Proposed mechanism for the thermal activation
behavior of the CP-1
catalyst (reproduced from ref (13)). A series of schematic diagrams which illustrate the thermal
evolution process of the (a) CP-1 (acid-into-base), (b) CP-2 (base-into-acid),
and (c) DP-1 (acid-into-base) catalysts. The CP-1 catalyst (column
a) has a much larger amount of atomic Au species buried inside the
support material after only being dried as compared to the CP-2 and
DP-1 catalysts (columns b and c, respectively). Therefore, after calcination
at 300 °C, the loss of the more active smaller Au species (i.e.,
sub-nm clusters and 1–3 nm Au particles) due to agglomeration
can be replenished in the CP-1 catalysts by the outward diffusion
of the “trapped” internal Au species, which is not possible
in the case of the CP-2 and DP-1 catalysts. As a result, the CP-1
catalyst after calcination at 300 °C can be even more active
than the dried only stage (as highlighted by the dashed box). However,
after prolonged calcination at higher temperatures (i.e., the 500
°C treatment) the Au reserves inside the CP-1 support particle
eventually get depleted, and the catalytic activity decreases close
to zero due to agglomeration of the surface Au species.