Nanoscale Surface Compositions and Structures Influence Boron Adsorption Properties of Anion Exchange Resins

Boron adsorption properties of poly(styrene-co-divinylbenzene) (PSDVB)-based anion-exchange resins with surface-grafted N-methyl-d-glucamine (NMDG) depend strongly on their local surface compositions, structures, and interfacial interactions. Distinct boron adsorption sites have been identified and quantified, and interactions between borate anions and hydroxyl groups of NMDG surface moieties have been established. A combination of X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (NMR), and Fourier-transform infrared (FT-IR) spectroscopy were used to characterize the atomic-level compositions and structures that directly influence the adsorption of borate anions on the NMDG-functionalized resin surface. Surface-enhanced dynamic-nuclear-polarization (DNP)-NMR enabled dilute (3 atom % N) tertiary alkyl amines and quaternary ammonium ions of the NMDG groups to be detected and distinguished with unprecedented sensitivity and resolution at natural abundance ¹⁵N (0.4%). Two-dimensional (2D) solid-state ¹¹B{¹H}, ¹³C{¹H}, and ¹¹B{¹¹B} NMR analyses provide direct atomic-scale evidence for interactions of borate anions with the NMDG moieties on the resin surfaces, which form stable mono- and bischelate complexes. FT-IR spectra reveal displacements in the stretching vibrational frequencies associated with the O-H and N-H bonds of NMDG groups that corroborate the formation of chelate complexes on the resin surfaces. The atomic-level compositions and structures are related to boron adsorption properties of resin materials synthesized under different conditions, which have important remediation applications.