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dc.contributor.authorSzécsényi, Ágnes
dc.contributor.authorLi, Guanna
dc.contributor.authorGascon, Jorge
dc.contributor.authorPidko, Evgeny A.
dc.date.accessioned2019-03-11T07:13:45Z
dc.date.available2019-03-11T07:13:45Z
dc.date.issued2018-07-18
dc.identifier.citationSzécsényi Á, Li G, Gascon J, Pidko EA (2018) Mechanistic Complexity of Methane Oxidation with H2O2 by Single-Site Fe/ZSM-5 Catalyst. ACS Catalysis 8: 7961–7972. Available: http://dx.doi.org/10.1021/acscatal.8b01672.
dc.identifier.issn2155-5435
dc.identifier.issn2155-5435
dc.identifier.doi10.1021/acscatal.8b01672
dc.identifier.urihttp://hdl.handle.net/10754/631522
dc.description.abstractPeriodic density functional theory (DFT) calculations were carried out to investigate the mechanism of methane oxidation with HO over the defined Fe sites in Fe/ZSM-5 zeolite. The initial Fe site is modeled as a [(HO)-Fe(III)-(μO)-Fe(III)-(HO)] extraframework cluster deposited in the zeolite pore and charge-compensated by two anionic lattice sites. The activation of this cluster with HO gives rise to the formation of a variety of Fe(III)-oxo and Fe(IV)-oxo complexes potentially reactive toward methane dissociation. These sites are all able to promote the first C-H bond cleavage in methane by following three possible reaction mechanisms: namely, (a) heterolytic and (b) homolytic methane dissociation as well as (c) Fenton-type reaction involving free OH radicals as the catalytic species. The C-H activation step is followed by formation of MeOH and MeOOH and regeneration of the active site. The Fenton-type path is found to proceed with the lowest activation barrier. Although the barriers for the alternative heterolytic and homolytic pathways are found to be somewhat higher, they are still quite favorable and are expected to be feasible under reaction conditions, resulting ultimately in MeOH and MeOOH products. HO oxidant competes with CH substrate for the same sites. Since the oxidation of HO to O and two [H] is energetically more favorable than the C-H oxofunctionalization, the overall efficiency of the latter target process remains low.
dc.description.sponsorshipWe thank Elena Khramenkova (ITMO University) for carrying out some of the calculations. The Dutch Science Foundation (NWO) is gratefully acknowledged for financial support through the VIDI personal grant MetMOFCat. G.L. acknowledges financial support from NWO for her personal VENI grant (016.Veni.172.034). E.A.P. acknowledges partial support from the Ministry of Education and Science of the Russian Federation (Project 11.1706.2017/4.6). SurfSARA and NWO (The Netherlands Organisation for Scientific Research) are acknowledged for providing access to supercomputer resources.
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/acscatal.8b01672
dc.rightsThis is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License, which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
dc.rights.urihttp://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html
dc.subjectcatalytic reaction networks
dc.subjectcomputational chemistry
dc.subjectDFT calculations
dc.subjectheterogeneous catalysis
dc.subjectselective oxidation
dc.subjectselectivity control
dc.subjectzeolites
dc.titleMechanistic Complexity of Methane Oxidation with H2O2 by Single-Site Fe/ZSM-5 Catalyst
dc.typeArticle
dc.contributor.departmentChemical and Biological Engineering Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.identifier.journalACS Catalysis
dc.eprint.versionPublisher's Version/PDF
dc.contributor.institutionInorganic Systems Engineering Group, Chemical Engineering Department, Delft University of Technology, Van der Maasweg 9, 2629 HZ Delft, The Netherlands
dc.contributor.institutionCatalysis Engineering Group, Chemical Engineering Department, Chemical Engineering Department, Delft University of Technology, Van der Maasweg 9, 2629 HZ Delft, The Netherlands
dc.contributor.institutionTheoMAT Group, ITMO University, Lomonosova Street 9, St. Petersburg 191002, Russia
kaust.personSzécsényi, Ágnes
kaust.personGascon, Jorge
refterms.dateFOA2019-03-12T14:01:27Z
dc.date.published-online2018-07-18
dc.date.published-print2018-09-07


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