Decomposition of Urea in the SCR Process: Combination of DFT Calculations and Experimental Results on the Catalytic Hydrolysis of Isocyanic Acid on TiO₂ and Al₂O₃

In selective catalytic reduction (SCR) systems for diesel vehicles the injected urea solution decomposes to ammonia and isocyanic acid (HNCO), which reacts with water to another ammonia molecule and carbon dioxide over the SCR catalyst or a special urea decomposition catalyst. The second reaction step, i.e. the catalytic hydrolysis of HNCO was studied on the anatase TiO₂(101) surface and Al₂O₃(100) surface with ab initio density functional theory (DFT) calculations using a cluster model as well as with in situ diffuse reflectance infrared Fourier transform spectra (DRIFTS) investigations and kinetic experiments. The following mechanistic pathway has been identified to be most feasible: HNCO dissociatively adsorbs on the metal oxide surface as isocyanates, which are attacked by water, thereby forming carbamic acid at the surface. In a further step this intermediate is transformed to a carbamate complex, which leads to CO₂ desorption and consequently NH₃ formation. The comparison between the sum of the theoretical vibrational spectra of the reaction intermediates with the in situ DRIFT spectra also strongly supports the accuracy of the second reaction pathway. This mechanism holds also for the HNCO hydrolysis over γ-Al₂O₃ and the reactivity compared to TiO₂ was found to be consistent with the heights of the barriers in the energy diagrams. Based on these promising preliminary results a computational screening has been started in order to predict the most active metal oxides and surfaces for this reaction.