Hydrogen sensors and hydrogen-activated switches were fabricated from arrays of mesoscopic palladium wires. These palladium "mesowire" arrays were prepared by electrodeposition onto graphite surfaces and were transferred onto a cyanoacrylate film. Exposure to hydrogen gas caused a rapid (less than 75 milliseconds) reversible decrease in the resistance of the array that correlated with the hydrogen concentration over a range from 2 to 10%. The sensor response appears to involve the closing of nanoscopic gaps or "break junctions" in wires caused by the dilation of palladium grains undergoing hydrogen absorption. Wire arrays in which all wires possessed nanoscopic gaps reverted to open circuits in the absence of hydrogen gas.

The charge-storage mechanism in manganese dioxide (MnO2)-based electrochemical supercapacitors was investigated and discussed toward prepared MnO2 microstructures. The preparation of a series of MnO2 allotropic phases was performed by following dedicated synthetic routes. The resulting compounds are classified into three groups depending on their crystal structures based on 1D channels, 2D layers, or 3D interconnected tunnels. The 1D group includes pyrolusite, ramsdellite, cryptomelane, Ni-doped todorokite (Ni-todorokite), and OMS-5. The 2D and 3D groups are composed of birnessite and spinel, respectively. The prepared MnO2 powders were characterized using X-ray diffraction, scanning electron microscopy, the Brunauer-Emmett-Teller technique, cyclic voltammetry (CV), and electrochemical impedance spectroscopy. The influence of the MnO2 microstructure on the electrochemical performance of MnO2-based electrodes is commented on through the specific surface area and the electronic and ionic conductivities. It was demonstrated that the charge-storage mechanism in MnO2-based electrodes is mainly faradic rather than capacitive. The specific capacitance values are found to increase in the following order: pyrolusite (28 Fx g(-1)) < Ni-todorokite < ramsdellite < cryptomelane < OMS-5 < birnessite < spinel (241 Fx g(-1)). Thus, increasing the cavity size and connectivity results in the improvement of the electrochemical performance. In contrast with the usual assumption, the electrochemical performance of MnO2-based electrodes was not dependent on the specific surface area. The electronic conductivity was shown to have a limited impact as well. However, specific capacitances of MnO2 forms were strongly correlated with the corresponding ionic conductivities, which obviously rely on the microstructure. The CV experiments confirmed the good stability of all MnO2 phases during 500 charge/discharge cycles.

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Arrays of mesoscopic palladium wires prepared by electrodeposition form the basis for hydrogen sensors and hydrogen-actuated switches that exhibit a response time ranging from 20 ms to 5 s, depending on the hydrogen concentration. These devices were constructed by electrodepositing palladium mesowires on a highly oriented pyrolytic graphite surface and then transferring these mesowires to a cyanoacrylate film supported on a glass slide. The application of silver contacts to the ends of 10-100 mesowires, arrayed electrically in parallel, produced sensors and switches that exhibited a high conductivity state in the presence of hydrogen and a low conductivity state in the absence of hydrogen. After an initial exposure to hydrogen, 15-50 nanoscopic gaps are formed in each mesowire. These nanoscopic gaps or "break junctions" close in the presence of hydrogen gas and reopen in its absence as hydrogen is reversibly occluded by the palladium grains in each wire, and the palladium lattice expands and contracts by several percent. The change in resistance for sensors and switches was related to the hydrogen concentration over a range from 1 to 10%.

Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

Electrospinning is the most facile and highly versatile approach to produce 1D polymeric, inorganic, and hybrid nanomaterials with a small diameter, controllable dimensions, and designed architectures. In particular, with large surface area, high porosity, low density, good directionality, and tunable composition, electrospun nanofibers and mats are regarded as ideal candidates for various kinds of electrochemical energy storage devices such as supercapacitors (SCs). In this review, the recent progress in electrospun electrode materials for SCs is presented, covering the architecture design and their electrochemical performance. After a brief introduction about SCs, the basic principles of the electrospinning technique are discussed. Following, attention is paid to the discussion of various electrospun nanofibers and mats including 1D carbons, metal oxides, metal sulfides, metal nitrides, conducting polymers and composite nanomaterials with various types of architectures as electrodes for SCs. The relationship between the composition, architecture, and the electrochemical performance is discussed in detail. Finally, some challenges and perspectives of future research of the electrospun nanofibers and mats for high performance SCs are highlighted. It is anticipated that this review would provide the researchers some inspiration for constructing new types of energy storage devices.

The electrochemical synthesis of nanoparticles of γ-Fe2O3 was performed in an organic medium. The size was directly controlled by the imposed current density, and the resulting particles were stabilized as a colloidal suspension by the use of cationic surfactants. The size distributions of the particles were narrow, with the average sizes varying from 3 to 8 nm. The amorphous character of the nanoparticles was clearly established by X-ray powder diffraction and TEM analysis. The microstructure of this phase could nevertheless be spectroscopically related to maghemite, γ-Fe2O3. 57Fe Mossbauer spectroscopy and magnetization measurements indicated that the dry powders exhibit superparamagnetic behavior at room temperature.

A general method is described for the electrodeposition of long (>500 μm) nanowires composed of noble or coinage metals including nickel, copper, silver, and gold. Nanowires of these metals, with diameters in the range from 60 to 750 nm, were obtained by electrochemical step edge decoration (ESED), the selective electrodeposition of metal at step edges. Nanowire growth by ESED was accomplished on highly oriented pyrolytic graphite surfaces by applying three voltage pulses in succession:  An oxidizing “activation” pulse, a large amplitude, reducing “nucleation” pulse, and a small amplitude reducing “growth” pulse. The activation pulse potential was optimized to oxidize step edges on the graphite surface just prior to deposition. The nucleation pulse had an overpotential for metal deposition of between −150 and −500 mV and a duration of 5−100 ms. The growth pulse had a small deposition overpotential of less than −100 mV. Nanowire growth was characterized by a time-independent deposition current, and consequently, the nanowire radius was proportional to the square root of the deposition time in accordance with the expected growth law.