An efficient ZnS-UV photocatalysts generated in situ from ZnS(en)0.5 hybrid during the H2 production in methanol–water solution

Highly active ZnS-UV was obtained in situ from ZnS(en)_0.5 hybrid during the hydrogen formation using a methanol–water solution under UV irradiation. X-ray diffraction patterns and UV spectroscopy for both ZnS-UV and ZnS-400 obtained from the calcination of the ZnS(en)_0.5 hybrid showed similar structural and photophysical properties; however, the efficiency of the ZnS-UV semiconductor was 7 times higher (4825 μmol h⁻¹ g⁻¹) compared to the ZnS-400. The highest H₂ production was obtained using a UV lamp of very low intensity (2.2 mW cm⁻¹) and it is attributed to a quantum size effect caused by the slow elimination of ethylenediamine (en) in the structural ZnS layer during the UV irradiation.     

Stabilized β-Bi2O3 nanoparticles from (BiO)4CO3(OH)2 precursor and their photocatalytic properties under blue light

Stabilized tetragonal Bi₂O₃ nanoparticles (β-Bi₂O₃) were obtained by annealing treatments of amorphous Bi-based precursors, obtained by chemical precipitations, at temperatures between 350 and 450?°C. The formation of the stabilized β-Bi₂O₃ phase was possible by using (BiO)₄CO₃(OH)₂ while other precursors such as amorphous bismuth carbonate ((BiO)₂CO₃) and amorphous basic bismuth nitrate (Bi₆O₆(OH)₂(NO₃)₄·2H₂O) led to the formation of the thermodynamically stable monoclinic α-Bi₂O₃ and Bi₅O₇NO₃ phases. The Bi-based precursors were prepared by the chemical precipitation method at room temperature in ethylenediamine-solvent varying the HNO₃/Bi³⁺ molar ratio (10, 26 and 56). The physicochemical properties of the three as-prepared amorphous precursors and the formed-after-calcination β-Bi₂O₃, α-Bi₂O₃ and Bi₅O₇NO₃ phases were analyzed by X-ray diffraction, scanning electron microscopy, thermogravimetry, X-ray photoelectron spectroscopy (XPS), FTIR analysis, diffuse reflectance spectroscopy and surface area by BET method. The photocatalytic activity of all annealed solids containing the β-Bi₂O₃ phase was tested in the photodegradation of the indigo carmine (IC) dye under specific blue light. A schematic diagram of the Bi₂O₃ phases obtained as a function of the annealing conditions and initial amorphous precursor is proposed and explained in terms of the amount of CO₃^2-, NO₃^- and amine (ENH₂²⁺ ? ENH⁺) ions present in each bismuth precursor.     

Boosting the photocatalytic hydrogen production of TiO2 by using copper hexacyanocobaltate as co-catalyst

The development of cheap and efficient co-catalysts is crucial to improve the performance of well-known photocatalysts towards the hydrogen evolution reaction. Here, copper hexacyanocobaltate was evaluated for the first time as a potential candidate to be used as co-catalyst coupled with conventional TiO₂. Copper hexacyanocobaltate was formed by chemical precipitation in the presence of TiO₂, without needing further treatments. The composite exhibited paramount performance towards hydrogen generation, surpassing by up to 16 times the behavior reached with bare TiO₂. This composite also overcome the performance of conventional TiO₂ modified with copper and cobalt oxides derived from copper hexacyanocobaltate. The enhanced behavior of TiO₂/Cu₃[Co(CN)₆]₂ composite was promoted by the efficient separation of photogenerated charge carries, and the faster charge transfer from photocatalyst towards species in solution, as it was proved by the photoelectrochemical characterization of the materials. Furthermore, the composite experienced a slight detriment (15%) in its hydrogen production rate after four consecutive photocatalyst tests. This variation was attributed to the slow leaching of copper in the co-catalyst caused by its partial transformation into metal hydroxides, as it was suggested by the ex-situ XPS characterization. Nevertheless, the structural characterization evinced the presence of the Cu₃[Co(CN)₆]₂ in the composite after long-term use. This study should be considered a proof of concept on a reliable route to obtain appropriate composites for hydrogen production using light as primary energy source.     

Microparticles of α-Bi2O3 Obtained from Bismuth Basic Nitrate [Bi6O6(OH)2(NO3)4·2H2O] with Photocatalytic Properties

Topics in Catalysis - Alpha phase bismuth oxide (α-Bi2O3) microparticles were prepared through the annealing at 600 °C of basic bismuth nitrate [Bi6O6(OH)2(NO3)4·2H2O]...