Aminophosphonates were chosen for a first step functionalization of TiO 2 grown on titanium, as they possess a phosphonate group on one end, that can be exploited for coupling with the oxide surface, and an amino group on the other end to enable further functionalization of the surface. The deposition of aminophosphonates with different chain lengths (6 and 12 methylenes) was investigated. Oxygen plasma treatment proved useful in increasing the number of −OH groups at the TiO 2 surface, thus helping to anchor the aminophosphonates. By combining different surface-sensitive experimental techniques, we found the existence of a discontinuous monolayer where the molecules are covalently coupled to the TiO 2 surface. For the molecules with longer chains, we find evidence of their covalent coupling to the surface through Ti−O−P bond formation, of the exposure of the amino groups at the outer surface, and of an increase in the order of the layer upon thermal annealing.
Nontoxic and biodegradable pollutant-mobilizing agents, instead of chemical surfactants, were tested in the washing of an actual-site chloroaromatic-contaminated soil. A soil historically contaminated by chlorinated anilines and benzenes, thiophenes and several polycyclic aromatic hydrocarbons was subjected to washing by suspending it (15% w/v) in water or in water with 1.0% (w/v) beta-clodextrin (beta-CD), hydroxypropyl-beta-cyclodextrin (HP-beta-CD), rhamnolipid (RL), dissolved humic substances (HS), or Triton X-100 (TX) in shaken batch reactors for 24 hr. The resulting wastewaters were amended with nutrients and treated aerobically in shaken reactors for 65 days. The biogenic agents markedly enhanced (by 237%, beta-CD; 265%, HP-beta-CD; 400%, RL; 566%, HS) the capability of water of eluting organic pollutants from the soil. TX enhanced the overall pollutant removal by about 660%; however, a lower depletion of the initial soil ecotoxicity, along with a more extensive impact on the soil organic matter, was observed. Furthermore, TX adversely affected the bioremediation of the resulting effluent by apparently inducing a premature decrease of specialized bacterial biomass. By contrast, the biogenic agents, and in particular HS and RL, sustained the biodegradation and dechlorination of pollutants by apparently enhancing the availability of specialized bacteria in the reactors. Thus, the biogenic agents proposed here seem to be promising nontoxic and nonaggressive soil washing agents for the integrated physicochemical (washing) and biological (aerobic posttreatment) restoration of poorly bioremediable (chloro) organics-contaminated soils.
Excitons dominate
the light absorption and re-emission spectra
of monolayer transition-metal dichalcogenides (TMD). Microscopic investigations
of the excitonic response in TMD almost invariably extract information
from the radiative recombination step, which only constitutes one
part of the picture. Here, by exploiting imaging spectroscopic ellipsometry
(ISE), we investigate the spatial dependence of the dielectric function
of chemical vapor deposition (CVD)-grown WS2 flakes with
a microscopic lateral resolution, thus providing information about
the spatially varying, exciton-induced light absorption in the monolayer
WS2. Comparing the ISE results with imaging photoluminescence
spectroscopy data, the presence of several correlated features was
observed, along with the unexpected existence of a few uncorrelated
characteristics. The latter demonstrates that the exciton-induced
absorption and emission features are not always proportional at the
microscopic scale. Microstructural modulations across the flakes,
having a different influence on the absorption and re-emission of
light, are deemed responsible for the effect.
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