Electrostatic reaction inhibition in nanoparticle catalysis

TL;DR

This paper investigates how electrostatic effects inhibit reactions on nanoparticle surfaces, combining simulations and theoretical models to quantify the impact across different reaction regimes and conditions.

Contribution

It introduces a combined simulation and theoretical framework to quantify electrostatic inhibition effects in nanoparticle catalysis, extending understanding from diffusion- to reaction-controlled limits.

Findings

Electrostatic inhibition significantly slows reactions at low ionic strength and high adsorption.

Theoretical models accurately predict reaction rate reductions due to electrostatic effects.

An interpolation formula effectively describes electrostatic inhibition across reaction regimes.

Abstract

Electrostatic reaction inhibition in heterogeneous catalysis emerges if charged reactants and products are adsorbed on the catalyst and thus repel the approaching reactants. In this work, we study the effects of electrostatic inhibition on the reaction rate of unimolecular reactions catalyzed on the surface of a spherical model nanoparticle by using particle-based reaction-diffusion simulations. Moreover, we derive closed rate equations based on approximate Debye-Smoluchowski rate theory, valid for diffusion-controlled reactions, and a modified Langmuir adsorption isotherm, relevant for reaction-controlled reactions, to account for electrostatic inhibition in the Debye-H\"uckel limit. We study the kinetics of reactions ranging from low to high adsorptions on the nanoparticle surface and from the surface- to diffusion-controlled limits for charge valencies 1 and 2. In the diffusion-controlled limit, electrostatic inhibition drastically slows down the reactions for strong adsorption and low ionic concentration, which is well described by our theory. In particular, the rate decreases with adsorption affinity, because in this case the inhibiting products are generated at high rate. In the (slow) reaction-controlled limit, the effect of electrostatic inhibition is much weaker, as semi-quantitatively reproduced by our electrostatic-modified Langmuir theory. We finally propose and verify a simple interpolation formula that describes electrostatic inhibition for all reaction speeds (`diffusion-influenced' reactions) in general.