Copper-silver bimetallic system supported on natural clinoptilolite from Tasajeras deposit (Cuba) was studied. Bimetallic samples were prepared by simultaneous ion exchange, and reduced in a wide temperature range in a hydrogen flow. The main goal of the work was analysis of the mutual influence of both metals on their reduction process and the properties of the resultant particles. Analysis was done by combined use of XRD and UV-Vis spectroscopy. The reduction of Cu2+ and Ag+ cations shows existence of notable inter-influence between both cations during this process. The Cu2+ reduction is favored by the presence of Ag+, which should be related with the synergetic influence of silver cations and/or clusters formed on the first stages of reduction on Cu(2+)-framework interaction, facilitating the Cu2+ reduction even at low temperature (25 and 50 degrees C). The aggregation of the reduced highly dispersed species both for copper and silver is limited in this bimetallic system. The introduction of Ag+ as the second cation in the copper-exchanged zeolites favors the copper reduction at lower temperatures (25 and 50 degrees C), and appears to be the efficient tool for the control of the size of the resultant reduced nanoparticles (it means their dispersion).
Natural purified mordenite from Palmarito de Cauto (ZP) deposit, Cuba, was subjected to a hydrothermal ion exchange process in acid medium with Fe2+ or Fe3+ salts (Fe2+ZP and Fe3+ZP). The set of samples was characterized regarding their textural properties, morphology, and crystallinity, and tested in the NO reduction with CO/C3H6. Infrared spectroscopy coupled with NO as a probe molecule was used to give a qualitative description of the Fe species’ nature and distribution. The exchange process caused an increase in the iron loading of the samples and a redistribution, resulting in more dispersed Fe2+ and Fe3+ species. When contacted with the NO probe, Fe2+ZP showed the highest intensity of nitrosyl bands, assigned to NO adducts on isolated/highly dispersed Fe2+/Fe3+ extra-framework sites and FexOy clusters. This sample is also characterized by the highest NO sorption capacity and activity in NO reduction. Fe3+ZP showed a higher intensity of nitrosonium (NO+) species, without a correlation to NO storage and conversion, pointing to the reactivity of small FexOy aggregates in providing oxygen atoms for the NO to NO+ reaction. The same sites are proposed to be responsible for the higher production of CO2 observed on this sample, and thus to be detrimental to the activity in NO SCR.
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