Enhancement of the Rate of Surface Reactions by the Elastocapillary Effect

We examined the effect of deformability of a solid substrate on the kinetics of a surface reaction that occurs between chemical species present in it and a liquid dispensed on it. In particular, we have dispensed aqueous solutions of gold and silver salt as sessile drops or as a liquid pool on a cross-linked film of poly(dimethylsiloxane) (PDMS). The PDMS surface contains organosilane (SiH), which reduces the salt, producing metallic nanoparticles at the solid-liquid interface. These experiments reveal that, for a sufficiently soft solid, the reaction proceeds about three times faster in the drop mode than in the pool mode. The reaction conditions in both cases remain exactly identical except that, for the drop, the vertical component of the liquid surface tension deforms the solid substrate at the three-phase contact line. We have estimated the solid-liquid and solid-air interfacial energy, which along with the surface energy of the liquid gives an estimate of excess free energy. This energy is found to be different for the drop and pool modes. By considering that this excess free energy decreases the activation energy barrier for the reaction, we have shown that the reaction rate constant in the drop mode should indeed exceed that in the pool mode by about three times.