Roberto Dragone

TPR and XPS study of cobalt–copper mixed oxide catalysts: evidence of a strong Co–Cu interaction

In this work the results of a TPR and XPS investigation of CoxOy–CuO mixed oxides in the range of composition Co : Cu=100:0–8:92 are reported and compared. The final catalysts were obtained by thermal decomposition in air and N2 at 723 K for 24 h of single‐phase cobalt–copper hydroxycarbonates prepared by coprecipitation at constant pH. The Co : Cu=100 : 0 specimen calcined in air formed the Co2+[Co3]2O4 (Co3O4) spinel phase. The copper‐containing catalysts (Co : Cu=85 : 15–8 : 92) showed mainly two phases: (i) spinels, like Co2+[Co3+]2O4, Co1-x2+Cux2+[Co3+]2O4 and (ii) pure CuO, the relative amount of each phase depending on the Co : Cu atomic ratio. The results of the XPS study are consistent with the bulk findings and revealed the presence of Co2+, Co3+ and Cu2+ species at the catalyst surface. Moreover, the surface quantitative analysis evidenced a cobalt enrichment, in particular for the most diluted cobalt samples. The TPR study showed that the catalyst reduction is affected by a strong mutual influence between cobalt and copper. The reducibility of the mixed oxide catalysts was always promoted with respect to that of the pure Co3O4 and CuO phases and the reduction of cobalt was markedly enhanced by the presence of copper. Cobalt and copper were both reduced to metals regardless of the catalyst composition. On the other hand, the Co : Cu=100 : 0 specimen calcined in N2 formed, as expected, CoO. The initial addition of copper resulted in the formation of the Cu+Co3+O2 compound, besides CoO, up to a Co/Cu=1 atomic ratio at which the CuCoO2 phase was the main component. A further addition of copper led to the formation of CuCoO2 and CuO phases. The XPS results were in good agreement with these findings and the surface quantitative analysis revealed a less enrichment of cobalt with respect to the catalysts calcined in air. The TPR analysis confirmed that the reduction of the N2‐calcined catalysts was also remarkably promoted by the presence of copper. Also in this case cobalt and copper metal were the final products of reduction.

Preparation and characterisation of cobalt–copper hydroxysalts and their oxide products of decomposition

Three cobalt–copper hydroxysalts with chemical formulae Co(CO3)0.5(OH)1.0· 0.11H2O, Co0.67Cu0.33(CO3)0.4(OH)1.2 and Co0.49Cu0.51(CO3)0.43(OH)1.14 have been obtained and characterised by powder X-ray diffraction (XRD), thermal analysis (TG, DTG and DTA), diffuse reflectance spectroscopy (DRS), magnetic susceptibility and X-ray photoelectron spectroscopy (XPS). The above precursors treated at 723 K for 24 h both in N2 and in air give several cobalt and copper oxides which were characterised by magnetic susceptibility, X-ray diffraction, X-ray photoelectron spectroscopy and diffuse reflectance. Depending on the Co : Cu atomic ratios and on the treatments with various gases, the products consist of oxides such as CoO, CuxCo1–xO, CuCoO2 and CuxCo3–xO4 for the samples calcined in N2, and Co3O4, CuxCo3–xO4 and CuO for those calcined in air.

Manganese ions in the monoclinic, tetragonal and cubic phases of zirconia: an XRD and EPR study

Mn-doped monoclinic, tetragonal and cubic zirconia samples were characterized by XRD and EPR. The cubic modification was obtained by doping hydrous zirconia with Y2O3 (YSZ). The ZrO2 structure influences the solid solution formation and the nature of manganese species. EPR analysis revealed the following manganese paramagnetic species: isolated Mn4+ and Mn2+ in the monoclinic phase; isolated Mn2+ in the tetragonal phase; isolated Mn2+ in the cubic YSZ; and clustered Mn2+ in Mn3O4 and in MnO particles on the zirconia surface. Quantitative EPR suggested Mn3+ in all zirconia phases. After heating in air, Mn3+ and Mn4+ ions entered the monoclinic zirconia phase at 1273–1623 K and surface Mn3O4 particles formed, whereas Mn3+ and Mn2+ entered the tetragonal zirconia phase at 973–1173 K and at 1623 K into cubic YSZ. In all zirconia phases, subsequent heating in H2 at 773–973 K reduced Mnn+ ions to Mn2+ and converted Mn3O4 particles on the surface into MnO. In monoclinic zirconia heated in air at 1623 K the Mn-solubility limit was 0.2 wt.%.

