Redox properties and catalytic activity relationships in methane combustion for pt-ceo2/tio2 supported catalysts
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2022-06-10 21:22
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544+544.47 (1)
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CIOBANU, Madalina, PETCU, Gabriela, PAPA, Florica, APOSTOL, Nicoleta G., PARVULESCU, Viorica. Redox properties and catalytic activity relationships in methane combustion for pt-ceo2/tio2 supported catalysts. In: Ecological and environmental chemistry : - 2022, Ed. 7, 3-4 martie 2022, Chișinău. Chisinau: Centrul Editorial-Poligrafic al USM, 2022, Ediția 7, Vol.1, pp. 62-63. ISBN 978-9975-159-07-4.. 10.19261/eec.2022.v1
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Ecological and environmental chemistry
Ediția 7, Vol.1, 2022
Conferința "Ecological and environmental chemistry 2022"
7, Chișinău, Moldova, 3-4 martie 2022

Redox properties and catalytic activity relationships in methane combustion for pt-ceo2/tio2 supported catalysts

CZU: 544+544.47

Pag. 62-63

Ciobanu Madalina1, Petcu Gabriela1, Papa Florica1, Apostol Nicoleta G.2, Parvulescu Viorica1
 
1 “Ilie Murgulescu” Institute of Physical Chemistry of the Romanian Academy,
2 National Institute of Materials Physics Bucharest-Magurele
 
 
Disponibil în IBN: 3 martie 2022


Rezumat

Aim and methods: The great interest and continuous efforts are dedicated to obtain better catalysts for conversion of the saturated hydrocarbons from air. One of the less explored strategies to enhance the catalytic activity of supported noble/transition metal catalysts is the addition of a second transition metal to the first one. For this purpose, Ce can be a good alternative for the oxidation catalysts reason why this paper evidences the effect of ceria on redox properties and catalytic activity of Pt/TiO2 high dispersed on mesoporous silica (KIT-6, SBA-15) support. The obtained materials were characterized by various techniques and catalytic activity was tested in total oxidation of methane from air, as a model for understanding the mechanisms of oxidation and catalytic combustion on such catalysts. Results: Characterization results showed that ceria addition (1%) increased Pt dispersion, reduced the crystallinity of metallic platinum and modified its percentage on the surface. Significant is the different effect of the interaction of Pt species with TiO2 and CeO2 which influences the concentration of Pt0 on the surface. XRD, TPR and XPS results evidenced the effects of ceria immobilization method, Pt (0.25, 0.5, 1%) and titania (5, 10, 30%) loading on Pt0/Pt+, Ce4+/Ce3+, TiO2/TiOx atomic ratio on the surface with significant influence on redox properties, respectively catalytic reaction. Thus, considering that combustion of methane on these catalysts is a Mars van-Krevelen type reaction, with CH4 chemisorbed on surface Pt atoms, C-H bond dissociation is the rate determining step due to the relatively large activation energy and greater entropy loss for this molecule. The oxidation on PtO species with lattice oxygen provided by TiO2-CeO2 and finally refill of the oxygen vacancies by gas-phase O2. Ti and Ce oxides high disppersed on the support are the oxygen carriers and the existence of PtO and metallic Pt is essential to provide activity. This explained the reduction in catalytic performance for sample with Pt coated by ceria for which the XPS results indicated the absence of PtO on the surface. In oxidation reactions the oxygen storage capacity provided by the redox couple Ce4+/Ce3+, ratio which varied around 1.1, under a small variation of Ce and Ti species on the surface. High combustion of methane (100% conversion) at low temperature (300-500 °C) was obtained for catalysts with 1% Pt. More significant on the conversion was the increase of the concentration of Pt and TiO2, in the conditions of a low concentration of CeO2. Conclusions: This study showed that both CeO2 and TiO2 are beneficial to stabilize the active PtO and Pt0 playing important role in the complete oxidation of methane. Their loading and dispersion, with significant influence on redox properties, determine the catalytic activity.