Ab initio Investigation of Effect of Vacancy on Dissociation of Water Molecule on Cu(111) Surface

TL;DR

This study uses density functional theory to show that vacancies on Cu(111) surfaces significantly lower the activation energy for water dissociation, facilitating the reaction process.

Contribution

It provides the first detailed computational analysis of how vacancies influence water dissociation on Cu(111) surfaces.

Findings

Vacancies reduce activation energy by nearly 0.2 eV.

Water dissociation involves a two-step process with hydrogen evolution.

Surface modification pathways are identified for water dissociation.

Abstract

Water dissociation is a rate limiting step in many industrially important chemical reactions. In this investigation, climbing image nudged elastic band (CINEB) method, within the framework of density functional theory, is used to report the activation energies (E a ) of water dissociation on Cu(111) surface with a vacancy. Introduction of vacancy results in a reduced coordination of the dissociated products, which facilitates their availability for reactions that involve water dissociation as an intermediate step. Activation energy for dissociation of water reduces by nearly 0.2 eV on Cu(111) surface with vacancy, in comparison with that of pristine Cu(111) surface. We also find that surface modification of the Cu upper surface is one of the possible pathways to dissociate water when the vacancy is introduced. Activation energy, and the minimum energy path (MEP) leading to the transition state remain same for various product configurations. CINEB corresponding to hydrogen gas evolution is also performed which shows that it is a two step process involving water dissociation. We conclude that the introduction of vacancy facilitates the water dissociation reaction, by reducing the activation energy by about 20%.