Twinning in fcc lattice creates low-coordinated catalytically active sites in porous gold

Marian Krajčí; Satoshi Kameoka; An-Pang Tsai

doi:10.1063/1.4961508

Twinning in fcc lattice creates low-coordinated catalytically active sites in porous gold

J Chem Phys. 2016 Aug 28;145(8):084703. doi: 10.1063/1.4961508.

Authors

Marian Krajčí¹, Satoshi Kameoka², An-Pang Tsai²

Affiliations

¹ Institute of Physics, Slovak Academy of Sciences, Dúbravská cesta 9, SK-84511 Bratislava, Slovak Republic.
² Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan.

PMID: 27586937
DOI: 10.1063/1.4961508

Abstract

We describe a new mechanism for creation of catalytically active sites in porous gold. Samples of porous gold prepared by de-alloying Al2Au exhibit a clear correlation between the catalytic reactivity towards CO oxidation and structural defects in the fcc lattice of Au. We have found that on the stepped {211} surfaces quite common twin boundary defects in the bulk structure of porous gold can form long close-packed rows of atoms with the coordination number CN = 6. DFT calculations confirm that on these low-coordinated Au sites dioxygen chemisorbs and CO oxidation can proceed via the Langmuir-Hinshelwood mechanism with the activation energy of 37 kJ/mol or via the CO-OO intermediate with the energy barrier of 19 kJ/mol. The existence of the twins in porous gold is stabilized by the surface energy.