Acidity of SiO2-Supported Metal Oxides in the Presence of H2O Using the Adsorption Equilibrium Infrared Spectroscopy Method: 1. Adsorption and Coadsorption of NH3 and H2O on SiO2.

The present study is dedicated to the characterization (identification, heats of adsorption, and coverages) of the adsorbed species formed by the adsorption and coadsorption of NH3 and H2O on two SiO2 solids. Adsorption equilibrium infrared spectroscopy allowed us (a) to show that NH3 and H2O are mostly adsorbed on free SiOH groups via H bonds and (b) to determine their individual heats of adsorption: 53 and 49 kJ/mol, whatever be their coverages (Langmuir adsorption model), for NH3ads and H2Oads, respectively. These values consistent with the microcalorimetry literature data explain that their coverages are decreased upon NH3-H2O coadsorption, considering a competitive Langmuir model. However, the temperature-programmed adsorption equilibrium procedure achieved from MS data indicated that a minor amount of other NH3 species (not detected using Fourier-transform infrared) is more strongly adsorbed and that hydrolysis of SiOSi siloxane by H2O could occur in parallel. NH3-H2O coadsorption leads to the formation of NH4+ species, which involves H2O adsorbed species. Both NH3 and H2O are not adsorbed above 450 K, which means that the SiO2 contribution to the characterization of the acidity of metal oxide catalysts supported on SiO2 using NH3 as the probe molecule in the presence of H2O is negligible above this temperature.

Acidity of SiO2-Supported Metal Oxides in the Presence of H2O Using the AEIR Method: 2. Adsorption and Coadsorption of NH3 and H2O on TiO2/SiO2 Catalysts.

Two different TiO2/SiO2 compounds containing TiO2 nanodomains dispersed over SiO2 were investigated applying the AEIR method at the adsorption equilibrium of NH3 and H2O from 300 to 723 K, particularly for the measurement of the individual heats of adsorption of the different species on Lewis acidic sites (LAS) and Brønsted acidic sites (BAS) as evaluation of the strength of the sites. It revealed two types of NH3 adsorption sites: the first ones could correspond either to NH3 species H-bonded to free OH groups or to coordinated weak LAS (named L1). The second ones (L2) were attributed to strongest LAS similar to those present at the surface of TiO2 nanocrystallites. They also correspond to the stronger adsorption sites of H2O. Two types of Brønsted acid sites (BAS) were additionally evidenced by the AEIR method and proposed to be specifically located on the Si-O-Ti bridging bonds at the TiO2/SiO2 interface. The heats of adsorption of the different adsorbed species provided by the AEIR method were consistent with literature data on average values of the heats of adsorption of NH3 and H2O from microcalorimetry measurements. The surface acidity of the two compounds in the presence of H2O was determined using NH3-H2O coadsorption. At T ≥ 473 K, the NH3 species on the L2 sites were not significantly displaced from the surface whatever the partial pressure of H2O studied in agreement with the Temkin competitive model using the individual heats of adsorption of the NH3 and H2O species. This model also revealed the presence of a small amount of H2O species adsorbed on L2 sites allowing H2O dissociation or/and hydrolysis of SiOTi or TiOTi bridges, leading to the formation of a much higher amount of BAS. Therefore, this original work combining the AEIR method and the Temkin competitive model provided new insights for understanding water effects on acidic oxide catalysts.

Invasive rhino-orbital-cerebral aspergillosis in an immunocompetent patient.

