Multinuclear Solid-State NMR Spectroscopy of Doped Lanthanum Fluoride Nanoparticles

Abstract

Multinuclear solid-state NMR spectroscopy and powder X-ray diffraction (XRD) experiments are applied to comprehensively characterize a series of pure and lanthanide-doped LaF3 nanoparticles (NPs) that are capped with di-n-octadectyldithiophosphate ligands (Ln3+ = diamagnetic Y3+ and Sc3+ and paramagnetic Yb3+ ions), as well as correlated bulk microcrystalline materials (LaF3, YF3, and ScF3). Solid-state 139La and 19F NMR spectroscopy of bulk LaF3 and the LaF3 NPs reveal that the inorganic core of the NP retains the LaF3 structure at the molecular level; however, inhomogeneous broadening of the NMR powder patterns arises from distributions of 139La and 19F NMR interactions, confirming a gradual change in the La and F site environments from the NP core to the surface. 139La and 19F NMR experiments also indicate that low levels (5 and 10 mol %) of Ln3+ doping do not significantly change the LaF3 structure in the NP core. Similar doping levels of paramagnetic Yb3+ ions severely broaden 19F resonances, but only marginally effect 139La powder patterns, suggesting that the dopant ions are uniformly distributed throughout the NP core and occupy vacant La sites. Measurements of 139La T1 and T2 relaxation constants are seen to vary between the bulk material and NPs and between samples with diamagnetic and paramagnetic dopants. 45Sc NMR experiments confirm that the dopants are integrated into the La sites of the LaF3 core. Solid-state 1H and 31P magic-angle spinning (MAS) NMR spectra aid in probing the nature of the capping ligands and their interactions at the NP surface. 31P cross-polarization (CP)/MAS NMR experiments identify not only the dithiophosphate head groups but also thiophosphate and phosphate species which may form during NP synthesis. Finally, 19F-31P CP/MAS and 1H MAS experiments confirm that ligands are coordinated to the NP surface.

27Al NMR Studies of Aluminosilicate Glasses

“…Moreover, their higher quadrupolar moments of Q j j¼ 22:0 fm 2 ( 45 Sc) and Q ¼ 20.0 fm 2 ( 139 La) may induce very substantial quadrupolar coupling constants spanning tens of MHz. Consequently, while 45 Sc MAS NMR was only recently demonstrated on glasses [116,128,129], the few current 139 La MAS applications involved either highly symmetric La environments in ordered/crystalline structures [130][131][132][133][134], or NMR on static powders of metallocenes [135] or ceramics [136], for which very high 139 [51], no 139 La MAS NMR results are to our knowledge reported from glasses, presumably owing to a substantial CT signal broadening stemming from very large C Q values and the modest magnetogyric ratio of 139 La (which is close to that of 17 O). Moreover, significant distributions of both C Qη and δ iso parameters are expected to deteriorate the NMR signal resolution and sensitivity further.…”

Local Structure of Rare-Earth Fluorides in Bulk and Core/Shell Nanocrystalline Materials

“…As such, SSNMR spectra can act as exquisite probes of the cores and surfaces within the NC, revealing critical information about NC composition, short-and long-range order, and interactions at interfaces (e.g., core/shell, surface/ligand). [29][30][31] One of the most common hosts for Ln 3+ -dopants is NaYF 4 . Bulk NaYF 4 crystallizes in two distinct phases.…”

Application of Advanced Solid‐State NMR Techniques to the Characterization of Nanomaterials: A Focus on Interfaces and Structure

“…Nevertheless, a combination of NMR methods can be of great help to perform structural investigation as well as studies of interaction between the particle surface and ligands and reactants in case of catalytic applications. The materials under study may be very large: nanoparticles from natural sources [70][71][72], silicon-based compounds [73,74], metals [75][76][77][78][79][80], metal oxides [81][82][83][84][85][86], and other systems [87][88][89]. The surface chemistry and the nanoparticle/ligand interaction attracted most attention.…”