Enhanced oxidation activity from modified ceria: MnOx-ceria, CrOx-ceria and Mg doped VOx-ceria
| dc.check.date | 2018-03-09 | |
| dc.check.info | Access to this article is restricted until 24 months after publication by request of the publisher. | en |
| dc.contributor.author | Nolan, Michael | |
| dc.contributor.author | Ganduglia-Pirovano, M. Verónica | |
| dc.contributor.funder | Science Foundation Ireland | en |
| dc.contributor.funder | Seventh Framework Programme | en |
| dc.contributor.funder | European Cooperation in Science and Technology | en |
| dc.contributor.funder | Ministerio de Economía y Competitividad | en |
| dc.date.accessioned | 2016-11-11T09:41:26Z | |
| dc.date.available | 2016-11-11T09:41:26Z | |
| dc.date.issued | 2016-03-09 | |
| dc.description.abstract | Ceria is an important component of catalysts for oxidation reactions that proceed through the Mars-van Krevelen mechanism, promoting activity. A paradigm example of this is the VOx–CeO2 system for oxidative dehydrogenation reactions, where vanadium oxide species are supported on ceria and a special synergy between them is behind the enhanced activity: reduction of the catalyst is promoted by ceria undergoing reduction. This leads to favourable oxygen vacancy formation and hydrogen adsorption energies—useful descriptors for the oxidation activity of VOx–CeO2 catalysts. In this paper, we examine if this promoting effect on ceria-based catalysts holds for other metal oxide modifiers and we investigate MnOn– and CrOn–CeO2(111) (n = 0 − 4) as examples. We show, combining density functional theory calculations and statistical thermodynamics that similarly to the vanadia modifier, the stable species in each case is MnO2– and CrO2–CeO2. Both show favourable energetics for oxygen vacancy formation and hydrogen adsorption, indicating that VO2–CeO2 is not the only system of this type that can have an enhanced activity for oxidation reactions. However, the mechanism involved in each case is different: CrO2–CeO2 shows similar properties to VO2–CeO2 with ceria reduction upon oxygen removal stabilising the 5+ oxidation state of Cr. In contrast, with MnO2–CeO2, Mn is preferentially reduced. Finally, a model system of VO2–Mg:CeO2 is explored that shows a synergy between VO2 modification and Mg doping. These results shed light on the factors involved in active oxidation catalysts based on supported metal oxides on ceria that should be taken into consideration in a rational design of such catalysts. | en |
| dc.description.sponsorship | Science Foundation Ireland (Grant Numbers SFI 09/SIRG/I1620 and SFI 14/US/E2915); European Commission (FP7 Project BIOGO, contract number 604296; COST Action CM1104 “Reducible Oxide Chemistry, Structure and Functions”); Ministry of Economy and Competitiveness (Project CTQ2012-32928) | en |
| dc.description.status | Peer reviewed | en |
| dc.description.version | Accepted Version | en |
| dc.format.mimetype | application/pdf | en |
| dc.identifier.citation | NOLAN, M. and GANDUGLIA-PIROVANO, M. V. (2016) ‘Enhanced oxidation activity from modified ceria: MnOx–ceria, CrOx–ceria and Mg doped VOx–ceria’, Applied Catalysis B: Environmental, 197, pp. 313-323. doi:10.1016/j.apcatb.2016.03.015 | en |
| dc.identifier.doi | 10.1016/j.apcatb.2016.03.015 | |
| dc.identifier.endpage | 323 | en |
| dc.identifier.issn | 0926-3373 | |
| dc.identifier.journaltitle | Applied Catalysis B: Environmental | en |
| dc.identifier.startpage | 313 | en |
| dc.identifier.uri | https://hdl.handle.net/10468/3265 | |
| dc.identifier.volume | 197 | en |
| dc.language.iso | en | en |
| dc.publisher | Elsevier B.V. | en |
| dc.relation.project | info:eu-repo/grantAgreement/EC/FP7::SP1::NMP/604296/EU/Catalytic Partial Oxidation of Bio Gas and Reforming of Pyrolysis Oil (Bio Oil) for an Autothermal Synthesis Gas Production and Conversion into Fuels/BIOGO-FOR-PRODUCTION | en |
| dc.rights | © 2016, Elsevier B.V. All rights reserved. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ | en |
| dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | en |
| dc.subject | Ceria | en |
| dc.subject | Oxidation | en |
| dc.subject | Adsorption | en |
| dc.subject | DFT | en |
| dc.title | Enhanced oxidation activity from modified ceria: MnOx-ceria, CrOx-ceria and Mg doped VOx-ceria | en |
| dc.type | Article (peer-reviewed) | en |
