Enhanced Electrocatalytic Oxygen Reduction Reaction of TiO2 Nanotubes by Combining Surface Oxygen Vacancy Engineering and Zr Doping.

This work examines the cooperative effect between Zr doping and oxygen vacancy engineering in anodized TiO2 nanotubes (TNTs) for enhanced oxygen reduction reactions (ORRs). Zr dopant and annealing conditions significantly affected the electrocatalytic characteristics of grown TNTs. Zr doping results in Zr4+ substituted for Ti4+ species, which indirectly creates oxygen vacancy donors that enhance charge transfer kinetics and reduce carrier recombination in TNT bulk. Moreover, oxygen vacancies promote the creation of unsaturated Ti3+(Zr3+) sites at the surface, which also boosts the ORR interfacial process. Annealing at reductive atmospheres (e.g., H2, vacuum) resulted in a larger increase in oxygen vacancies, which greatly enhanced the ORR activity. In comparison to bare TNTs, Zr doping and vacuum treatment (Zr:TNT-Vac) significantly improved the conductivity and activity of ORRs in alkaline media. The finding also provides selective hydrogen peroxide production by the electrochemical reduction of oxygen.

Enhanced electrocatalytic oxygen redox reactions of iron oxide nanorod films by combining oxygen vacancy formation and cobalt doping.

A synergistic effect of Co-doping and vacuum-annealing on electrochemical redox reactions of iron oxide films is demonstrated in the present work. In this research, a series of defect-rich iron oxy/hydroxide nanorod arrays: α-FeOOH, Fe2O3, and FeOx nanorod thin film catalysts were synthesized via a hydrothermal approach followed by thermal and vacuum treatments. Besides, a cobalt doping process was employed to prepare the thin film of Co-doped FeOx nanorods. The morphology, crystallinity, and electrochemical activities of Co-doped oxygen-deficient FeOx (Co-FeOx/FTO) show strong correlations with metal concentration and thermal treatments. The electrochemical measurements demonstrated that the as-deposited Co-doped FeOx NR catalyst could achieve a maximum OER current of 30 mA cm-2, which was six times greater than that recorded by as-deposited Co-doped FeOOH NR catalysts (5.7 mA cm-2) at 1.65 V vs. RHE, confirming the superior electrocatalytic OER activity at the as-deposited Co-doped FeOx NR catalyst after cobalt doping. It is believed that these results are attributed to two factors: the synergistic effect of Co doping and the defect-rich nature of FeOx nanorod catalysts that are used in sustainable energy systems.

Foam Synthesis of Nickel/Nickel (II) Hydroxide Nanoflakes Using Double Templates of Surfactant Liquid Crystal and Hydrogen Bubbles: A High-Performance Catalyst for Methanol Electrooxidation in Alkaline Solution.

This work demonstrates the chemical synthesis of two-dimensional nanoflakes of mesoporous nickel/nickel (II) hydroxide (Ni/Ni(OH)2-NFs) using double templates of surfactant self-assembled thin-film and foam of hydrogen bubbles produced by sodium borohydride reducing agent. Physicochemical characterizations show the formation of amorphous mesoporous 2D nanoflakes with a Ni/Ni(OH)2 structure and a high specific surface area (165 m2/g). Electrochemical studies show that the electrocatalytic activity of Ni/Ni(OH)2 nanoflakes towards methanol oxidation in alkaline solution is significantly enhanced in comparison with that of parent bare-Ni(OH)2 deposited from surfactant-free solution. Cyclic voltammetry shows that the methanol oxidation mass activity of Ni/Ni(OH)2-NFs reaches 545 A/cm2 gcat at 0.6 V vs. Ag/AgCl, which is more than five times higher than that of bare-Ni(OH)2. Moreover, Ni/Ni(OH)2-NFs reveal less charge transfer resistance (10.4 Ω), stable oxidation current density (625 A/cm2 gcat at 0.7 V vs. Ag/AgCl), and resistance to the adsorption of reaction intermediates and products during three hours of constant-potential methanol oxidation electrolysis in alkaline solution. The high-performance electrocatalytic activity of Ni/Ni(OH)2 nanoflakes is mainly derived from efficient charge transfer due to the high specific surface area of the 2D mesoporous architecture of the nanoflakes, as well as the mass transport of methanol to Ni2+/Ni3+ active sites throughout the catalyst layer.

Structure and electrochemical activity of nickel aluminium fluoride nanosheets during urea electro-oxidation in an alkaline solution.

An electrocatalyst of potassium nickel aluminium hexafluoride (KNiAlF6) nanosheets has been prepared using solid-phase synthesis at 900 °C. X-ray diffraction, scanning electron microscopy, and conductivity studies confirmed the formation of KNiAlF6 nanosheets having a cubic defect pyrochlore structure with an average thickness of 60-70 nm and conductivity of 1.297 × 103 S m-1. The electrochemical catalytic activity of the KNiAlF6 nanosheets was investigated for urea oxidation in alkaline solution. The results show that the KNiAlF6 nanosheets exhibit a mass activity of ∼395 mA cm-2 mg-1 at 1.65 V vs. HRE, a reaction activation energy of 4.02 kJ mol-1, Tafel slope of 22 mV dec-1 and an oxidation onset potential of ∼1.35 V vs. HRE which is a significant enhancement for urea oxidation when compared with both bulk Ni(OH)2 and nickel hydroxide-based catalysts published in the literature. Chronoamperometry and impedance analysis of the KNiAlF6 nanosheets reveal lower charge transfer resistance and long-term stability during the prolonged urea electro-oxidation process, particularly at 60 °C. After an extended urea electrolysis process, the structure and morphology of the KNiAlF6 nanosheets were significantly changed due to partial transformation to Ni(OH)2 but the electrochemical activity was sustained. The enhanced electrochemical surface area and the replacement of nickel in the lattice by aluminium make KNiAlF6 nanosheets highly active electrocatalysts for urea oxidation in alkaline solution.