Can the Observed Changes in the Size or Shape of a Colloidal Nanocatalyst Reveal the Nanocatalysis Mechanism Type: Homogeneous or Heterogeneous?

The surface energy of metallic nanocrystals is relatively high compared to bulk materials due to the metal–metal bond deficiency of the surface atoms. This results in an insufficient chemical valency. In addition, smaller nanoparticles possess a higher degree of curvature, weakening the bonding of their surface atoms. This is especially true for non-spherical shapes, which are comprised of a large number of sharp corner and edge sites. These atomic sites possess higher surface energies due to the lower number of shared bonds with the nanoparticle, resulting in instability of the surface atoms and rendering them physically unstable and chemically active. In many instances, the constant “bombardment” of these surface atoms by the solvent molecules as well as by the reactant molecules when these nanocrystals are in colloidal solution could lead to surface atom dissolution, both physically and/or chemically. This phenomenon could alter the functionality of the metallic colloidal nanoparticle from supplying catalytically active sites (in heterogeneous catalysis) to serving as a reservoir of catalytically active species to the solution (in homogeneous catalysis). In the latter type, if the atoms of the nanocatalyst appear in the products, the nanoparticle is no longer a catalyst but a reactant. In this review we attempt to answer the question raised in the title by examining our previous work on the changes in size, shape, and other physical and chemical properties of colloidal transition metal nanoparticles during the nanocatalysis of two fundamentally different and important reactions: (1) the gentle electron-transfer reaction at room temperature involving the reduction of hexacyanoferrate (III) ions with thiosulfate ions and (2) the more harsh Suzuki cross-coupling reaction between phenylboronic acid and iodobenzene that takes place at 100 °C for 12 h. Changes in the nanoparticle dimensions were followed with TEM and HRTEM. Raman and FTIR spectroscopies were used to follow the chemical changes. For each change, we will use the above definition to see if the observed change can help us determine whether the catalysis is homogeneous or heterogeneous.