The adsorption of triethylenediamine on Al(2)O(3)-I: a vibrational spectroscopic and desorption kinetic study of surface bonding

The adsorption of triethylenediamine (TEDA) at 300 K is observed to occur via hydrogen bonding to isolated Al-OH groups on the surface of partially dehydroxylated high area gamma-Al(2)O(3) powder. This form of bonding results in +0.3 to +0.4% blue shifts in the CH(2) scissor modes at 1455 cm(-1) and a -0.4% red shift in the CN skeletal mode at 1060 cm(-1), compared to the gas-phase frequencies. Other modes are red shifted less than 0.1%. The isolated OH modes are red shifted by -200 to -1000 cm(-1) due to the strong hydrogen bonding association of Al-OH groups with an N atom in TEDA. Thermal desorption of adsorbed TEDA from the surface occurs in the range 300-700 K. Mass spectral and infrared studies indicate that the decomposition of TEDA occurs on Al(2)O(3) above 725 K, and that C-H bonds are broken, forming adsorbed species with N-H bonds which are stable to 1000 K or above. In contrast to adsorption at 300 K, adsorption of TEDA at 85 K results in the formation of a condensed ice of TEDA, which covers the outer surface of the porous Al(2)O(3) and which does not interact with Al-OH groups inside the porous powder due to immobility.