An Efficient Electrochemical Sensor Driven by Hierarchical Hetero-Nanostructures Consisting of RuO2 Nanorods on WO3 Nanofibers for Detecting Biologically Relevant Molecules.

By means of electrospinning with the thermal annealing process, we investigate a highly efficient sensing platform driven by a hierarchical hetero-nanostructure for the sensitive detection of biologically relevant molecules, consisting of single crystalline ruthenium dioxide nanorods (RuO2 NRs) directly grown on the surface of electrospun tungsten trioxide nanofibers (WO3 NFs). Electrochemical measurements reveal the enhanced electron transfer kinetics at the prepared RuO2 NRs-WO3 NFs hetero-nanostructures due to the incorporation of conductive RuO2 NRs nanostructures with a high surface area, resulting in improved relevant electrochemical sensing performances for detecting H2O2 and L-ascorbic acid with high sensitivity.

Selectivity enhancement of amperometric nitric oxide detection via shape-controlled electrodeposition of platinum nanostructures.

Nitric oxide (NO) is a biologically multifunctional gaseous signaling molecule. For electrochemical NO detections, complex membranes are commonly adopted to acquire the selectivity for NO over other oxidizable biological species. In this study, we demonstrate the improved selectivity in amperometric NO measurements at nanostructured Pt. The Pt layers were electrodeposited on Au substrate electrodes at a constant potential (-0.2 V vs. Ag/AgCl) with a constant deposition charge (0.08 C). The various distinctive nanostructures of Pt deposits were obtained via either changing the precursor concentrations (from 5 to 75 mM K2PtCl4) or using a different precursor (75 mM H2PtCl6). With a higher K2PtCl4 concentration, the Pt deposition became less sharp and the smoothest Pt was deposited with 75 mM H2PtCl6. The most greatly sharp-pointed nanostructures were generated with the lowest precursor concentration (5 mM K2PtCl4) and exhibited the highest sensitivity, which was attributed to the hydrophobic property of sharply nanostructured Pt. A hydrophobic neutral gas molecule, NO, possibly has a more favorable access to the inner surface of more hydrophobic Pt deposition and eventually increases the oxidation current. NO current sensitivity was enhanced at the more hydrophobic Pt surface, whereas the oxidation currents of acetaminophen, l-ascorbic acid, nitrite and hydrogen peroxide, four oxidizable biological interfering species, were independent of the Pt nanostructure. Conclusively, the enhanced amperometric selectivity to NO was achieved by the simple electrodeposition method without any additional membranes.

Synthesis and catalytic activity of electrospun NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation.

NiO/NiCo2O4 nanotubes with a diameter of approximately 100 nm are synthesized using Ni and Co precursors via electro-spinning and subsequent calcination processes. The tubular structure is confirmed via transmission electron microscopy imaging, whereas the structures and elemental compositions of the nanotubes are determined using x-ray diffraction, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. N2 adsorption isotherm data reveal that the surface of the nanotubes consists of micropores, thereby resulting in a significantly higher surface area (∼20 m2 g-1) than expected for a flat-surface structure (<15 m2 g-1). Herein, we present a study of the catalytic activity of our novel NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation. The catalytic activity of NiO/NiCo2O4 is superior to Pt below 100 °C for CO oxidation. For acetaldehyde oxidation, the total oxidation activity of NiO/NiCo2O4 for acetaldehyde is comparable with that of Pt. Coexistence of many under-coordinated Co and Ni active sites in our structure is suggested be related to the high catalytic activity. It is suggested that our novel NiO/NiCo2O4 tubular structures with surface microporosity can be of interest for a variety of applications, including the catalytic oxidation of harmful gases.

Enhanced electrochemical performance of a ZnO-MnO composite as an anode material for lithium ion batteries.

