Photocatalytic-induced cleaving of the ether C–O bond in model lignin compounds was studied with a closely-coupled compo-site material consisting of Ni(OH)2 and gold nanoparticles (NPs) on a zirconia support (Au/ZrO2–Ni(OH)2). The three important ether bond types consisting of α-O-4, β-O-4, and 4-O-5 linkages can all be cleaved using this catalyst at reaction temperatures 40, 85 and 95 °C when under low-flux visible light irradiation. The Au NPs action as a light-harvesting antenna provided light-generated hot electrons that reduced Ni2+ to Ni0. The Ni0 was the active catalytic site where reductive cleavage of ether C–O bonds occurred while it was oxidized to Ni2+ to complete the catalysis cycle. The plasmonic antenna system with supported Ni(OH)2 exhibited better ability for the catalytic reductive ether cleavages under visible light irradiation compared to photocata-lysts of Au NPs and Ni2+ ions immobilized on alumina fibers.
SnS2/MoS2 heterojunction nanocomposite was prepared by a one-step hydrothermal synthesis method. The nanocomposite exhibited much improved photocatalytic hydrogen evolution performance in CO2 saturated solution compared with pure MoS2 and SnS2 samples. The improved photocatalytic activity was attributed to the S-scheme heterojunction structure between SnS2 quantum dots and MoS2 nanosheets which facilitate electron-hole separation both in MoS2 and SnS2. In the S-scheme structure, the strong reduction ability of SnS2 quantum dots was well maintained for the improved H2 evolution. In situ DRIFT studies allowed us to suggest reaction pathways from CO2 and H2O to photocatalytic H2, CO, and CH4 generation.
Fungicide application in viticulture is a major source of surface and groundwater contamination. It is therefore essential to find solutions to stop this environmental pollution. Heterogeneous photocatalysis is an advanced oxidation method for the degradation and mineralization of organic pollutants in water. TiO2 P25 photocatalyst in suspension has been used for removing the fungicides Myclobutanil and Penconazol, and their respective commercial formulations Systhane and Topas, in contaminated water. The apparent kinetic constants kapp of fungicides removal over 30 min batch treatment was higher for a mixture of pure molecules of Myclobutanil and Penconazol than for a mixture of their commercial formulations (17.5 × 10−3 by comparison with 10.3 × 10−3 min−1 for Myclobutanil, and 10.0 × 10−3 by comparison with 2.80 × 10−3 min−1 for Penconazol). TOC removal constants kTOC were similar for the two mixtures, due to the presence of mineral and organic additives in the commercial formulations. To easily recover the photocatalyst after fungicide removal, TiO2 P25 has been supported on β-SiC foam. Fungicides degradation was lower with supported photocatalysts than with the suspension of photocatalyst nanoparticles (NPs) because of a lower concentration of active sites on the supported photocatalyst than in the catalyst suspension. However, catalyst recovery and reuse after fungicide removal is obviously easier with TiO2/β-SiC material than with a suspension of TiO2 which requires long and expensive filtration operations.
This article commemorates the outstanding Russian scientists E.F. Gross and A.N. Terenin. It revisits their successors’ efforts to develop Terenin’s idea of using excitons, discovered by Gross, for photocatalytic redox reactions on wide-gap semiconductors. Terenin proposed ZnO as the subject of study. To explore the possibility of replacing photogenerated electrons and holes in a redox reaction by an exciton being a quasi-neutral particle, the test reaction of the photoactivated oxygen isotope exchange (POIE) was studied. It was found that many years of initial unsuccessful attempts were due to the fact that the exciton energy is spent on luminescence. In our experiments, the excitons decayed non-radiatively, and the long-lived electron-donor F-type and hole V-type active centers were formed by creating the 2D surface nanostructure ZnO/ZnO1−x/O−. These centers allowed to obtain the reaction efficiency 5–8 times higher than with the interband transitions. Thus, the developed 2D surface nanostructure ZnO/ZnO1−x/O− resolved the problem of using an exciton in photocatalysis and demonstrated the perspective of this nanostructure as an efficient photocatalyst.
