Quantum Monte Carlo method for metal-film catalysis: water addition to carbon monoxide adsorbed on Pt/Al(111), a route to hydrogen

TL;DR

This paper introduces a novel Quantum Monte Carlo methodology to accurately study the water-gas shift reaction on Pt/Al(111) catalysts, providing insights into hydrogen production mechanisms crucial for sustainable energy.

Contribution

It demonstrates the application of Quantum Monte Carlo methods to investigate bond-breaking steps in catalysis, surpassing traditional DFT accuracy for this purpose.

Findings

QMC activation barrier: 64.8 ± 1.5 kJ/mol

Water addition to CO is rate-limiting

Method shows promise for catalytic system studies

Abstract

Hydrogen production as a clean, sustainable replacement for fossil fuels is gathering pace. Doubling the capacity of Paris-CDG airport has been halted, even with the upcoming Olympic Games, until hydrogen powered planes can be used. It is thus timely to work on catalytic selective hydrogen production and optimise catalyst structure. Over 90 % of all chemical manufacture uses a solid catalyst. This work describes adsorption of carbon-monoxide (CO) on platinum thin films, supported by cheap Al(111). CO reacts with water to produce hydrogen (water-gas shift). Quantum Monte Carlo methods are the only ones accurate enough to investigate the early steps of this catalysed reaction at close-packed Pt/Al(111). Many chemical reactions involve bond-dissociation. This process is often the key to rate-limiting reaction steps at solid surfaces. Since bond-breaking is poorly described by Hartree-Fock and DFT methods, our embedded active site approach is used This work demonstrates a novel Quantum Monte Carlo (QMC) methodology. The water-gas shift reaction step studied is water addition to CO pre-adsorbed on a Pt-monolayer supported by Al(111). The water molecule is only partially dissociated. Its oxygen atom binds to CO giving adsorbed COOH and Pt-H. This concerted addition is rate-limiting. In subsequent steps, the adsorbed formate species (with acidic hydrogen) decomposes to carbon dioxide and, after proton migration to Pt-H, the clean product H$_2$ is obtained. The QMC activation barrier found is 64.8 $\pm$ 1.5 kJ/mol. Thus, QMC is shown to be encouraging for investigating similar catalytic systems.