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Nanostructuring of semiconductor films offers the potential means for producing photoelectrodes with improved minority charge carrier collection. Crucial to the effective operation of the photoelectrode is also the choice of a suitable electrolyte. The behaviour of the nanostructured WO(3) photoanodes in methane sulfonic acid solutions, which allow one to obtain large, perfectly stable visible-light driven water splitting photocurrents, is discussed. The important effect of the electrolyte concentration upon the current distribution and the related photocurrent losses within the nanoporous photoelectrodes is pointed out.

Oscillatory electroreduction of the thiocyanate complexes of nickel(II) at stationary mercury electrodes is complicated by the formation and accumulation of the heterogeneous Ni amalgam and a surface active NiS adsorbate. Consequently, dynamic instabilities observed at such electrodes always have a transient character. To overcome these difficulties, following our previous studies of the Ni(II)-SCN- oscillator, we describe the new experimental approach, based on the application of the streaming mercury electrode to the studies of nonlinear dynamic instabilities of this system. A special experimental setup was assembled. We found that in the presence of an appropriate serial ohmic resistance in the electric circuit, not only the sustained oscillations, but also the bistable behavior in the current−voltage characteristics occurred, which was not reported for this process so far. The experimental diagram of regions of the bistability, monostability and oscillations in the U−R s parameter space is constructed. For the explanation of the bistability, the numerical models were elaborated which quantitatively confirmed the observed phenomena as originating from the coupling of the negative differential polarization resistance with ohmic potential drops.

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An important role of the electrochemical impedance spectroscopy (EIS) is the characterization of the electrical double layer formed at the electrode/electrolyte interfaces. The phenomenological double layer studies with an aqueous and ionic liquid electrolytes are reviewed with a conclusion that the double layer capacitance is frequency dependent as the rule rather than the exception. We discuss the impedance consequences of the nonuniform current distribution along the electrochemical interface, which also contributes to the apparent frequency dependence of the capacitance. Finally we show recent articles on nonconventional EIS techniques with high lateral resolution or enabling fast measurements.

We report the first solid-state impedance study of hydrogen-rich ammonia borane, AB, and its three alkali metal amidoborane derivatives. Temperature-dependent impedance spectra of solid M(NH(2)BH(3)) salts are predominated by ionic conductivity, which at room temperature ranges from 5.5 μS cm(-1) (M = Li) to 2.2-3.0 mS cm(-1) (Na, Na(0.5)Li(0.5)), while the activation energy for conductivity is rather high (140-158 kJ mol(-1)). Variation of conductivity with time can be used to extract information about the evolution of the system during thermal decomposition. By using a combination of impedance spectroscopy, thermogravimetric analysis, scanning calorimetry, evolved gas analysis, infrared absorption spectroscopy as well as (11)B and (1)H MAS NMR, we were able to reconfirm the complex pathway of thermal decomposition of amidoboranes postulated by two of us earlier (J. Mater. Chem. 2009, 19, 2043).

We report here the results of electrochemical studies on CO2 electroreduction at multilayered catalyst composed of the monatomic layer of copper covering palladium overlayers (0.8-10 monolayers) deposited on the well-defined Au(111) surface. These multilayered systems were obtained by successive underpotential deposition steps: Pd on Au(111) as well as Cu on Pd/Au(111). Low index orientation of Au substrate was chosen to compare Pd overlayers with bulk Pd(111), which is known to reduce CO2 to CO adsorbates in acidic solutions. The process of CO2 electroreduction was studied by using classical transient electrochemical methods. Catalytic activity of bare Pd layers was investigated in acidic and neutral solutions. In the latter case, much higher activity of Pd overlayers was observed. The results showed that the palladium layer thickness significantly changed the catalytic activities of both bare Pd overlayers and the one Cu monolayer covered electrodes toward CO2 electroreduction. Results show that catalytic activity can be finely tuned by using the multilayered near-surface-alloy approach.

Divalent silver is stabilized in concentrated sulphuric acid and oleums. The formal redox potential of the Ag(II)/Ag(I) redox pair is markedly dependent on the Hammett acidity function and it reaches +2.90 V vs. NHE in 33% oleum thus rivalling E° for the F2/2F(-) redox pair (+2.87 V).