Drastic change in selectivity caused by addition of oxygen to the hydrogen stream for the hydrogenation of nitrite in water over a supported platinum catalyst†
Abstract
In the present study, we investigated the influence of the addition of O2 to the H2 reactant stream during the hydrogenation of NO2− in water on the catalytic performances of Al2O3-supported precious metal catalysts including Pd, Pt, Ir, Rh, and Ru with 0.3 mmol g−1 of the metal. Pd/Al2O3 showed high selectivity for N2 irrespective of the presence and absence of O2, and Rh and Ru/Al2O3 were inactive towards the hydrogenation of NO2− even in the absence of O2. In contrast, while Pt/Al2O3 showed high selectivity for NH3 (90%) in the absence of O2 (PH2 = 0.2 atm and PO2 = 0 atm), the product drastically changed to N2 with 93% selectivity when O2 was added (PH2 = 0.2 atm and PO2 = 0.1 atm). Since Pt/Al2O3 was completely inactive towards the oxidation of NH3 with O2 in water under the reaction conditions, oxidative decomposition of the formed NH3 was not the reason for the high selectivity for N2 in the presence of O2. Kinetic analysis of the reaction in the absence and presence of O2 and studies on the effects of the Pt size suggested that hydrogen atoms activated on the Pt particles were mainly consumed by O2 upon H2O formation in the presence of O2. We concluded that the inactivation of the Pt sites active for NH3 formation and furthermore the change in the function of the sites to N2 formation caused by the O2 addition lead to the drastic change in the selectivity from NH3 to N2 in the presence of O2.