A ZnO-MnO composite was synthesized using a simple solvothermal method combined with a high-temperature treatment. To observe the phase change during the heating process, in situ high-temperature XRD analysis was performed under vacuum conditions. The results indicated that ZnMn2O4 transformed into the ZnO-MnO composite phase starting from 500 °C and that this composite structure was retained until 700 °C. The electrochemical performances of the ZnO-MnO composite electrode were evaluated through galvanostatic discharge-charge tests and cyclic voltammetry analysis. Its initial coulombic efficiency was significantly improved to 68.3% compared to that of ZnMn2O4 at 54.7%. Furthermore, the ZnO-MnO composite exhibited improved cycling performance and enhanced rate capability compared with untreated ZnMn2O4. To clarify the discharge-charge mechanism of the ZnO-MnO composite electrode, the structural changes during the charge and discharge processes were also investigated using ex situ XRD and TEM.

RuO2-ReO3 composite nanofibers for efficient electrocatalytic responses.

We present a facile synthetic route to ruthenium dioxide (RuO2)-rhenium oxide (ReO3) electrospun composite nanofibers and their electrocatalytic responses for capacitance and H2O2 sensing. The contents of rhenium oxide of electrospun ruthenium dioxide (RuO2) were carefully controlled by an electrospinning process with the preparation of the precursor solutions followed by the thermal annealing process in air. The electrochemical applications of RuO2-ReO3 electrospun composite nanofibers were then investigated by modifying these materials on the surface of glassy carbon (GC) electrodes, RuO2-ReO3(n)/GC (n = 0.0, 0.07, 0.11, and 0.13), where n denotes the relative atomic ratio of Re to the sum of Ru and Re. Specific capacitance and H2O2 reduction sensitivity were remarkably enhanced depending on the amount of ReO3 increased. Among the four compositions of RuO2-ReO3(n), RuO2-ReO3(0.11)/GC showed the highest performances, i.e., a 20.9-fold higher specific capacitance (205 F g(-1) at a potential scan rate (v) of 10 mV s(-1); a capacity loss of 19% from v = 10 to 2000 mV s(-1)) and a 7.6-fold higher H2O2 reduction sensitivity (668 µA mM(-1) cm(-2), normalized by GC disk area), respectively, compared to only RuO2/GC.

Spongelike nanoporous Pd and Pd/Au structures: facile synthesis and enhanced electrocatalytic activity.

This paper reports the facile synthesis and characterization of spongelike nanoporous Pd (snPd) and Pd/Au (snPd/Au) prepared by a tailored galvanic replacement reaction (GRR). Initially, a large amount of Co particles as sacrificial templates was electrodeposited onto the glassy carbon surface using a cyclic voltammetric method. This is the key step to the subsequent fabrication of the snPd/Au (or snPd) architectures by a surface replacement reaction. Using Co films as sacrificial templates, snPd/Au catalysts were prepared through a two-step GRR technique. In the first step, the Pd metal precursor (at different concentrations), K2PdCl4, reacted spontaneously to the formed Co frames through the GRR, resulting in a snPd series. snPd/Au was then prepared via the second GRR between snPd (prepared with 27.5 mM Pd precursor) and Au precursor (10 mM HAuCl4). The morphology and surface area of the prepared snPd series and snPd/Au were characterized using spectroscopic and electrochemical methods. Rotating disk electrode (RDE) experiments for oxygen reduction in 0.1 M NaOH showed that the snPd/Au has higher catalytic activity than snPd and the commercial Pd-20/C and Pt-20/C catalysts. Rotating ring-disk electrode (RRDE) experiments reconfirmed that four electrons were involved in the electrocatalytic reduction of oxygen at the snPd/Au. Furthermore, RDE voltammetry for the H2O2 oxidation/reduction was used to monitor the catalytic activity of snPd/Au. The amperometric i-t curves of the snPd/Au catalyst for a H2O2 electrochemical reaction revealed the possibility of applications as a H2O2 oxidation/reduction sensor with high sensitivity (0.98 mA mM(-1) cm(-2) (r = 0.9997) for H2O2 oxidation and -0.95 mA mM(-1) cm(-2) (r = 0.9997) for H2O2 reduction), low detection limit (1.0 µM), and a rapid response (<∼1.5 s).

Oxidation-state dependent electrocatalytic activity of iridium nanoparticles supported on graphene nanosheets.