INTRODUCTION: Rhino-orbital-aspergillosis (ROA) is a rare but serious disease in immunocompetent patients. Diagnosis is often delayed due to the absence of specific clinical symptoms. We describe the case of a patient who presented initially with ROA which spread progressively to the right ethmoid-sphenoid sinuses and then to the brain. OBSERVATION: A 61-year-old patient with a history of well-controlled diabetes presented with a sudden severe decrease in right visual acuity. Cerebral MRI showed the presence of an infiltrate in the right orbital apex extending to the homolateral cavernous sinus without any cerebral involvement. A diagnosis of right orbital myositis was made and corticosteroid therapy was started. His symptoms worsened progressively leading to quasi-blindness. A new MRI showed the development of right sphenoid-ethmoid osteolytic lesions. A fungal aetiology was suspected and tests for fungal biomarkers found a ß-(1-3)-D-glucan level of 99pg/ml but negative galactomannan. An ethmoid biopsy was performed for histological and mycological investigations, including the detection of Aspergillus DNA by qPCR. qPCR was positive and culture resulted in the isolation of multi-sensitive Aspergillus fumigatus. Treatment was initiated with voriconazole. Due to persistence of blindness and the appearance of a lesion extending to the right frontal lobe, surgical excision was performed followed by antifungal treatment for a total duration of 1year. The patient is currently stable, but has persistence of blindness in the right eye. CONCLUSION: Invasive ROA is a rare but serious disease in immunocompetent patients which should be evoked in the differential diagnosis of a tumour or vasculitis. Early diagnosis is essential for optimal management.

Invasive pulmonary aspergillosis in an ICU patient with Legionnaires' disease: A diagnostic challenge.

Aspergillus fumigatus can cause a wide range of diseases, from hypersensitivity to invasive infection. Invasive disease usually occurs in severely immunocompromised patients with deep and prolonged neutropenia. It is a less well-recognized complication in critically ill patients without traditional risk factors. We describe a case of early invasive pulmonary aspergillosis (IPA) secondary to Legionella pneumophila serogroup 1 pneumonia in a patient on an intensive care unit (ICU). In addition to commonly accepted risk factors for IPA in ICU patients, we hypothesis that L. pneumophilia pneumonia could enhance this type of infection. We also reviewed all published cases of coinfection with L. pneumophila and A. fumigatus to assess whether Legionnaires' disease could be a risk factor for IPA.

MoS2 formation induced by amorphous MoS3 species under lubricated friction.

Amide molybdate has been recently introduced as a friction modifier for tribological applications. Combined with zinc dithiophosphate (ZDDP) and fatty amines, it provides an ultralow friction coefficient. The ultimate product of Mo compound transformations in tribological contact, due to frictional heating and shearing, as well as chemical interactions with oil additives, is molybdenum sulfide (MoS2). Understanding the decomposition of amide molybdate leading to MoS2 is of primary importance to the optimization of the design of lubricant formulations. This study focuses on the investigation by Raman spectroscopy of amide molybdate decomposition intermediates. Raman spectra of tribofilms, obtained after friction tests under different temperatures and pressures, revealed the formation of an amorphous MoS3 intermediate coexisting with MoS2. However, under severe conditions, the tribofilms are mostly composed of MoS2.

Impregnation of decamolybdocobaltate heteropolyanions over γ-alumina: detailed description of the physico-chemical phenomena.

In this work, the physicochemical phenomena occurring during equilibrium impregnation of Anderson-like decamolybdocobaltate H(4)Co(2)Mo(10)O(38)(6-) heteropolyanion aqueous solutions over γ-Al(2)O(3) were described in detail comprising chemical analysis, pH measurements, Raman, and UV-vis spectra. For a surface density lower than 2.5 Mo atoms nm(-2), the buffering effect of the support leads to decomposition of H(4)Co(2)Mo(10)O(38)(6-) into monomolybdates MoO(4)(2-) and Co(2+) cobalt cations that are then adsorbed by electrostatic and covalent interactions with γ-alumina. Between 2.5 and 3.8 Mo atoms nm(-2), MoO(4)(2-) monomers condense into heptamolybdates Mo(7)O(24)(6-) that are then adsorbed by electrostatic interactions and H(4)Co(2)Mo(10)O(38)(6-) becomes stable because of the lowering of the pH. Above 3.8 Mo atoms nm(-2), the quantities of adsorbed MoO(4)(2-) and Mo(7)O(24)(6-) become much smaller than that of electrostatically adsorbed H(4)Co(2)Mo(10)O(38)(6-). Adsorption of preserved H(4)Co(2)Mo(10)O(38)(6-) could be consecutive to the decomposition of the first molecules leading to prior adsorption of MoO(4)(2-) and Co(2+), and decrease in the buffering effect of γ-Al(2)O(3) and in the pH value. For dry impregnation, the same physicochemical phenomena occur considering a given Mo surface density. The methodology used in this work to rationalize the preparation of hydrotreatment catalysts from H(4)Co(2)Mo(10)O(38)(6-) heteropolyanions can be transposed to any supported catalyst.

