Local environment and composition of magnesium gallium layered double hydroxides determined from solid-state 1H and 71Ga NMR spectroscopy

• Ga is ordered in our magnesium gallium layered double hydroxides.
• Ga depletion due to formation of soluble Ga complexes during synthesis.
• No sign of Ga rich regions in magnesium gallium LDHs.
• Solid state 1H and 71Ga give detailed insight into the structure.

Ordering of gallium(III) in a series of magnesium gallium (MgGa) layered double hydroxides (LDHs), [Mg1−xGax(OH)2(NO3)x·yH2O] was investigated using solid-state 1H and 71Ga NMR spectroscopy as well as powder X-ray diffraction. Three different proton environments from Mg3OH, Mg2GaOH and intergallery water molecules were assigned and quantified using {1H,71Ga} HETCOR and 1H MAS NMR. A single 71Ga site originating from the unique Ga site in the MgGa LDH׳s was observed in 71Ga MAS and 3QMAS NMR spectra. Both 1H MAS NMR spectra recorded at 21.1 T (900 MHz) and elemental analysis show that the synthesized MgGa LDH׳s had a lower Mg:Ga ratio than that of the starting reactant solution. The origin of this is the formation of soluble [Ga(OH)4]− complexes formed during synthesis, and not due to formation of insoluble gallium (oxy)hydroxides. No sign of GaOGa connectivities or defects were detected for the MgGa LDH׳s.

Two types of hydroxides groups are observed in magnesium gallium layered double hydroxides revealing an ordering of Ga in the cation layer.Figure optionsDownload as PowerPoint slide