Structural Characterization of Ni-Substituted Hexaaluminate Catalysts Using EXAFS, XANES, XPS, XRD, and TPR

The structure of five Ni-substituted Ba0.75NiyAl12-yO19-δ hexaaluminate catalysts at various Ni loadings (y = 0.2, 0.4, 0.6, 0.8 and 1.0) was investigated using EXAFS, XANES, XPS, XRD, and TPR. As Ni-substitution into the hexaaluminate lattice is increased, the unit cell dimension decreases along the c axis. This systematic change is consistent with Ni substitution for Al3+ in the hexaaluminate crystalline structure. XANES analysis suggests that Ni−O bonding is stronger for Ni substituted into the hexaaluminate lattice, relative to that of bulk NiO. The average coordination numbers obtained from EXAFS indicate that Ni is preferentially exchanging with tetrahedrally coordinated Al3+ in the structure which predominates in regions of the hexaaluminate unit cell near the mirror plane. It is at these sites that, preferential substitution of Ni2+ likely occurs to minimize strain in the crystalline lattice.