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Recently the urea and urinated wastewater electrolysis process has shown promising technology for hydrogen fuel green production in addition to denitrification of wastewater. However, to make the process economically valuable, the electrocatalysts nanoarchitecture, nanometer size, shape, facets, and composition need to be engineered to boost the urea oxidation reaction (UOR). This work demonstrates a simple and novel approach to the synthesis of mesoporous nickel phosphate nanoparticles (meso-NiPO) via chemical deposition from a surfactant liquid crystal template. Typically, the nickel ions dissolved in the aqueous domain of the hexagonal liquid crystalline phase of the Brij®78 template were chemically reacted with the sodium phosphate solution to precipitate the mesoporous nickel phosphate nanoarchitecture after washing up the surfactant. The physicochemical characterizations show the meso-NiPO exhibits an amorphous highly mesoporous structure with a higher specific surface area (43.50 m2/g) compared to the bare nickel phosphate (bare-NiPO, 4.26 m2/g) prepared in the absence of surfactant. The electrochemical performance of meso-NiPO electrocatalyst for the urea oxidation reaction in alkaline solution exhibits superior activity including a lower oxidation onset potential (0.30 V vs. Ag/AgCl), charge transfer resistance (3.35 O) and mass activity of 700.7 mA/cm2 mg at the oxidation potential of 0.6 V vs. Ag/AgCl. Moreover, the meso-NiPO reveals long-term stability, and 97.5% of the steady-state oxidation current was maintained after the 3-hour urea electrolysis test. Using an H-shape urea electrolyzer, the corresponding cathodic hydrogen production rate reached 415 µmol/h and a Faradic efficiency of 96.8 % at an applied bias of 2.0 V. The electroactivity high performance of the mesoporous nickel phosphate is ascribed to the high specific surface area and mesoporous architecture that provide efficient charge transfer, as well as mass transport of the electroactive species. The chemical deposition from a surfactant liquid crystal template has the advantages of a one-pot template, applicable to the synthesis of a wide range of nanomaterials with various compositions and nanoarchitectures at room temperature for application in electrochemical energy production and storage systems.

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.

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.