• 文献标题:   Kinetics of H-1-C-13 multiple-contact cross-polarization as a powerful tool to determine the structure and dynamics of complex materials: application to graphene oxide
  • 文献类型:   Article
  • 作  者:   RAYA J, BIANCO A, HIRSCHINGER J
  • 作者关键词:  
  • 出版物名称:   PHYSICAL CHEMISTRY CHEMICAL PHYSICS
  • ISSN:   1463-9076 EI 1463-9084
  • 通讯作者地址:   Univ Strasbourg
  • 被引频次:   1
  • DOI:   10.1039/d0cp00454e
  • 出版年:   2020

▎ 摘  要

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 H-1, C-13 relaxation and H-1-C-13 CP experiments are performed in graphene oxide (GO). HHCP is found to be inefficient in our GO sample due to very fast H-1 T-1 rho relaxation. By contrast, the MC-CP technique which alleviates most of the magnetization loss by H-1 T-1 rho 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 (similar to 90%) of these groups being in the unusual "slow CP regime" in which the rate of H-1 T-1 rho relaxation is fast compared to the rate of cross-polarization. This C-13 signal component is attributed to mobile C-OH groups interacting preferentially with fast-relaxing water molecules while the remaining carbons (similar to 10%) in the usual "fast CP regime" are assigned to C-OH groups involved in hydrogen bonding with neighboring hydroxyl and/or epoxy groups.