Nanocomposites of iridium nanoparticles (Ir NPs), supported on graphene nanosheets, are synthesized and their electrocatalytic acitivities in the oxygen reduction reaction (ORR) are studied depending on their Ir oxidation state. Graphene functionalized with poly(vinyl pyrrolidone) (pRGO) is a suitable support for Ir NPs, producing well-monodispersed Ir NPs anchored strongly on the pRGO surface (Ir NP/pRGO) with a very high density. This was confirmed by scanning electron microscopy and transmission electron microscopy. The ORR activity of the Ir NP/pRGO nanocomposites in 0.5 M H2SO4 solution was observed to be dependent on the oxidation state of the immobilized Ir NPs. In fact, the nanocomposite composed of Ir(0) metal NPs, rather than Ir oxide (IrOx) NPs, exhibits higher ORR activity, such as more positive onset potential, higher and flatter limiting current density, a greater n value, and a sharper curve shape in the rotating disk electrode voltammetry experiments. Higher ORR activity of Ir is ascribed to the stronger adsorption of oxygen on the surface of Ir compared to IrOx. The practical stability of the Ir NP/pRGO composite was also confirmed under O2 saturated/acidic conditions.

Synthesis and electrocatalytic activity of highly porous hollow palladium nanoshells for oxygen reduction in alkaline solution.

A series of hollow Pd nanoshells are prepared by employing Co nanoparticles as sacrificial templates with different concentrations of a Pd precursor (1, 6, 12, 20, and 40 mM K2PdCl4), denoted hPd-X (X: concentration of K2PdCl4 in mM unit). The synthesized hPd series are tested as a cathodic electrocatalyst for oxygen reduction reaction (ORR) in alkaline solution. The morphology and surface area of the hPd catalysts are characterized using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and cyclic voltammetry (CV). Rotating disk electrode (RDE) voltammetric studies show that the hPd-20 (prepared using 20 mM K2PdCl4) has the highest ORR activity among all the hPd series, while being comparable to commercial Pd and Pt catalysts (E-TEK). The more facilitated ORR at hPd-20 is presumably induced by the enhanced Pd surface area and efficiently high porosity of Pd nanoshells.

Hierarchically driven IrO2 nanowire electrocatalysts for direct sensing of biomolecules.

Applying nanoscale device fabrications toward biomolecules, ultra sensitive, selective, robust, and reliable chemical or biological microsensors have been one of the most fascinating research directions in our life science. Here we introduce hierarchically driven iridium dioxide (IrO(2)) nanowires directly on a platinum (Pt) microwire, which allows a simple fabrication of the amperometric sensor and shows a favorable electronic property desired for sensing of hydrogen peroxide (H(2)O(2)) and dihydronicotinamide adenine dinucleotide (NADH) without the aid of enzymes. This rational engineering of a nanoscale architecture based on the direct formation of the hierarchical 1-dimensional (1-D) nanostructures on an electrode can offer a useful platform for high-performance electrochemical biosensors, enabling the efficient, ultrasensitive detection of biologically important molecules.

Single carbon fiber decorated with RuO2 nanorods as a highly electrocatalytic sensing element.

We demonstrate highly efficient electocatalytic activities of single crystalline RuO(2) nanorods grown on carbon fiber (CF), i.e., RuO(2) nanorod-CF hybrid microelectrode, prepared by a simple thermal annealing process from the Ru(OH)(3) precursor at 300 °C. The general electrochemical activity of a RuO(2) nanorod-CF microelectrode represents faster electron transfer for the [Fe(CN)(6)](3-/4-) couple than that of the bare CF microelectrode which are confirmed from the cyclic voltammetry (CV) measurement. Also, the amperometric response for the H(2)O(2) oxidation is remarkably facilitated at the RuO(2) nanorod-CF microelectrode by not only the enlarged surface area but the high electrocatalytic activity of the RuO(2) nanorod material itself. Furthermore, a single microelectrode of RuO(2) nanorod-CF exhibits the superior tolerance to Cl(-) ion poisoning unlike Pt-based electrocatalysts, indicating the promising sensor candidate in physiological conditions.