Kinetics of 1H–13C multiple-contact cross-polarization as a powerful tool to determine the structure and dynamics of complex materials: application to graphene oxide

Abstract

Hartmann–Hahn cross-polarization (HHCP) is the most widely used solid-state NMR technique to enhance the magnetization of dilute spins from abundant spins. Furthermore, as the kinetics of CP depends on dipolar interactions, it contains valuable information on molecular structure and dynamics. In this work, analytical solutions are derived for the kinetics of HHCP and multiple-contact CP (MC-CP) using both classical and non-classical spin-coupling models including the effects of molecular dynamics and several ¹H, ¹³C relaxation and ¹H–¹³C CP experiments are performed in graphene oxide (GO). HHCP is found to be inefficient in our GO sample due to very fast ¹H T_1ρ relaxation. By contrast, the MC-CP technique which alleviates most of the magnetization loss by ¹H T_1ρ relaxation leads to a much larger polarization transfer efficiency reducing the measuring time by an order of magnitude. A detailed analysis of the HHCP and MC-CP kinetics indicates the existence of at least two different kinds of hydroxyl (C–OH) functional groups in GO, the major fraction (∼90%) of these groups being in the unusual “slow CP regime” in which the rate of ¹H T_1ρ relaxation is fast compared to the rate of cross-polarization. This ¹³C signal component is attributed to mobile C–OH groups interacting preferentially with fast-relaxing water molecules while the remaining carbons (∼10%) in the usual “fast CP regime” are assigned to C–OH groups involved in hydrogen bonding with neighboring hydroxyl and/or epoxy groups.