Interaction between charge-regulated metal nanoparticles in an electrolyte solution

TL;DR

This paper develops a theoretical model to calculate interactions between charge-regulated metal nanoparticles in electrolyte solutions, comparing it with simulations and analyzing boundary condition approximations.

Contribution

It introduces a microscopic model linking bulk and surface charge regulation, and applies it to compute interaction forces between metal nanoparticles.

Findings

Charge regulation boundary condition approximates constant surface charge well.

Constant surface potential boundary condition deviates significantly for asymmetric particles.

Theoretical results agree with Monte Carlo simulations for ionic density profiles.

Abstract

We present a theory which allows us to calculate the interaction potential between charge-regulated metal nanoparticles inside an acid-electrolyte solution. The approach is based on the recently introduced model of charge regulation which permits us to explicitly -- within a specific microscopic model -- relate the bulk association constant of a weak acid to the surface association constant for the same weak acid adsorption sites. When considering metal nanoparticles we explicitly account for the effect of the induced surface charge in the conducting core. To explore the accuracy of the approximations, we compare the ionic density profiles of an isolated charge-regulated metal nanoparticle with explicit Monte Carlo simulations of the same model. Once the accuracy of the theoretical approach is established, we proceed to calculate the interaction force between two charge-regulated metal nanoparticles by numerically solving the Poisson-Boltzmann equation with charge regulation boundary condition. The force is then calculated by integrating the electroosmotic stress tensor. We find that for metal nanoparticles the charge regulation boundary condition can be well approximated by the constant surface charge boundary condition, for which a very accurate Derjaguin-like approximation was recently introduced. On the other hand, a constant surface potential boundary condition often used in colloidal literature, shows a significant deviation from the charge regulation boundary condition for particles with large charge asymmetry.