It is known that the process of sintering occurs by mainly
two mechanisms; (a) crystallite migration where entire crystallites
migrate over the surface of the carrier followed by coalescence and
(b) Ostwald ripening, where metal species emitted by one crystallite
travels on the support or in the gas phase and are captured
by another crystallite [36]. In the present studies where the temperatures
were very high, it is postulated that Ostwald ripening is
the dominant cause of sintering. Sintering of the metal crystallites
is accelerated with the presence of steam in the atmosphere. DFT
calculations on Ni steam reforming catalysts show that the combined
energy of formation and diffusion for Ni2–OH complexes at
Ni (1 1 1) is 40 kJ/mol lower than that for Ni adatoms, strongly indicating
that the former species dominate the surface transport of Ni
at Ni surfaces when steam is present in the atmosphere [37,38]. The
reduced production of hydrogen from non-Rh catalysts suggests
higher partial pressure of unreacted steam in the local environment
around the catalyst. Higher concentration of steam leads to
higher concentration of Ni2–OH complexes, thereby leading to the
accelerated growth of Ni crystallites. In case of Rh-containing catalysts,
the concentration of steam was relatively low (because of
the higher conversion), which meant that the driving force for the
formation of Ni2–OH complexes was lower, thereby leading to less
sintering. The decrease in the activity in non-Rh catalysts can be
directly related to the loss in the surface area due to sintering.