Computational and FTIR spectroscopic studies on carbon monoxide and dinitrogen adsorption on a high-silica H-FER zeolite

Adsorption (at a low temperature) of carbon monoxide and dinitrogen on a high-silica ferrierite-type zeolite (H-FER, Si : Al = 27.5 : 1) was investigated by means of variable temperature infrared spectroscopy and theoretical calculations at the periodic DFT level. This combined experimental and computational approach led to detailed characterization of several types of hydrogen-bonded OH⋯CO and OH⋯N2 complexes, formed by interaction between the adsorbed molecules and the Brønsted acid OH groups of the zeolite. CO or N2, forming linear complexes with OH groups pointing towards a sufficiently ample void space, show the largest adsorption enthalpy which was found to be in the (approximate) range of −25 to −29 kJ mol−1 for CO and −15 to −19 kJ mol−1 for N2. Less stable OH⋯CO or OH⋯N2 complexes can be formed when either the Brønsted acid OH group is involved in intra-zeolite hydrogen bonding or when the free space available is too small to allow formation of linear complexes without previous re-location of the proton of the OH group involved. The details of experimental IR spectra in the O–H, C–O, and N–N stretching regions could be interpreted on the basis of good agreement between experimental and calculated results.