Photooxidation of Ammonia on TiO2 as a Source of NO and NO2 under Atmospheric Conditions

Ammonia is the most abundant reduced nitrogen species in the atmosphere and an important precursor in the industrial-scale production of nitric acid. A coated-wall flow tube coupled to a chemiluminescence NOx analyzer was used to study the kinetics of NH3 uptake and NOx formation from photochemistry initiated on irradiated (lambda > 290 tun) TiO2 surfaces under atmospherically relevant conditions. The speciation of NH3 on TiO2 surfaces in the presence of surface adsorbed water was determined using diffuse reflection infrared Fourier transform spectroscopy. The uptake kinetics exhibit an inverse dependence on NH3 concentration as expected for reactions proceeding via a Langmuir-Hinshelwood mechanism. The mechanism of NOx formation is shown to be humidity dependent: Water catalyzed reactions promote NOx formation up to a relative humidity of 50%. Less NOx is formed above 50%, where increasing amounts of adsorbed water may hinder access to reactive sites, promote formation of unreactive NH4+, and reduce oxidant levels due to higher OH radical recombination rates. A theoretical study of the reaction between the NH2 photoproduct and O-2 in the presence of H2O supports the experimental conclusion that NOx formation is catalyzed by water. Calculations at the MP2 and CCSD(T) level on the bare NH2 + O-2 reaction and the reaction of NH2 + O-2 in small water clusters were carried out Solvation of NH2OO and NHOOH intermediates likely facilitates isomerization via proton transfer along water wires, such that the steps leading ultimately to NO are exothermic. These results show that photooxidation of low levels of NH3 on TiO2 surfaces represents a source of atmospheric NOx, which is a precursor to ozone. The proposed mechanism may be broadly applicable to dissociative chemisorption of NH3 on other metal oxide surfaces encountered in rural and urban environments and employed in pollution control applications (selective catalytic oxidation/reduction) and during some industrial processes.