The photooxidation of CO on reduced, rutile TiO2(110) was studied on a millisecond timescale. For a saturation coverage of chemisorbed O2 (0sat) and for half that coverage, the CO2 photon-stimulated desorption (PSD) signal is initially zero, increases to a maximum after several tens of milliseconds, and then decreases at longer times. The CO2 PSD signal increases ~5 times more quickly for 0.50sat. The initial rate of increase of the CO2 PSD signal is proportional to the flux of UV photons. The intermediate species involved in the reactions is stable for at least 100 s at 30 K. These results show that two or more non-thermal reaction steps are required to photooxidize CO adsorbed on TiO2(110). In contrast, previous models had suggested that CO photooxidation required only one non-thermal reaction. The likely initial and final charge states of the system suggest that an electron-mediated reaction and a hole-mediated reaction are needed for the complete photooxidation reaction.
Revised: April 19, 2013 |
Published: February 7, 2013
Citation
Petrik N.G., and G.A. Kimmel. 2013.Multiple Non-Thermal Reaction Steps for the Photooxidation CO to CO2 on Reduced TiO2(110).The Journal of Physical Chemistry Letters 4, no. 3:344-349.PNNL-SA-92421.doi:10.1021/jz302012j