Low-Field Functional Group Resolved Nuclear Spin Relaxation in Mesoporous Silica

Solid-fluid interactions underpin the efficacy of functional porous materials across a diverse array of chemical reaction and separation processes. However, detailed characterization of interfacial phenomena within such systems is hampered by their optically opaque nature. Motivated by the need to bridge this capability gap, we report low-magnetic-field two-dimensional (2D) ¹H nuclear spin relaxation measurements as a noninvasive probe of adsorbate identity and interfacial dynamics, exploring the relaxation characteristics exhibited by liquid hydrocarbon adsorbates confined to a model mesoporous silica. For the first time, we demonstrate the capacity of this approach in distinguishing functional group-specific relaxation phenomena across a diverse range of alcohols and carboxylic acids employed as solvents, reagents, and liquid hydrogen carriers, with distinct relaxation responses assigned to the alkyl and hydroxyl moieties of each confined liquid. Uniquely, this relaxation behavior is shown to correlate with adsorbate acidity, with the observed relationship rationalized on the basis of surface-adsorbate proton-exchange dynamics. Our results demonstrate that nuclear spin relaxation provides a molecular-level perspective on sorbent/sorbate interactions, motivating the exploration of such measurements as a unique probe of adsorbate identity within optically opaque porous media.