RESUMEN
It is well known that the trivacant anions α-B-[XW9O33]9- react with vanadyl ions to give the sandwich-type polyoxometalates [(VIVO)3(XW9O33)2]12- with X = AsIII or SbIII. Nevertheless, the oxidized derivatives have been obtained selectively by electrochemical oxidation from the fully reduced derivatives [(VIVO)3(XW9O33)2]12- allowing full characterization both in solution using UV-vis and multinuclear (17O, 51V, and 183W) NMR spectroscopies and in the solid state by single-crystal X-ray diffraction. Structural analysis of the oxidized [(VVO)3(XW9O33)2]9- polyanions is consistent with the idealized D3h symmetry, while solution studies reveal a fair hydrolytic stability in a wide pH range from 0 to 6. Besides, the D3h polyanions either as reduced or oxidized forms [(VO)3(AsW9O33)2]9/12- have been identified as the thermodynamic product that results from the conversion of the C2v polyanion [(H2O)(VO)3(AsW9O33)2]9/12- through moderate heating. Conversely, the SbIII-containing derivative gives exclusively the D3h polyanion, probably either due to the extended lone pair of the trigonal SbIII heterogroup that prevents the formation of the C2v arrangement or the lability of the oxo-metalate bonds that favor chemical exchange. The electrochemical studies of sandwich-type polyoxometalates revealed that each {VâO} group gives rise to a one-electron transfer process. At last, the redox properties appear strongly altered in the 0.3-5 pH range, consistent with proton-coupled electron transfers.
Asunto(s)
Vanadio , Aniones , Modelos Moleculares , Oxidación-Reducción , Polielectrolitos , Vanadio/químicaRESUMEN
Host-guest complexes between native cyclodextrins (α-, ß- and γ-CD) and hybrid Lindqvist-type polyoxovanadates (POVs) [V6 O13 ((OCH2 )3 C-R)2 ]2- with R = CH2 CH3 , NO2 , CH2 OH and NH(BOC) (BOC = N-tert-butoxycarbonyl) were studied in aqueous solution. Six crystal structures determined by single-crystal X-ray diffraction analysis revealed the nature of the functional R group strongly influences the host-guest conformation and also the crystal packing. In all systems isolated in the solid-state, the organic groups R are embedded within the cyclodextrin cavities, involving only a few weak supramolecular contacts. The interaction between hybrid POVs and the macrocyclic organic hosts have been deeply studied in solution using ITC, cyclic voltammetry and NMR methods (1D 1 H NMR, and 2D DOSY, and ROESY). This set of complementary techniques provides clear insights about the strength of interactions and the binding host-guest modes occurring in aqueous solution, highlighting a dramatic influence of the functional group R on the supramolecular properties of the hexavanadate polyoxoanions (association constant K1:1 vary from 0 to 2 000â M-1 ) while isolated functional organic groups exhibit only very weak intrinsic affinity with CDs. Electrochemical and calorimetric investigations suggest that the driving force of the host-guest association involving larger CDs (ß- and γ-CD) is mainly related to the chaotropic effect. In contrast, the hydrophobic effect supported by weak attractive forces appears as the main contributor for the formation of α-CD-containing host-guest complexes. In any cases, the origin of driving forces is clearly related to the ability of the macrocyclic host to desolvate the exposed moieties of the hybrid POVs.
Asunto(s)
Ciclodextrinas , Cristalografía por Rayos X , Interacciones Hidrofóbicas e Hidrofílicas , Conformación Molecular , AguaRESUMEN
The present work evaluates the potential of the photocatalysis (PC) process for the degradation of butylparaben (BPB). Relatively high treatment efficiency was achieved by comparison to photochemical process. Prior to photocatalytic degradation, adsorption (AD) of BPB occurred on the titanium dioxide (TiO2)-supported catalyst. AD was described by Langmuir isotherm (KL = 0.085 L g(-1), qm = 4.77 mg g(-1)). The influence of angle of inclination of the reactor, pH, recirculation flow rate and initial concentration of BPB were investigated. The PC process applied under optimal operating conditions (recirculation flow rate of 0.15 L min(-1), angle of inclination of 15°, pH = 7 and 5 mg L(-1) of BPB) is able to oxidize 84.9-96.6% of BPB and to ensure around 38.7% of mineralization. The Langmuir-Hinshelwood kinetic model described well the photocatalytic oxidation of BPB (k = 7.02 mg L(-1) h(-1), K = 0.364 L mg(-1)).
Asunto(s)
Parabenos/química , Procesos Fotoquímicos , Titanio/química , Catálisis , Cinética , Oxidación-ReducciónRESUMEN
In order to remove pesticides from water, a basic photoreactor has been built. We evaluated the performance of this photoreactor using two commercial photocatalytic materials from Ahlstrom group and from Saint-Gobain, with solar and artificial UV-lamps. We compared the kinetics of photocatalytic degradation and mineralization of Diuron in the same reactor with of both photocatalyst supports. We showed that Diuron is easily degraded under solar or artificial irradiation, while the kinetics of mineralization in the same condition are very slow. The behaviour of these commercial materials has been studied after several uses in the same conditions. We showed the effectiveness of this basic and cheap photoreactor for the elimination of pesticide in water.