamethoxazole. SrFe@Dop@Mn was observed to portray best photocatalytic performance of around 3 times than that of bare SrFe and SrFe@Dop, attributable to its lowest energy band gap value and highest electron transfer rate. The SrFe@Dop@Mn glassy carbon electrode (GCE) was further employed as an electrochemical sensor towards detection of levofloxacin in waste water samples, providing impressive linear range from 55.2 nM to 772.8 nM and limit of detection as low as 0.037 nM. The real sample (tap water, lake water, river water and urine sample) analysis was evaluated to realize the practical applicability of modified sensor.     

Poly(glutamic acid) nanofibre modified glassy carbon electrode: Characterization by atomic force microscopy, voltammetry and electrochemical impedance

Glassy carbon electrodes (GCE) were modified with poly(glutamic acid) acid films prepared using three different procedures: glutamic acid monomer electropolymerization (MONO), evaporation of poly(glutamic acid) (PAG) and evaporation of a mixture of poly(glutamic acid)/glutaraldehyde (PAG/GLU). All three films showed good adherence to the electrode surface. The performance of the modified GCE was investigated by cyclic voltammetry and differential pulse voltammetry, and the films were characterized by atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). The three poly(glutamic acid) modified GCEs were tested using the electrochemical oxidation of ascorbic acid and a decrease of the overpotential and the improvement of the oxidation peak current was observed. The PAG modified electrode surfaces gave the best results. AFM morphological images showed a polymeric network film formed by well-defined nanofibres that may undergo extensive swelling in solution, allowing an easier electron transfer and higher oxidation peaks.