Oxygenated heterocyclic compounds are often used as solvents in liquid-phase catalytic reactions, such as hydrogenation and oxidation over porous oxide-based catalysts. It has often been reported that such compounds inhibit catalyst activity relative to the use of hydrocarbons as the solvent media. In this work we use $\mathrm{<mrow\; data-mjx-texclass="ORD">1</mrow>}$H pulsed-field gradient (PFG) NMR diffusion studies to study diffusion properties of binary mixtures 1,4-dioxane/cyclohexane in mesoporous TiO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ over the whole composition range in order to understand the effect of the solid surface on molecular transport and molecular interactions within the pore space. The results reveal that whilst the diffusion of the hydrocarbon is only affected by geometrical restrictions, the diffusion profile of 1,4-dioxane is highly influenced by interactions within the catalyst pore, which is thought to be due to the presence of lone electron pairs on the oxygen atoms of 1,4-dioxane, allowing the molecule to act as a Lewis base when in contact with the solid surface. This agrees with findings on the inhibitory capacity of oxygenated heterocyclic compounds when used either as solvent in catalysis or present as impurities in some chemical feedstocks. The work shows that it is possible to use $\mathrm{<mrow\; data-mjx-texclass="ORD">1</mrow>}$H PFG NMR in order to characterise the effect of surfaces on molecular transport and hence understand catalytic behaviour in liquid-phase catalytic reactions.