Interaction of water with titania: implications for high-temperature gas sensing.
High-temperature gas sensors based on semiconducting metal oxides show potential for optimization of combustion processes, resulting in efficient energy use and minimization of emissions. Such metal oxides can function as gas sensors because of the reaction of the sensing gas (e.g., CO) with ionosorbed oxygen species on the oxide surface with the resulting increase in conductivity. A limitation of metal oxide sensors is their difficulty of distinguishing between different gases. Designing selectivity into sensors necessitates a better understanding of the chemistry of gas-solid interactions at high temperatures. In this paper, we have used in situ infrared spectroscopy to monitor the dehydration of a hydrated anatase surface up to 600 degrees C and also to examine the hydration/dehydration of anatase held at 400 degrees C. When the O-H stretching region (3000-3800 cm(-1)) was primarily focused on, it was found that water loss from the titania surface proceeded at lower temperatures (<200 degrees C) through desorption, whereas at higher temperatures, water dissociation to terminal (approximately 3710 cm(-1)) and bridged (approximately 3660 cm(-1)) hydroxyl groups was noted. With a further increase in temperature to 600 degrees C, the bridged hydroxyl groups disappeared faster than the terminal ones. The electrical resistance of anatase at 600 degrees C was measured in the presence of moist gas streams and resulted in an increase in conductivity in the presence of water. In situ vibrational spectroscopy indicated a temporal correlation between the appearance of the bridging hydroxyl group and the change in electrical resistance. Several possible mechanisms are discussed. The chemical reaction of water with anatase at high temperatures necessitates that water be removed from the gas stream to avoid interference. A strategy involving the use of a hydrophobic microporous filter that can reject water and let gases such as CO pass unimpeded is examined. Successful use of such a concept has been demonstrated with a silicalite filter using moist CO gas streams.
Department of Chemistry, The Ohio State University, Columbus, Ohio 43210-1185, USA.
Joseph
J
Trimboli
Matthew
M
Mottern
Henk
H
Verweij
Prabir K
PK
Dutta