RESUMO

The photocatalytic hydrogen evolution reaction (HER) by water splitting has been studied, using catalysts based on crystalline TiO2 nanowires (TiO2NWs), which were synthesized by a hydrothermal procedure. This nanomaterial was subsequently modified by incorporating different loadings (1%, 3% and 5%) of gold nanoparticles (AuNPs) on the surface, previously exfoliated MoS2 nanosheets, and CeO2 nanoparticles (CeO2NPs). These nanomaterials, as well as the different synthesized catalysts, were characterized by electron microscopy (HR-SEM and HR-TEM), XPS, XRD, Raman, Reflectance and BET surface area. HER studies were performed in aqueous solution, under irradiation at different wavelengths (UV-visible), which were selected through the appropriate use of optical filters. The results obtained show that there is a synergistic effect between the different nanomaterials of the catalysts. The specific area of the catalyst, and especially the increased loading of MoS2 and CeO2NPs in the catalyst substantially improved the H2 production, with values of ca. 1114 µm/hg for the catalyst that had the best efficiency. Recyclability studies showed only a decrease in activity of approx. 7% after 15 cycles of use, possibly due to partial leaching of gold nanoparticles during catalyst use cycles. The results obtained in this research are certainly relevant and open many possibilities regarding the potential use and scaling of these heterostructures in the photocatalytic production of H2 from water.

Assuntos

Ouro , Nanopartículas Metálicas , Ouro/química , Molibdênio , Hidrogênio/química , Água/química , Biomimética

RESUMO

Different Ag@TiO2 and Ag@ZnO catalysts, with nanowire (NW) structure, were synthesized containing different amounts of silver loading (1, 3, 5, and 10 wt.%) and characterized by FE-SEM, HRTEM, BET, XRD, Raman, XPS, and UV-vis. The photocatalytic activity of the composites was studied by the production of hydrogen via water splitting under UV-vis light and the degradation of the antibiotic ciprofloxacin. The maximum hydrogen production of all the silver-based catalysts was obtained with a silver loading of 10 wt.% under irradiation at 500 nm. Moreover, 10%Ag@TiO2 NWs was the catalyst with the highest activity in the hydrogen production reaction (1119 µmol/hg), being 18 times greater than the amount obtained with the pristine TiO2 NW catalyst. The most dramatic difference in hydrogen production was obtained with 10%Ag@TiO2-P25, 635 µmol/hg, being 36 times greater than the amount reported for the unmodified TiO2-P25 (18 µmol/hg). The enhancement of the catalytic activity is attributed to a synergism between the silver nanoparticles incorporated and the high surface area of the composites. In the case of the degradation of ciprofloxacin, all the silver-based catalysts degraded more than 70% of the antibiotic in 60 min. The catalyst that exhibited the best result was 3%Ag@ZnO commercial, with 99.72% of degradation. The control experiments and stability tests showed that photocatalysis was the route of degradation and the selected silver-based catalysts were stable after seven cycles, with less than 1% loss of efficiency per cycle. These results suggest that the catalysts could be employed in additional cycles without the need to be resynthesized, thus reducing remediation costs.