Identification of Cation Clustering in Mg–Al Layered Double Hydroxides Using Multinuclear Solid State Nuclear Magnetic Resonance Spectroscopy

A combined X-ray diffraction and magic angle spinning nuclear magnetic resonance (MAS NMR) study of a series of layered double hydroxides (LDHs) has been utilized to identify cation clustering in the metal hydroxide layers. High resolution (multiple quantum, MQ) ²⁵Mg NMR spectroscopy was successfully used to resolve different Mg local environments in nitrate and carbonate-containing layered double hydroxides with various Al for Mg substitution levels, and it provides strong evidence for cation ordering schemes based around Al–Al avoidance (in agreement with ²⁷Al NMR), the ordering increasing with an increase in Al content. ¹H MAS double quantum NMR spectroscopy verified the existence of small Mg₃OH and Mg₂AlOH clusters within the same metal hydroxide sheet and confirmed that the cations gradually order as the Al concentration is increased to form a honeycomb-like Al distribution throughout the metal hydroxide layer. The combined use of these multinuclear NMR techniques provides a structural foundation with which to rationalize the effects of different cation distributions on properties such as anion binding and retention in this class of materials