This
investigation explores optimum synthetic conditions for novel
polymer-metal organic framework hybrid composites composed of Zr-terephthalate-based
MOF UiO-66 and conductive polyaniline (PANI) nanofibers in an effort
to optimize conductivity while minimizing MOF structural deformation.
Successful syntheses of self-assembled PANI nanofibers in PANI@UiO-66
and PANI@UiO-66-NH2 composites were confirmed using scanning
electron microscopy, infrared spectroscopy, and powder X-ray diffraction.
The polymer-MOF composites show different bonding synergies to the
PANI nanofibers depending on the organic linker used. Electronic properties
of the post-synthetically modified PANI@UiO-66 and PANI@UiO-66-NH2 were investigated using UV–vis diffuse reflectance
spectroscopy. Sheet resistivity of the self-assembled polymer-MOF
composites was determined under an inert atmosphere at room temperature
using four-point probe measurements to confirm tunable semiconductivity
ranging from 40 to 2 mS/sq. Furthermore, the effects of aniline oxidation
on the crystallinity and coordination of UiO-66 and UiO-66-NH2 were determined through analysis of these results.
Ce(2)MnN(3)F(2-delta) has been synthesised via low-temperature fluorination of the ternary nitride Ce(2)MnN(3). To the best of our knowledge, Ce(2)MnN(3)F(2-delta) is the first quaternary nitride-fluoride to be reported. The reaction of Ce(2)MnN(3) with 10% F(2)/N(2) at 95-115 degrees C yields the fluorinated phase Ce(2)MnN(3)F(2-delta), with tetragonal symmetry (P4/nmm a = 3.8554(4) A and c = 13.088(4) A based on neutron powder diffraction), accompanied by starting material. Rietveld refinement supports a staged fluorine insertion reaction (into alternate rocksalt layers) to give a product with stoichiometry Ce(2)MnN(3)F(2-delta). A comparison with the formation of Sr(2)TiO(3)F(2) and the isostructural LaSrMnO(4)F indicates that two F(-) anions are inserted but no F(-)/N(3-) substitution takes place. Magnetic susceptibility measurements show a transition from Pauli paramagnetic behaviour, in Ce(2)MnN(3), to paramagnetic behaviour upon fluorination. The effective magnetic moment in Ce(2)MnN(3)F(2-delta), mu(eff) = 5.38 mu(B), is consistent with an intermediate value between that of Mn(3+) (4.9 mu(B)) and Mn(2+) (5.9 mu(B)) supporting the proposed stoichiometry, Ce(2)MnN(3)F(2-delta).
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