The activation of NO and CH4 for NO-SCR reaction

LONYI, FERENC; SOLT, HANNA; VALYON, JOZSEF; BOIX, ALICIA V.; GUTIERREZ, LAURA

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2011 vol. 345 p. 75 - 80

1381-1169

The catalytic oxidation of NO to NO2 (NO-COX) and the selective catalytic reduction of NO to N2 by methane in the presence of excess oxygen (NO-SCR) was studied over zeolite In,H-, Co,H-, and Co,In,HZSM- 5 catalysts. The catalysts were characterized by temperature-programmed H2 reduction (H2-TPR) and operando DRIFT spectroscopy. The cobalt was present in the catalysts predominantly in Co-oxide clusters, whereas the charge of the zeolite framework was balanced by H+ and cationic indium species. The Brønsted acid sites promoted the NO-COX reaction; however, the Co-oxide clusters were much more active in this reaction. In absence of indium the catalysts were inactive in the NO-SCR reaction. The NO/NO2 mixture formed in the NO-COX reaction was shown to further react with the InO+/(InOH)2+- zeolite resulting in the simultaneous formation of InNO3 and NO+ species. The Co-oxide clusters increased the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture zeolite resulting in the simultaneous formation of InNO3 and NO+ species. The Co-oxide clusters increased the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture The Brønsted acid sites promoted the NO-COX reaction; however, the Co-oxide clusters were much more active in this reaction. In absence of indium the catalysts were inactive in the NO-SCR reaction. The NO/NO2 mixture formed in the NO-COX reaction was shown to further react with the InO+/(InOH)2+- zeolite resulting in the simultaneous formation of InNO3 and NO+ species. The Co-oxide clusters increased the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture zeolite resulting in the simultaneous formation of InNO3 and NO+ species. The Co-oxide clusters increased the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture and operando DRIFT spectroscopy. The cobalt was present in the catalysts predominantly in Co-oxide clusters, whereas the charge of the zeolite framework was balanced by H+ and cationic indium species. The Brønsted acid sites promoted the NO-COX reaction; however, the Co-oxide clusters were much more active in this reaction. In absence of indium the catalysts were inactive in the NO-SCR reaction. The NO/NO2 mixture formed in the NO-COX reaction was shown to further react with the InO+/(InOH)2+- zeolite resulting in the simultaneous formation of InNO3 and NO+ species. The Co-oxide clusters increased the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture zeolite resulting in the simultaneous formation of InNO3 and NO+ species. The Co-oxide clusters increased the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture The Brønsted acid sites promoted the NO-COX reaction; however, the Co-oxide clusters were much more active in this reaction. In absence of indium the catalysts were inactive in the NO-SCR reaction. The NO/NO2 mixture formed in the NO-COX reaction was shown to further react with the InO+/(InOH)2+- zeolite resulting in the simultaneous formation of InNO3 and NO+ species. The Co-oxide clusters increased the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture zeolite resulting in the simultaneous formation of InNO3 and NO+ species. The Co-oxide clusters increased the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture have been closed by the oxidation of In+ to InO+/(InOH)2+ by the reactant mixture the rate of NO2 generation and, thereby, the InNO3/NO+ formation. It was substantiated that an Ncontaining organic intermediate was obtained in the reaction of methane and nitrate group. Nitrogen was generated in the reaction between the obtained intermediate and the NO+. The catalytic cycle must have been closed by the oxidation of In