Adsorbate interactions of Cu(II) in Cu(II)-exchanged K-L gallosilicate studied by CW and pulsed electron spin resonance

Abstract

The interactions of Cu(II) in Cu(II)-exchanged K-L gallosilicate with adsorbates containing coordinative nitrogens in ammonia, pyridine, aniline, acetonitrile and hydrazine, and with the adsorbates carbon monoxide, benzene, propanol and dimethyl sulfoxide are investigated by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies. These results are compared with those in Cu(II)-exchanged K-L aluminosilicate and the differences are discussed. Adsorption of ammonia produces a complex containing four molecules of ammonia based on resolved nitrogen superhyperfine interaction. Upon equilibrium with pyridine, Cu(II) forms a complex containing four molecules of pyridine in CuK-L gallosilicate and a complex containing only three molecules of pyridine in CuK-L aluminosilicate based on resolved nitrogen superhyperfine. Upon adsorption of aniline and acetonitrile, Cu(II) forms complexes containing two molecules of each in CuK-L gallosilicate based on resolved nitrogen superhyperfine. However, no resolved nitrogen superhyperfine between hydrazine and Cu(II) is seen. Adsorption of carbon monoxide, benzene, propanol and dimethyl sulfoxide causes changes in the ESR spectrum of Cu(II), indicating migration of Cu(II) into cation positions in the main channels where adsorbate coordination can occur. Cu(II) forms complexes with one molecule of benzene and two molecules of propanol based on ESEM data in both K-L gallosilicate and K-L aluminosilicate. However, Cu(II) interacts directly with one dimethyl sulfoxide in K-L aluminosilicate but only indirectly at a longer distance with one dimethyl sulfoxide in K-L gallosilicate based on ESEM data.