Quantitative EPR spectroscopy: Comparison between primary standards and application to MgO-MnO and α-Al2O3-Cr2O3 solid solutions

To study their reliability as primary standards in the quantitative EPR spectroscopy, a large series of pure paramagnetic compounds with known spin concentrations, whose spectra vary considerably in intensity, shape, structure and overall width are compared. The paramagnetic species examined as pure solid compounds and solutions, were free radicals (DPPH and TEMPO), vanadyl and Cu2+ ions (S = 1/2), Cr3+ (S = 3/2) and Mn2+ (5 = 5/2) ions. The quantitative EPR findings suggest that all theS = 1/2 paramagnetic compounds investigated and MnSO4 · H2O (S = 5/2) are reliable primary standards. By contrast, none of the pure Cr3+ compounds proved useful as primary standards because of their large fine-structure terms or high Néel temperature that invalidated the simple Curie law. Application of quantitative EPR in the study of dilute MgO-MnO and α-Al2O3-Cr2O3 solid solutions, focussing on the circumstances making paramagnetic species undetectable, is reported. In MgO-MnO solid solutions of high surface area, detection problems arising from the variation of local site symmetry can be circumvented and almost all Mn2+ are detected only by reducing the surface area. In concentrated α-Al2O3-Cr2O3 solid solutions, magnetic interactions lead to paramagnetic species being undetectable.

Manganese oxide–zirconium oxide solid solutions. An X-ray diffraction, Raman spectroscopy, thermogravimetry and magnetic study

Manganese oxide-doped zirconium oxide samples, prepared by heating mixtures of coprecipitated hydroxides at 1073 K in a hydrogen stream (water content 0.2% by volume), were analysed to obtain information on the solid solution formation. The state and the thermal stability of the incorporated species were also investigated. The samples (manganese content up to 14.74 mass%), were studied ‘as-prepared’ and after subsequent thermal treatments in oxygen up to 753 K. The results of several techniques [X-ray diffraction (XRD), Raman spectroscopy, thermogravimetry (TG) and magnetic susceptibility measurements] show that in the ‘as-prepared’ samples (1073 K, H2) a high fraction of manganese is incorporated in the zirconia structure, only a small fraction being present as an MnO separate phase. Most of the manganese in solid solution is present in the +2 oxidation state, the remainder as + 3 and +4. TG experiments and magnetic susceptibility measurements reveal that the Mn3+ and/or Mn4+ are formed both during the cooling in hydrogen by reaction with water present as an impurity in the gas phase, and during the exposure to the atmosphere. As the amount of manganese in solid solution increases, the volume of the zirconia unit cell slightly decreases. The solid-solution formation favours the tetragonal and the cubic modifications at the expense of the thermodynamically stable monoclinic phase. When the samples are heated up to 753 K in oxygen, the Mn2+ in solid solution is partially oxidized to Mn3+ and/or Mn4+. TG and XRD experiments show that the oxidation starts at low temperature and takes place in solid solution without appreciable manganese oxide segregation.

Copper–cobalt hydroxysalts and oxysalts: bulk and surface characterization

Copper–cobalt oxysalts of various Cu : Co atomic ratios (100 : 0. 92 : 8, 85 : 15, 77 : 23, 67 : 33, 15 : 85, 0 : 100) have been prepared by coprecipitation, at constant pH, from solutions of copper and cobalt nitrates added to a solution of NaHCO3; the structure and chemical nature of the Cu—Co oxysalts have been investigated by several complementary techniques such as X-ray diffraction (XRD), magnetic susceptibility, reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS) to obtain information both on their bulk and on their surface properties.In the range of Cu : Co atomic ratios from 100 : 0 to 67 : 33 the materials consist of Co-containing malachite, Cu2 –xCoxCO3(OH)2, while for Cu : Co equal to 0 : 100 and 15 : 85 the products are CoCO3, spherocobaltite, and Cu-containing spherocobaltite Co0.85Cu0.15CO3, respectively. From both reflectance spectroscopy and magnetic susceptibility measurements the presence of only Cu2+ and Co2+ species has been ascertained in all materials. Antiferromagnetic interactions are strong at high copper content and become weaker at increasing cobalt loading. The observed decrease in volume of the malachite monoclinic unit cell with incorporation of Co2+ ions, in spite of the larger Co2+ ion radius with respect to that of Cu2+, indicates that distortion of the MO6 polyhedra at the cation site of the malachite lattice is less when Cu2+ is replaced by Co2+. The presence of Cu2+ in the spherocobaltite trigonal lattice shows a small cell volume decrease as expected from ionic radii difference. XPS has confirmed the presence of only Cu2+ and Co2+ species at the surface of the materials. It is also shown that the local nature of the chemical bond is essentially determined by the nature of the first-neighbour ligands. At higher copper content, where the materials are cobalt-containing malachite, the surface is enriched in cobalt.

