KINETICS FINAL ESSAY

  
Introduction
In the paper by Hansen et al, the sintering of catalytic nanoparticles is studied. Postulations
about the underlying mechanisms of this sintering are made. In the article sintering is divided
into three phases. Phase 1 which is the rapid loss of catalyst activity, phase 2 which is the
slowing down of the sintering process and phase 3 which is stable catalytic performance. The
two underlying mechanisms considered are Ostwald Ripening (OR) and Particle Migration and
Coalescence (PMC). Using combinations of in-situ observation techniques and models, evidence
for the times at which each process occurs is evaluated.

Sintering Phase I
This phase is the rapid loss in catalyst activity due to a loss in surface area. Evidence from the
article suggests that this process occurs extremely fast. The article also concludes that this
phase is dominated by the OR process. OR is thermodynamically driven. In OR theory larger
particles are more energetically favored. Molecules on the surface of a particle are less stable
than ones on the interior. In larger particles there are more atoms on the interior (i.e. inside the
bounds of the surface layer) than there are on the surface, consequently making larger particles
more stable. Evidence from the article states that only particles that are near together may join
by PMC. This is a gap from the theory since it is rather expected that during phase I, due to the
small size of the particle, PMC would prevail since it is based on Brownian-motion. Evidence
does not support this. From analysis of the kinetics data of this phase, the growth of the larger
particles is seen to be steady. This is in line with the OR process theory since this process is
driven by a gradient in Gibbs free Energy. This gradient is what moderates the rate and makes it
steady, although fast.

Sintering Phase II
This phase is the slowing down of sintering. From theory, it could be assumed that due to the
large particle size, Brownian-motion supported sintering does not occur. Evidence from the
article is consistent with this claim since it was determined experimentally that there was
particle growth of immobile particles. This phase is slow for two reasons. Due to the large
particle size, Brownian-motion is limited. Lastly, due to similar sizes amongst the particles the
OR process is slowed as a result of a reduction in the free energy gradient since all particles
have grown to a certain extent.

Sintering Phase III

This phase is where stable catalytic performance is achieved. At this point, the particles are too
large to move around and the last of any two large particles in close proximity would have
joined together at this point. Therefore PMC is easily ruled out. Experimental evidence suggests
that the OR process occurs at this point at such a slow rate that it might not be detectable. This
is consistent with theory since at this point the particles would be very close in size. They will
therefore have very similar free energies and this causes slow rate of growth of the slightly
larger particles at the expense of the slightly smaller particles.

Conclusion
The sintering of catalytic nanoparticles is a complex process with huge implications on the
performance of catalytic nanoparticles. The article by Hanson et al divided sintering into 3
processes. However, sintering is basically the joining together of fine particles to form bigger
ones which has a net effect of reducing surface area and therefore reducing catalytic
performance. Ostwald Ripening and Particle Migration and Coalescence are two aspects of the
underlying mechanism of sintering and they were both evaluated. OR is the growth of larger
particles at the expense of smaller particles due to differences in free energy. PMC is the
Brownian-motion of particles with additional coalescence when particles near each other.