Issue 9, 2014

Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

Abstract

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous–solid interface: the direct or indirect activation of O2 by surface hydrogen or the hydrolysis of O2 following a Langmuir–Hinshelwood mechanism or an Eley–Rideal mechanism. Among them, the Eley–Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

Graphical abstract: Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

Supplementary files

Article information

Article type
Paper
Submitted
16 Oct 2013
Accepted
26 Nov 2013
First published
28 Nov 2013

Phys. Chem. Chem. Phys., 2014,16, 4176-4185

Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

J. Liu, X. Cao and P. Hu, Phys. Chem. Chem. Phys., 2014, 16, 4176 DOI: 10.1039/C3CP54384F

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