In Situ Transient FTIR and XANES Studies of the Evolution of Surface Species in CO Oxidation on Au/TiO2

• Published in: The journal of physical chemistry. B Vol. 110; no. 17; pp. 8689 - 8700
• Main Authors: Henao, Juan D, Caputo, Tiziana, Yang, Jeff H, Kung, Mayfair C, Kung, Harold H
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04-05-2006
• Subjects: Adsorption; Carbon Monoxide - chemistry; Gold - chemistry; Oxidation-Reduction; Sensitivity and Specificity; Spectroscopy, Fourier Transform Infrared - methods; Spectrum Analysis - methods; Surface Properties; Time Factors; Titanium - chemistry; X-Rays
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp0568733

The adsorption of CO and its reaction with oxygen were investigated using a combination of in situ Fourier transform infrared spectroscopy, step response measurements in a microreactor, 18O isotopic labeling, and X-ray absorption near edge structure spectroscopy. An as-prepared sample in which Au is present as a surface oxyhydroxy complex does not adsorb CO. On an activated sample in which only metallic Au is detected, 0.18 ± 0.03 mol CO/(mol Au) are adsorbed on Au at −60 °C, which shows an IR band at 2090 cm-1. When oxygen is present in the gas phase, this species reacts with a turnover rate of 1.4 ± 0.2 mol CO(mol Au min)-1, which is close to the steady-state turnover rate. In contrast, there is a very small quantity of adsorbed oxygen on Au. A small IR peak at 1242 cm-1 appears when an activated sample is exposed to CO. It reacts rapidly with oxygen and is shifted to 1236 cm-1 if 18O is used. It is assigned to the possible intermediate hydroxycarbonyl.