Oluwaniyi Mabayoje

Visible-light-enhanced interactions of hydrogen sulfide with composites of zinc (oxy)hydroxide with graphite oxide and graphene.

Composites of zinc(oxy)hydroxide-graphite oxide and of zinc(oxy)hydroxide-graphene were used as adsorbents of hydrogen sulfide under ambient conditions. The initial and exhausted samples were characterized by XRD, FTIR, potentiometric titration, EDX, thermal analysis, and nitrogen adsorption. An increase in the amount of H(2)S adsorbed/oxidized on their surfaces in comparison with that of pure Zn(OH)(2) is linked to the structure of the composite, the relative number of terminal hydroxyls, and the kind of graphene-based phase used. Although terminal groups are activated by a photochemical process, the graphite oxide component owing to the chemical bonds with the zinc(oxy)hydroxide phase and conductive properties helps in electron transfer, leading to more efficient oxygen activation via the formation of superoxide ions. Elemental sulfur, zinc sulfide, sulfite, and sulfate are formed on the surface. The formation of sulfur compounds on the surface of zinc(oxy)hydroxide during the course of the breakthrough experiments and thus Zn(OH)(2)-ZnS heterojunctions can also contribute to the increased surface activity of our materials. The results show the superiority of graphite oxide in the formation of composites owing to its active surface chemistry and the possibility of interface bond formation, leading to an increase in the number of electron-transfer reactions.

Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions.

Facile growth of porous Fe2V4O13 films for photoelectrochemical water oxidation

Porous n-type Fe2V4O13 films on FTO substrates were prepared by a simplified successive ion layer adsorption and reaction method and characterized as photoelectrodes for photoelectrochemical (PEC) water oxidation. Synthesis parameters such as film thickness and annealing temperatures and durations were investigated to optimize the PEC performance. A band gap of ∼2.3 eV and a flat band potential of 0.5 V vs. RHE make Fe2V4O13 a promising photoanode material. Water oxidation was kinetically limited at the surface of Fe2V4O13 film as confirmed by tests in electrolyte with a hole scavenger (Na2SO3). Improved PEC performance was achieved by Mo and W doping because of enhanced carrier densities. The best performance was obtained by 2.5% W-doped Fe2V4O13 films (actual 0.8% W-doped), which efficiently oxidize water to O2via photogenerated holes as confirmed by oxygen evolution measurements. Moreover, the Fe2V4O13 photoanode displayed very stable photocurrent under illumination. Due to the suitable band gap and valence band position, Fe2V4O13 is a promising photoanode for solar water splitting. Co-catalyst loading and doping optimization are identified as routes to improve this materials performance further.

Band gap energies of solar micro/meso-porous composites of zinc (hydr)oxide with graphite oxides

The band gap energies of micro/meso-porous zinc (hydr)oxide and its composites with 2 wt. % and 5 wt. % graphite oxides are reported using three optical characterization techniques. The obtained energy gaps (from 2.84 eV to 2.95 eV) of the composites are smaller than that for zinc oxide (∼3.2 eV) and zinc (hydr)oxide (∼3.06 eV). The band gap narrowing of the composite materials is due to the presence of defects, larger particle size, and weaker confinement. The bonds between zinc (hydr)oxide lattice and the carbon of graphene phase also contribute to this phenomenon. The structural properties of these materials are presented using Transmission Electron Microscopy, Scanning Tunneling Electron Microscopy, X-Ray analysis, and Two-Photon Fluorescence imaging Microscopy.

NH3-assisted chloride flux-coating method for direct fabrication of visible-light-responsive SrNbO2N crystal layers

Perovskite-type SrNbO2N crystal layers were prepared on niobium substrates by using an NH3-assisted chloride flux-coating method. The optimization of synthesis parameters (holding temperature and strontium source : flux molar ratio) was performed using a NaCl–KCl flux. By choosing the optimal synthesis conditions, platelet SrNbO2N crystals were grown over the entire substrate surface, and each SrNbO2N platelet has a single-crystalline structure in a cubic symmetry. The optimal crystal layer possesses a well-adhered SrNbO2N/NbNx/Nb structure and absorbed photons with wavelengths up to 680 nm. In addition, the optimal SrNbO2N/NbNx photoelectrode was used for photoelectrochemical water oxidation (2H2O → 4H+ + 4e− + O2↑), as one half of the water splitting reaction. A photocurrent density of 113 μA cm−2 at 1.23 VRHE was recorded on the SrNbO2N/NbNx electrode without any additional co-catalyst loading and treatment under simulated sunlight, due to the higher crystallinity of SrNbO2N and higher interface-adhesion of the SrNbO2N/NbNx/Nb structure, which suppress the recombination of photogenerated electrons and holes at the defects and lead to an increase of the photogenerated electron collection efficiency in a niobium substrate, respectively. This study is the first to address the fabrication of quaternary oxynitride crystal layers on a conductive substrate using an NH3-assisted flux-coating method.