DRIFTS studies on CO and NO adsorption and NO+CO reaction over Pd2+-substituted CeO2 and Ce0.75Sn0.25O2 catalysts

• Published in: Journal of catalysis 2013-07, Vol.303, p.117-129
• Main Authors: Baidya, Tinku, Bera, Parthasarathi, Mukri, Bhaskar Devu, Parida, Sanjit Kumar, Kröcher, Oliver, Elsener, Martin, Hegde, M.S.
• Format: Article
• Language: English
• Subjects: Adsorption; Carbon dioxide; Catalysis; catalysts; Ce0.73Sn0.25Pd0.02O2−δ; Ce0.98Pd0.02O2−δ; ceric oxide; Chemistry; DRIFTS; Exact sciences and technology; General and physical chemistry; nitrates; nitric oxide; nitrites; Nitrous oxide; Reaction; Surface physical chemistry; temperature; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2013.03.020

CO adsorption followed by NO adsorption on Ce0.73Sn0.25Pd0.02O2−δ immediately leads to partial reduction of NO to N2O at 25°C. CO adsorption on this catalyst pre-adsorbed with NO results in mainly Pd2+–CO species and slow surface reduction occurs leading to Pdδ+–CO species due to the presence of stable nitrate/nitrite species. •Pd is in +2 state in Ce0.98Pd0.02O2−δ and Ce0.73Sn0.25Pd0.02O2−δ catalysts.•Pdδ+–CO species is formed when CO adsorbed over the catalysts.•Pd2+–CO band is observed when CO is adsorbed over NO pre-adsorbed catalysts.•NO is molecularly adsorbed on Ce0.98Pd0.02O2−δ and Ce0.73Sn0.25Pd0.02O2−δ.•Ce0.73Sn0.25Pd0.02O2−δ shows lowest temperature NO conversion and N2 selectivity. Sequential adsorption of CO and NO as well as equimolar NO+CO reaction with variation of temperature over Pd2+ ion–substituted CeO2 and Ce0.75Sn0.25O2 supports has been studied by DRIFTS technique. The results are compared with 2at.% Pd/Al2O3 containing Pd0. Both linear and bridging Pd0–CO bands are observed over 2at.% Pd/Al2O3. But, band positions are shifted to higher frequencies in Ce0.98Pd0.02O2−δ and Ce0.73Sn0.25Pd0.02O2−δ catalysts that could be associated with Pdδ+–CO species. In contrast, a Pd2+–CO band at 2160cm−1 is observed upon CO adsorption over Ce0.98Pd0.02O2−δ and Ce0.73Sn0.25Pd0.02O2−δ catalysts pre-adsorbed with NO and a Pd+–CO band at 2120cm−1 is slowly developed on Ce0.73Sn0.25Pd0.02O2−δ over time. An intense linear Pd0–NO band at 1750cm−1 found upon NO exposure to CO pre-adsorbed 2at.% Pd/Al2O3 indicates molecular adsorption of NO. On the other hand, a weak Pd2+–NO band at 1850cm−1 is noticed after NO exposure to Ce0.98Pd0.02O2−δ catalyst pre-adsorbed with CO indicating dissociative adsorption of NO which is crucial for NO reduction. Pd0–NO band is initially formed over CO pre-adsorbed Ce0.73Sn0.25Pd0.02O2−δ which is red-shifted over time along with formation of Pd2+–NO band. Several intense bands related to nitrates and nitrites are observed after exposure of NO to fresh as well as CO pre-adsorbed Ce0.98Pd0.02O2−δ and Ce0.73Sn0.25Pd0.02O2−δ catalysts. Ramping the temperature in a DRIFTS cell upon NO and CO adsorption shows the formation of N2O and NCO surface species, and N2O-formation temperature is comparable with the reaction done in a reactor.