Hydride Reduction of BaTiO3 ? Oxyhydride Versus O Vacancy Formation

We investigated the hydride reduction of tetragonal BaTiO3 using the metal hydrides CaH2, NaH, MgH2, NaBH4, and NaAlH4. The reactions employed molar BaTiO3/H ratios of up to 1.8 and temperatures near 600 \ub0C. The air-stable reduced products were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy, thermogravimetric analysis (TGA), and 1H magic angle spinning (MAS) NMR spectroscopy. PXRD showed the formation of cubic products - indicative of the formation of BaTiO3-xHx - except for NaH. Lattice parameters were in a range between 4.005 \uc5 (for NaBH4-reduced samples) and 4.033 \uc5 (for MgH2-reduced samples). With increasing H/BaTiO3 ratio, CaH2-, NaAlH4-, and MgH2-reduced samples were afforded as two-phase mixtures. TGA in air flow showed significant weight increases of up to 3.5% for reduced BaTiO3, suggesting that metal hydride reduction yielded oxyhydrides BaTiO3-xHx with x values larger than 0.5. 1H MAS NMR spectroscopy, however, revealed rather low concentrations of H and thus a simultaneous presence of O vacancies in reduced BaTiO3. It has to be concluded that hydride reduction of BaTiO3 yields complex disordered materials BaTiO3-xHy?(x-y) with x up to 0.6 and y in a range 0.04-0.25, rather than homogeneous solid solutions BaTiO3-xHx. Resonances of (hydridic) H substituting O in the cubic perovskite structure appear in the ?2 to ?60 ppm spectral region. The large range of negative chemical shifts and breadth of the signals signifies metallic conductivity and structural disorder in BaTiO3-xHy?(x-y). Sintering of BaTiO3-xHy?(x-y) in a gaseous H2 atmosphere resulted in more ordered materials, as indicated by considerably sharper 1H resonances