Pyridine adsorption on NiSn/MgO–Al2O3: An FTIR spectroscopic study of surface acidity

• Published in: Applied surface science 2014-10, Vol.317, p.241-251
• Main Authors: Penkova, Anna, Bobadilla, Luis F., Romero-Sarria, Francisca, Centeno, Miguel A., Odriozola, José A.
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts; Cation vacancy; Cations; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Formations; FTIR spectroscopy; Lewis acid; Lewis acidity; Physics; Probe molecules; Pyridine; Pyridines; Surface chemistry; Vacancies; α-Pyridone
• ISSN: 0169-4332; 1873-5584
• DOI: 10.1016/j.apsusc.2014.08.093

•The surface acidity of MgO–Al2O3 supports and NiSn/MgO–Al2O3 catalysts were studied by pyridine adsorption.•The progressive reduction of the number and strength of the Lewis acid sites in the alumina is due to a competitive formation of the two types of spinels, MgAl2O4 and NiAl2O4.•In the catalyst NiSn/30MgO–Al2O3 no cationic vacancies were detected and the surface reaction with α-pyridone formation did not occur. The acid–base properties of MgO–Al2O3 supports and NiSn/MgO–Al2O3 catalysts were evaluated by IR spectroscopy using pyridine as a probe molecule. The results indicate that only Lewis acid sites were detected on the surface of the supports as well as on the catalysts. Nevertheless, Brønsted acid sites were not detected. In the support without MgO three kinds of coordinatively unsaturated acid sites were detected: Al3+ cations occupying octahedral, tetrahedral and tetrahedral with cationic vacancy in the neighbourhood. The last sites appear as the strongest. Moreover, they are able to activate the pyridine molecules leading to the formation of an intermediate α-pyridone complex. When MgO or NiO were added to the alumina, the number and strength of the Lewis acid sites decreased and significant changes were observed in the tetrahedral sites with adjoining cation vacancies. The incorporation of the Mg2+ cations into the alumina's structure takes place on the vacant tetrahedral positions, forming spinel MgAl2O4. As a result, the fraction of tetrahedral sites with adjoining cationic vacancy diminished and the intermediate α-pyridone complex in the support with the highest MgO loading was hardly detected. The addition of Ni2+ cations leads to the filling of the free octahedral positions, resulting in the formation of a NiAl2O4 spinel structure and the thermal stability of the α-pyridone species decreases. In the catalysts, the progressive reduction of the number and strength of the Lewis acid sites is due to a competitive formation of the two types of MgAl2O4 and NiAl2O4 spinels. In the catalyst NiSn/30MgO–Al2O3 no cationic vacancies were detected and the surface reaction with α-pyridone formation did not occur.