Intermediates of CO Oxidation on Iron Oxides.pdf

THE JOURNAL OF CHEMICAL PHYSICS 134, 034305 (2011) Intermediates of CO oxidation on iron oxides: An experimental and theoretical study Zhang-Hui Lu and Qiang Xua) National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka 563-8577 Japan and Graduate School of Engineering, Kobe University, Nada Ku, Kobe, Hyogo 657-8501, Japan (Received 25 May 2010; accepted 12 November 2010; published online 19 January 2011) Reactions of laser-ablated iron oxides with CO in excess argon are investigated by infrared adsorp- tion spectroscopy and density functional theoretical calculations. The carbonyl iron oxides OFe(CO)n (n = 1–3) and O2Fe(CO)m (m = 1, 2) are generated during sample deposition or annealing, whereas CO2 is greatly produced at the expense of these carbonyl iron oxides upon UV irradiation, showing the formation of intermediate carbonyl iron oxides in the oxidation of carbon monoxide to carbon dioxide. These intermediate carbonyl iron oxides are characterized on the basis of isotopic sub- stitution, stepwise annealing, change of CO concentration and laser energy, and comparison with theoretical calculations. The overall agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these complexes from the matrix infrared spectra. The reaction pathways for the formation of the products are proposed based on the experimental and theoretical results presented. ? 2011 American Institute of Physics. [doi:10.1063/1.3523648] I. INTRODUCTION The oxidation of carbon monoxide is of considerable in- terest from an academic and an industrial viewpoint due to its importance in many practical applications such as com- bustion exhaust, fuel gas cleanup, the development of CO detection device, and improved efficiency of CO2 lasers.1 Extensive research efforts have been made both experimen- tally and theoretically to search for suitable catalysts to en- hance this