31P NMR as a tool for studying incorporation of Ni, Co, Fe, and Mn into aluminophosphate zeotypes

The incorporation of moderate amounts of Ni(II), Co(II), Fe(II/III), and Mn(II/III) into aluminophosphate zeotype AlPO4-34 and Fe(II/III) into aluminophosphate zeotype AlPO4-36 was studied by broadline P-31 NMR. The technique provided direct evidence on isomorphous substitution of framework aluminum by transition metals and allowed us to determine the extent of the substitution. 31P NMR proved to be complementary to other spectroscopic techniques such as X-ray absorption spectroscopy (XAS), Mossbauer, electron paramagnetic resonance (EPR), and electron nuclear double resonance (ENDOR) spectroscopies. The position of the NMR signal belonging to phosphorus in the P(OAl)(3)(OMe) environment depended mostly on the magnitude of the hyperfine interaction between a phosphorus nucleus and an unpaired electron, which was delocalized from the transition metal atom Me by covalent bonding. The width of the NMR signal was dominated by dipolar coupling among phosphorus nuclei and nearest paramagnetic centers. In addition, broadline NMR of ethylenediamine-templated manganese phosphate (C2H10N2)[Mn-2(HPO4)3(H2O)], which was used as a model compund, showed that on the basis of line positions and line widths different P-31 signals could easily be assigned to different phosphorus crystallographic sites. The technique could thus be applied to extract valuable structural information about metal phosphates as well.