Characterization of highly dispersed Ni/Al2O3 catalysts by EXAFS analysis of higher shells

The size and morphology of Ni/Al2O3 catalysts in the oxidic, reduced, and passivated state were determined by EXAFS analysis of the higher shells around the Ni atoms. In the oxidic state, the Ni cations were present in small NiOx particles with predominant (111) plane. Below 4.5 wt% Ni loading, the NiOx particles consisted of one Ni layer, and of two or three Ni layers above 4.5 wt% Ni. A Ni–Al contribution was observed in samples with low Ni loading. The layer which is in contact with the Al2O3 surface is affected by the support surface and its structure is highly distorted, while the other layers were not distorted and have a structure similar to that in bulk NiO. In the reduced state, the number of Ni metal atoms in the reduced Ni particles was smaller than 100 with a narrow distribution below a loading of 15.6 wt% Ni. Above this loading, the particle size suddenly increased and the distribution became wider. The distances and Debye–Waller factors were similar to those of bulk nickel which suggested a weak interaction between the particles and the support. In the passivated state, Ni kernels with 20–40 metal atoms were covered by a one layer thick NiO skin.