A new respirometric endpoint-based biosensor to assess the relative toxicity of chemicals on immobilized human cells

Several functional and biochemical parameters have been proposed as biomarkers of effect of environmental pollutants. A rapid biosensor working with immobilized human U-937 cells was developed and applied to environmentally relevant chemicals with different structures and toxicological pathways, i.e. benzalkonium chloride, clofibric acid, diclofenac, mercury nitrate, ofloxacin, and sodium dodecyl sulphate. Respiration of cells was relied upon as a comprehensive biochemical effect for screening purposes. Analytical parameter (DeltappmO(2)) and toxicological index (respiratory inhibition, delta%) measured after 1h of exposure were utilized for dose-response relationship study. Results (toxicity rating scales based on delta(50)% and steepness) were compared with those obtained by the same approach previously optimized on Saccharomyces cerevisiae. The toxicity rating scale obtained by the biomarker based on human mitochondrial and cell metabolic activities compared well with previous scale obtained on yeast cells and with available in-vivo acute toxicity indexes; respiration was confirmed as toxicological endpoint reliably measurable by the biosensor.

New investigation of the isothermal oxidation of extra virgin olive oil: determination of free radicals, total polyphenols, total antioxidant capacity, and kinetic data.

As a follow-up of the research programs carried out by our group concerning the artificial isothermal rancidification process in extra virgin olive oil (EVOO), in the present work the trends of both the total antioxidant capacity and the total polyphenols concentration as well as the main kinetic parameters of the process during the thermal oxidation of EVOO were studied and compared. In addition, the possibility of evaluating the increase in radicals concentration during the thermal oxidation process using a superoxide dismutase biosensor was also studied. The present investigation concerning this important food product is highly topical as it refers to the state of alteration of the EVOO used for cooking or frying, as a function of the temperature reached.

The reduction process of copper-zinc oxide-(alumina) methanol catalysts

Abstract CuO-ZnO-Al2O3 catalysts at different copper and zinc contents were obtained by thermal decomposition of hydroxycarbonate precursors at 350°C in air. They were characterized by using X-ray diffraction, diffuse reflectance spectroscopy and surface area determination. We find disticnt CuO and ZnO phases whose particle sizes, determined by XRD line broadening, are in the range 65–90 A for CuO and around 100 A for ZnO in the binary CuO/ZnO systems. For pure CuO the particle dimensions are higher (D~140 A ) . For the three component oxide, CuO|ZnO|Al2O3=60|30|10, the particle sizes of both CuO and ZnO phases are around 60 A. The BET surface areas are around 70 m2/g for the two components oxides, ~40 for pure CuO and for the three component systems. The reduction of the copper oxide (CuO) has been studied by in situ XRD. The reduction to metallic copper proceeds through the formation of intermediate Cu2O which is present together with metallic copper even at relatively high extents of reduction. It has also been observed that the reduction process is much slower in the three component system than for pure CuO or the two component, CuO-ZnO, system. The presence of alumina in intimate contact with CuO and ZnO (due to the preparation conditions of the precursors) thus seems to hinder the reduction of the Cu2+ species (to Cu+ or Cuo) and to prevent the nucleation of both cuprous oxide and metallic copper partcles.

Microbial screening for quinolones residues in cow milk by bio-optical method

The use of antibiotics on lactating cows should be monitored for the possible risk of milk contamination with residues. Accordingly, Maximum Residue Levels (MRLs) are established by the European Commission to guarantee consumers safety. As pointed out by Dec 2002/657/EC, screening is the first step in the strategy for antibiotic residue control, thus playing a key role in the whole control procedure. However, current routine screening methods applied in milk chain still fail to detect residues of quinolones at concentrations of interest. This paper reports the findings of a new bio-optical method for the screening of quinolones residues in bovine milk, based on E. coli ATCC 11303 growth inhibition. The effect of blank and spiked cow milk samples (aliquots equivalents to 0.8%, v/v) is evaluated in Mueller Hinton Broth (MHb) and MHb enriched with MgSO4 2% (MHb-Mg) inoculated with the test strain at the concentration of 10(4)CFU/mL. The presence of quinolones inhibits the cellular growth in MHb, while this effect is neutralized in MHb-Mg allowing both detection and presumptive identification of quinolones. Growth of the test strain is monitored at 37 °C in a Bioscreen C automated system, and Optical Density (OD) at 600 nm is recorded every 10 min after shaking for 10s. Growth curves (OD vs. time) of E. coli ATCC 11303 are assessed in milk samples, with and without quinolones, and their differences in terms of ΔOD (ΔOD600nm=ODMHb-Mg-ODMHb) are calculated. The presence of quinolones is detected by the cellular growth inhibition (OD vs time, none increase in the value OD) and presumptively identified through the increase of the slope of ΔOD600nm curve (ΔOD vs. time), after about 3h of incubation. The detection limit for ciprofloxacin and enrofloxacin is at the level of MRL, for marbofloxacin is at 2-fold the MRL whereas for danofloxacin is at 4-fold the MRL. Although the sensitivity of the method could be further improved and the procedure automated, it is a promising step forward to integrate screening assays into the control process and, in particular, to fill in the gap for quinolones; moreover, these technological developments contribute to the One Health perspective through the monitoring of safe and correct use of veterinary antibiotics.