Enhancement of the Rate of Surface Reactions by Elasto-capillary Effect

TL;DR

This paper demonstrates that surface tension-driven deformation of soft substrates like PDMS can significantly accelerate surface reactions, effectively reducing activation energy and increasing reaction rates similarly to temperature increases.

Contribution

It introduces the elasto-capillary effect as a novel method to enhance surface reaction rates by substrate deformation, a factor previously unconsidered in reaction kinetics.

Findings

Reaction rate increases by approximately three times on soft PDMS surfaces.

Surface deformation reduces activation energy equivalent to raising temperature by over 30°C.

Surface tension effects at the contact line influence reaction acceleration.

Abstract

Rate of a reaction is enhanced by increase in temperature, partial pressure or the concentration of reactants, and/or via use of a catalyst or an enzyme. Whereas the former increases the probability of collision rate between different molecules, the latter provides an alternate reaction path that diminishes the activation energy barrier for reaction, both effects increase the reaction rate. The deformability of the substrate on which a reaction occurs is not known to affect this rate. In contrast, by carrying out reduction of Gold and Silver salt on soft, crosslinked layers of poly(dimethylsiloxane) (PDMS), we show here that surface tension driven deformation of the solid too can increase the reaction rate. The PDMS contains SiH groups as organosilanes which reduces the salt thereby producing the corresponding metallic nano-particles. When an aqueous solution of the salt is dispensed as a sessile drop on a sufficiently soft PDMS layer, nano-particles get generated at ~3 times the rate over which when the salt solution is dispensed as a pool on the same surface. Unlike the pool, the drop has a three-phase contact line, where it pulls up the solid forming a ridge. By balancing the resultant surface stresses at the vicinity of this ridge, we have estimated the excess surface free energy associated with it. We show that this excess energy can diminish the activation energy barrier and increase the reaction rate to the extent that would have been achieved by increasing the reaction temperature by over 30o C.