Spin-probe ESR study on the entrapment of organic solutes by the nanochannel of MCM-41 in benzene.

An ESR study has been made on the adsorption of three types of aminoxyl radicals with different substituent groups in the nanochannel of MCM-41 in benzene. In the suspensions of MCM-41, all the aminoxyl radicals, usually called as spin probes, show the ESR spectra composed of two signals: the main broader one from the spin probes trapped in the nanochannel, and a sharp minor signal from those in the bulk. The spin probes adsorbed in the nanochannel retain considerable mobility especially at higher temperatures over 300 K. When fumed silica, having a surface structure similar to that of MCM-41, is employed, on the other hand, the relatively hydrophobic spin probe mainly remains in the bulk, but the hydrophilic one is mostly adsorbed and immobilized rigidly. From these results, the adsorption by the MCM-41 nanochannel in benzene is characterized by medium selectivity and considerable motional allowance to the adsorbate molecule. The mobility of the spin probe in the MCM-41 nanochannel increases and the adsorption efficiency decreases by either of the following changes made to the system: (a) increasing the channel diameter, (b) increasing the hydrophobicity of the spin probe, (c) adding a small amount of 2-propanol in the solution, (d) methylation of the surface OH groups of the nanochannel, and (e) elevating the system temperature. A model of this special type of adsorption has been proposed on the basis of the thermodynamic parameters and the ESR spectra for the modified systems including those with different solvents.