Bimetallic Copper-Silver Systems Supported on Natural Clinoptilolite: Long-Term Changes in Nanospecies’ Composition and Stability

Inocente Rodríguez-Iznaga,Fernando Chávez-Rivas,Marina G Shelyapina,Vitalii Petranovskii

doi:10.3390/inorganics10030034

Abstract

Long-term changes in species of copper-silver bimetallic systems on natural clinoptilolite obtained by ion exchange of Cu2+ and Ag+ and then reduced at different temperatures were studied. Even after storage under ambient conditions, XRD and UV-Vis diffuse reflectance spectra indicate the presence of nanospecies and larger particles of reduced copper and silver. Scanning electron microscopy of aged bimetallic samples, reduced at the highest temperature (450 °C) and the pristine sample for their preparation, also aged, showed the presence of silver particles with a size of about 100 nm. They are formed in the initial ion-exchanged sample (without reduction) due to the degradation of Ag+ ions. The particles in the reduced sample are larger; in both samples they are evenly distributed over the surface. The presence of silver affects the stability and the mechanism of decomposition/oxidation of reduced copper species, and this stability is higher in bimetallic systems. The decomposition pattern of recently reduced species includes the formation of smaller nanoparticles and few-atomic clusters. This can occur, preceding the complete oxidation of Cu to ions. Quasicolloidal silver, which is present in fresh bimetallic samples reduced at lower temperatures, transforms after aging into Ag8 clusters, which indicates the stability of these nanospecies on natural clinoptilolite.

Highlights

Instituto de Ciencias y Tecnología de Materiales (IMRE), Universidad de La Habana, Zapata y G, s/n, La Havana 10400, Cuba
We reported the results for the Cu2+ -Ag+ bimetallic system, first subjected to ion exchange in natural clinoptilolite from the Tasajeras deposit (Cuba), and thermally reduced in a flow of hydrogen [26]
It turned out that even after 30 months of storage under ambient conditions, studies by UV-Vis diffuse reflectance spectroscopy and X-ray diffraction reliably confirm the presence of reduced copper and silver nanospecies, including clusters and nanoparticles, in the samples under study

Summary

Introduction

Instituto de Ciencias y Tecnología de Materiales (IMRE), Universidad de La Habana, Zapata y G, s/n, La Havana 10400, Cuba. Scanning electron microscopy of aged bimetallic samples, reduced at the highest temperature (450 ◦ C) and the pristine sample for their preparation, aged, showed the presence of silver particles with a size of about 100 nm. They are formed in the initial ion-exchanged sample (without reduction) due to the degradation of Ag+ ions. The decomposition pattern of recently reduced species includes the formation of smaller nanoparticles and few-atomic clusters. This can occur, preceding the complete oxidation of Cu to ions. A detailed characterization of the Cu species present in the de-NOx selective catalytic reduction zeolite-based catalyst undertaken before, during, and after the hydrothermal aging treatment of the material was carried out [24] to study changes in copper species, their location and their stability

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