Vivianite [Fe3(PO4)2·8H2O] is easily oxidized in the presence of air. In this work, we studied the oxidation and incongruent dissolution of vivianite in a calcareous medium containing an anion-exchange resin (AER) that acted as a sink for phosphate. Freshly prepared vivianite suspensions with calcite sand and an AER membrane were oxidized and stirred by bubbling air or CO2-free O2. Experiments were finished when oxidation rate and P removal by the AER became slow, which was at 53 days (air system) or 28 days (CO2free O2 system). At these times, the respective values of the Fe(II)/total Fe ratio were 0.29 and 0.12, and the respective values of the atomic P/Fe ratio were 0.15 and 0.11. The final product of the oxidation was poorly crystalline lepidocrocite in the form of thin (1 5 nm), irregular lamellae that were soluble in acid oxalate. The unit-cell edge lengths of this lepidocrocite were a= 0.3117, b= 1.2572, and c= 0.3870, vs. a= 0.3071, b= 1.2520 and c= 0.3873 nm for the reference lepidocrocite. The lepidocrocite lamellae contained occluded P (P/Fe atomic ratio = 0.03 0.04). The results of this and a previous study made us hypothesize that this occluded P is structural and occupies tetrahedral sites adjacent to the empty octahedral sites in the sheets extending on ﹛010﹜.
A series of mono-and bi-metallic (Pt and/or Pd) impregnated zeolite Beta samples have been prepared, characterized using a number of experimental techniques and catalytically tested for the hydroisomerization of a mixture of light paraffins. In particular, the effect of the order of Pt and Pd impregnation on the type/structure of the metallic species of the zeolite support and on the catalytic activity has been studied. Studied samples included a zeolite Beta in which both Pt and Pd (0.5 wt% of each) were simultaneously impregnated (and subsequently calcined and reduced) and two equally metal-loaded samples where the metals were sequentially impregnated (samples Pt*-Pd/Beta and Pd*-Pt/Beta, in which Pt and Pd were impregnated first, respectively). Mono-metallic samples were also prepared for comparison. TPR, DR-UV-visible, TEM, and XAS studies confirm that the order of impregnation plays a key role in the formation of metallic particles, influencing aspects as decisive in their catalytic behavior as their size, their dispersion and their composition (e.g., mono-or bi-metallic). The initial impregnation of Pd and subsequently of Pt produces a higher number of hetero-metallic (Pt-Pd) bonds than the simultaneous co-impregnation and especially for the impregnation in reverse order, which does not produce Pt-Pd bonds in a detectable amount. Based on the results from the different characterization techniques, a model of the metal distribution and composition of the particles was proposed for each bi-metallic sample. In good agreement, the order of the catalytic activity was found to be Pd*-Pt/Beta > Pd-Pt/Beta > Pt/Beta > Pt*-Pd/Beta > Pd/Beta, making clear that not only the presence of both metals, but also an adequate preparation method generating a high number of hetero-metallic bonds must be taken into account to improve the catalytic properties in relation to the mono-metallic samples.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.