Decamolybdocobaltate heteropolyanions in aqueous solutions: chemistry driving their formation and domains of stability.

In the present study, aqueous solutions of decamolybdocobaltate H(4)Co(2)Mo(10)O(38)(6-) heteropolyanions were prepared from molybdenum oxide, cobalt carbonate precursors and hydrogen peroxide used as oxidizing agent. The preparation was optimized adding a consecutive hydrothermal treatment at 150 °C to obtain pure H(4)Co(2)Mo(10)O(38)(6-) aqueous solutions for Co/Mo atomic ratio of 0.5. Combining quantitative Raman and UV-visible measurements and chemometric methods, it was demonstrated that a mixture of H(4)Co(2)Mo(10)O(38)(6-) and octomolybdate Mo(8)O(26)(4-) species is obtained for Co/Mo ratios lower than 0.5, and the relative quantities of H(4)Co(2)Mo(10)O(38)(6-) are determined by the presence of Mo(8)O(26)(4-) species and by the quantity of Co(2+) countercations available in the solutions to ensure the electroneutrality. As these quantities can be predicted for each Co/Mo ratio, this finding allows rationalization of the preparation of heterogeneous catalysts using impregnation by H(4)Co(2)Mo(10)O(38)(6-) aqueous solutions. Parameters relevant of the impregnation step such as the pH, the Co/Mo ratio, and the molybdenum concentration were varied to determine the domains of stability of H(4)Co(2)Mo(10)O(38)(6-) heteropolyanions after formation. Stable from pH 1 to 4.5, this dimeric Anderson species is destabilized above pH 4.5; Co(2+), monomolybdate MoO(4)(2-) ions, and precipitates are then formed. For Co/Mo ratios lower than 0.5, the relative quantity of dimer does not vary with the pH and with a change of the Co/Mo ratio consecutive to the hydrothermal treatment. On the contrary, the coproduced Mo(8)O(26)(4-) species can be transformed into other isopolymolybdates varying the pH according to their domains of stability. For all of the ratios, H(4)Co(2)Mo(10)O(38)(6-) dimers were also shown to be stable in a wide range of molybdenum concentrations.

WOx/ZrO2 catalysts prepared by anionic exchange: in situ Raman investigation from the precursor solutions to the calcined catalysts.

W/ZrO(2) catalysts were prepared using anionic exchange of peroxotungstate species with hydroxyl groups of zirconium hydroxide at low pH. The solids were dried and calcined under air at 700 degrees C. Each step of this novel method of preparation was investigated by Raman spectroscopy. A reference sample was also prepared by incipient wetness impregnation of ZrO(2).n(H2O) with an ammonium tungstate solution and characterized throughout its preparation process. Complementary data were collected from X-ray diffraction, chemical analysis, surface area measurements, and thermal analysis. The Raman spectra of the H2WO4-H2O2 precursor solutions evidenced the presence of (W2O3(O2)4(H2O)2)(2-) dimers. These low-nuclearity species were exchanged with zirconium hydroxide at low pH. The Raman spectra of the dried solids did not reveal peroxotungstate species but were typical of tetrahedral (WO4)(2-) species. A slight agglomeration of W species was observed with an increase in the W content. However, for an equivalent W loading, a higher W dispersion was obtained by anionic exchange, compared to the impregnation method. Furthermore, a remarkable homogeneity of the exchanged samples was evidenced by the micro-Raman spectra. The in situ Raman spectra recorded during calcination characterized both crystalline phases and supported tungsten species. Significant modifications were observed during the calcination process. The exchanged and the impregnated samples, with the same W loading, evidenced a similar type of tungsten species with one W=O bond. However, their behavior during calcination up to 700 degrees C was different. This was attributed to different strengths of interaction with the support. Moreover, the spectra recorded after calcination on various points of the exchanged sample with a high W content revealed a better spatial homogeneity than the impregnated one.