The
shape of metal nanoparticles can dramatically depend on reaction
conditions. While Pt nanoparticles are known to dynamically respond
to the partial pressure of CO, in situ TEM images show that, surprisingly,
Co nanoparticles do not change their shape under a CO atmosphere despite
going through several reconstructions. Detailed DFT calculations attribute
this contrasting behavior to two factors: (1) CO adsorption has a
higher stabilization effect on the high-index facets of Pt than on
those of Co; (2) the Co surface energy is more sensitive to the coordination
number, making high-index surfaces less stable relative to Pt. These
two factors combined can affect the stability of high-index surfaces
as is the case for Pt nanoparticles, which reconstruct already at
low CO pressures. In the case of Co nanoparticles, the low-index surface
remains the most stable even at high CO partial pressures. The robustness
of the shape of Co nanoparticles challenges recent proposals that
high-index facets, which facilitate direct CO dissociation, are present
on Co nanoparticle catalysts under Fischer–Tropsch conditions.
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