Papers by Keyword: Oxygen Evolution

Abstract: Cylindrical TiO₂ nanotubes and hexagonal TiO₂ nanotubes were obtained in the anodizing process of titanium in fluoride-containing electrolyte. Based on the experimental findings and viscous flow model, a mechanism of self-ordering process of hexagonal cells arrangement for porous anodic TiO₂ nanotubes (PATNT) is proposed in this paper. The analysis results show that oxygen evolution in the pore bottoms plays an important role in the self-ordering process. Oxide grows around the oxygen bubbles in the pore bottoms, which results in the formation of cylindrical TiO₂ nanotubes. Volume expansion of TiO₂ takes place during the anodizing process. Plastic deformation and repulsive force caused by volume expansion are responsible for self-ordering process of PATNT hexagonal cells.

Abstract: Different corrosion resistant stainless steels, nickel-based alloys, pure nickel, Ta-coated stainless steel (AISI 316L), niobium, platinum and gold rods were evaluated as possible materials for use in the intermediate temperature (200-400 °C) acidic water electrolysers. The corrosion resistance was measured under simulated conditions (molten KH2PO4) corresponding to the proton-conducting solid acids or transition metal phosphates as electrolytes. It was shown that, unlike at temperatures below 200 °C, gold is unstable with respect to corrosion in molten KH2PO4. Platinum demonstrated high corrosion resistance and the anodic and cathodic limits were for the first time found for the electrolyte. Nickel, niobium, Inconel®625, Hastelloy®C-276 and Ta-coated stainless steel (AISI 316L) demonstrated high corrosion stability and can be recommended as construction materials for bipolar plates.

Abstract: The PbO₂ film electrodes have been prepared by different electrodeposition process onto aluminum substrate.The electrochemical activity of the electrode for oxygen evolution reaction in 50g•L^-1Zn²⁺+150g•L^-1H₂SO₄ solutions have been studied. The results show that the best activity of the electrodes obtained A1/conductive coating was electrodepositing PbO₂ in alkaline lead solutions firstly, then plating PbO₂ in acidic lead nitrate solutions. This can be attributed to the conductivity of the substrate, the crystal phase structure and property of PbO₂. SEM-EDX analysis shows the beta-form, deposited from acidic solutions of Pb(II), has a distorted rutite structure, and the alpha-form, deposited from alkaline solutions, has the spherical cell. The high non- stoichiometry of PbO2 was obtained in alkaline lead solutions.

Abstract: A convincing interpretation to hexagonal prism ordered-arrangement and self-ordering cell in porous anodic alumina (PAA) is absent up to now. Based on the growth model of oxygen bubble mould effect (OBME) for PAA, a satisfactory explanation for the growth process of hexagonal cells is proposed. The columnar pores and hexagonal cells result from the oxide growth embracing oxygen bubbles. The avalanche electron multiplication at critical thickness dc leads to electronic current which gives rise to the evolution of oxygen gas under anion-contaminated alumina (ACA) layer. The holes on the surface are usually irregular whereas the pores under the surface layer (ACA layer) are big and regular. The thickness of the barrier oxide layer remains constant due to continuous releasing of the oxygen bubbles at the critical thickness. The self-ordering of cell arrangement and the ordered morphology are related to the dissolving process of the ACA layer on PAA surface.

Abstract: This review paper represents photocatalytic properties of metal cation-doped TiO2 (rutile) and SrTiO3 photocatalysts for O2 evolution from an aqueous silver nitrate solution and H2 evolution from an aqueous methanol solution under visible light irradiation. Photocatalytic activities for the O2 evolution of Cr/Sb and Rh/Sb-codoped TiO2 are strongly dependent on the codoping ratio and the amount of doped chromium and rhodium. The codopant controls the oxidation number of doped chromium and rhodium. Rh-doped SrTiO3 in which the doped Rh species possesses a reversible redox property is active for the H2 evolution reaction under visible light irradiation. Overall water splitting under visible light irradiation proceeds with Z-scheme photocatalyst systems consisting of the Rh-doped SrTiO3 as a H2 evolution photocatalyst combined with BiVO4 as an O2 evolution photocatalyst and an Fe3+/Fe2+ electron mediator.

Abstract: Dense ceramic anodes of perovskite-type La1-x-ySrxCo1-zAlzO3-δ ( x = 0.45-0.70; y = 0- 0.05; z = 0-0.20) and K2NiF4-type La2Ni1-xMexO4+δ (Me = Co, Cu; x = 0-0.20), synthesized by the glycine-nitrate technique, were assessed for oxygen evolution in alkaline media. The lowest overpotentials are observed for (La0.3Sr0.7)0.97CoO3-δ, which exhibits a significant oxygen deficiency in combination with high conductivity associated with the A-site cation nonstoichiometry compensation mechanism via Co4+ formation. Perovskite-type cobaltite anodes are essentially stable in alkaline solutions, whilst La2NiO4-based electrodes exhibit degradation at the potentials where the oxygen evolution occurs, probably due to the electrochemical oxygen intercalation in the lattice.

Abstract: Ceramic anodes, made of perovskite-type rare-earth and strontium cobaltites substituted in both sublattices, exhibit a high electrocatalytic activity towards oxygen evolution in alkaline media. This work analyzes the relationships between cation composition, defect structure, electronic conductivity and electrochemical performance for a wide group of perovskite-like cobaltites, including Ln1-yAyCoO3-δ (Ln= Pr, Nd, Sm; A= Sr, Ca; y= 0-0.4), La1-x-ySrxBiyCoO3-δ (x= 0-0.6, y= 0-0.1), La0.7-xSr0.3CoO3-δ (x= 0-0.10), Sr1-xBaxCoO3-δ (x= 0.1-0.2) and SrCo1-yMyO3-δ (M=Fe, Ni, Ti, Cu; y= 0.1-0.6). The materials were prepared by the standard ceramic technique and characterized employing XRD, TGA, iodometric titration, and total conductivity measurements. A relatively high electrochemical performance in alkaline solutions was observed for (La,Sr)CoO3-based compositions with a moderate A-site deficiency. For SrCoO3-based materials, an increase in the oxygen evolution rate was found when co-substituting cobalt with several transition metal cations, such as Fe3+/4+ and Cu2+/3+. The results show that, in general, the key composition-related factors influencing electrochemical activity in alkaline media include the oxygen vacancy concentration, the average positive charge density in the crystal lattice, and possible blocking of active sites on the electrode surface.