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Although Li-ion batteries have attracted significant interest due to their higher energy density, lack of high rate performance electrode materials and intrinsic safety issues challenge their commercial applications. Herein, we demonstrate a simple photocatalytic reduction method that simultaneously reduces graphene oxide (GO) and anchors (010)-faceted mesoporous bronze-phase titania (TiO2-B) nanosheets to reduced graphene oxide (RGO) through Ti(3+)-C bonds. Formation of Ti(3+)-C bonds during the photocatalytic reduction process was identified using electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) techniques. When cycled between 1-3 V (vs Li(+/0)), these chemically bonded TiO2-B/RGO hybrid nanostructures show significantly higher Li-ion storage capacities and rate capability compared to bare TiO2-B nanosheets and a physically mixed TiO2-B/RGO composite. In addition, 80% of the initial specific (gravimetric) capacity was retained even after 1000 charge-discharge cycles at a high rate of 40C. The improved electrochemical performance of TiO2-B/RGO nanoarchitectures is attributed to the presence of exposed (010) facets, mesoporosity, and efficient interfacial charge transfer between RGO monolayers and TiO2-B nanosheets.

Pure-phase CuWO4 photoanodes with 200 nm thickness were produced by spin-casting sol–gel precursors to evaluate their performance as photoelectrodes for water oxidation. The stability of CuWO4 in potassium phosphate (KPi) and potassium borate (KBi) buffers was evaluated as a function of pH and irradiance. CuWO4 photoanodes demonstrate higher stability at pH 3 and 5 in a 0.1 M KPi buffer and are significantly more stable over a 12 h period of illumination in a 0.1 M KBi buffer at pH 7 (∼75 μA/cm2 photocurrent at 1.23 V vs RHE (reversible hydrogen electrode) and 1 sun illumination) than in a 0.1 M KPi buffer at pH 7. The onset of photoelectrochemical water oxidation and electrochemical O2 reduction is dictated by Cu(3d x 2–y 2 ) states that reside at 0.4 V vs RHE, determined by linear sweep voltammetry. The onset for water oxidation is hindered by a large charge-transfer resistance, as high as 4.6 kΩ at 1 V vs RHE. Nevertheless, CuWO4 photoanodes show nearly quantitative faradic efficiency for water oxidation, even in the presence of chloride, an improvement over the binary oxide WO3.

Electrochemical impedance spectroscopy (EIS) was used to probe the electrode/electrolyte interface of CuWO4 thin films prepared by sol–gel methods for water oxidation under simulated solar irradiation. The presented results indicate that the onset of photocurrent is dictated by the presence of a midgap state that participates in water oxidation. The state is likely composed of Cu(3d) orbitals because of both experimental and theoretical evidence of Cu-based orbitals comprising the top of the valence band and the bottom of the conduction band in the bulk. This midgap state was identified experimentally by electrochemical impedance spectroscopy under simulated solar irradiation in borate buffer at pH 7.00. Our results show the evolution of two-charge-transfer events in the Nyquist and Bode plots of EIS data as well as the Fermi level pinning by Mott–Schottky analysis in the potential range of 0.81–1.01 V (reversible hydrogen electrode, RHE). The Mott–Schottky analysis at low frequencies in the dark suggests that it is not a photogenerated state but rather a permanent state in the electronic structure of CuWO4. The same results are observed in pH 9.24 borate buffer, and the midgap state shows a Nernstian pH response.

Electrodeposited thin films composed of CuWO 4 −WO 3 oxidize water under AM 1.5G irradiation with no electrical bias and simultaneous reduction of [Fe(CN) 6 ] 3− at a Pt-mesh auxiliary electrode with a faradaic efficiency of >85%. The quantum efficiency and apparent quantum yield are 7% (at 400 nm) and 0.038%, respectively, in a representative film. Although low, the photoanode is stable, maintaining its steady-state current density (17 μA/cm 2 ) over a 2.5 h illumination period. Through full photoelectrochemical characterization, we identify the specific drawbacks in our material and propose solutions.

Microcrystalline and submicrometer powders of Zn(1-x)Cu(x)WO(4) (0 ≤ x ≤ 1) have been prepared by a solid-state synthesis from stoichiometric quantities of the constituent d-block metal oxide and tungsten oxide as well as from a Pechini sol-gel synthesis starting from the d-block metal nitrate and ammonium metatungstate. The stoichiometry of the product is confirmed by inductively coupled plasma-atomic emission spectrometry (ICP-AES) analysis. X-ray diffraction shows that for the entire range of compositions, a single-phase product crystallizes in the wolframite structure, with a symmetry-lowering transition from P2/c to P1[overline] at x = 0.20, concomitant with the first-order Jahn-Teller distortion of Cu(2+). Far-IR spectroscopy corroborates that symmetry lowering is directly related to the tetragonal distortion within the CuO(6) octahedra, with the Zn-O A(u) symmetry mode at 320 cm(-1) (x = 0) splitting into two stretches at 295 and 338 cm(-1) (x = 0.3). UV-vis-NIR spectroscopy shows an optical absorption edge characteristic of an indirect band gap that linearly decreases in energy from 3.0 eV (x = 0) to 2.25 eV (x = 1). SQUID magnetometry shows that Zn(1-x)Cu(x)WO(4) (0.1 ≤ x ≤ 1) has an effective moment of 2.30 ± 0.19 μ(B) per mol copper, typical of Cu(2+) in extended solids. For high concentrations of copper (x ≥ 0.8), two transitions are observed: one at high-temperature, 82 K (x = 1.0) that decreases to 59 K (x = 0.8), and the Néel temperature, 23.5 K (x = 1.0) that decreases to 5.5 K (x = 0.8). For x < 0.8, no long-range order is observed. A physical 1:1 mixture of both CuWO(4):ZnWO(4) shows magnetic ordering identical to that of CuWO(4).

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The title compounds are prepared by solid state reaction of stoichiometric mixtures of ZnO, CuO, and WO3 (alumina crucible, 850 °C, 36 h) and by a Pechini‐type citric acid sol—gel method.