Synergetic effects of Cu-Zn bimetallic ions exchanged in NaX on acid sites of M(x)X zeolites (M = Cu2+ and/or Zn2+, x = level of exchange). An in situ FTIR study using pyridine adsorption/desorption

Abstract

X zeolites were prepared by ion-exchange with Cu2+ and/or Zn2+ cations, at different concentrations of the exchange solution, and characterized by thermal analysis and nitrogen adsorption. The acidity of the samples was investigated by pyridine adsorption–desorption followed by in situ Fourier transform infrared (FTIR) spectroscopy. Desorption was carried out at 150, 250 and 350 °C. The objective is to estimate the nature and concentration of acid sites. A comparison between the binary (Cu(x)X, Zn(x)X) and ternary (CuZn(x)X) exchanges was also established (x = level of exchange) through the Cu(43)X, Zn(48)X and CuZn(50)X samples. Lewis acidity decreases overall with desorption temperature and the level of exchange. As the latter increases, there is a conversion of some Lewis sites into those of Brønsted during thermal treatment. In return, the concentration of Brønsted sites increases with the degree of exchange. The Brønsted acidity of CuZn(50)X at 350 °C is more important than the sum of those of Cu(43)X and Zn(48)X with respectively values of 73, 32 and 15 μmol g−1. Besides, the concentration of Brønsted sites for CuZn(50)X increases with desorption temperature. These features indicate the presence of a synergetic effect amplifying the strength of these sites when Cu2+ and Zn2+ cations compete for the occupancy of sites distributed in zeolite cavities.