Methane reacts with heteropolyacids chemisorbed on silica to produce acetic acid under soft conditions

Handle URI:
http://hdl.handle.net/10754/562614
Title:
Methane reacts with heteropolyacids chemisorbed on silica to produce acetic acid under soft conditions
Authors:
Sun, Miao; Abou-Hamad, Edy; Rossini, Aaron J.; Zhang, Jizhe; Lesage, Anne; Zhu, Haibo; Pelletier, Jeremie ( 0000-0002-4709-4898 ) ; Emsley, Lyndon; Caps, Valerie; Basset, Jean-Marie ( 0000-0003-3166-8882 )
Abstract:
Selective functionalization of methane at moderate temperature is of crucial economic, environmental, and scientific importance. Here, we report that methane reacts with heteropolyacids (HPAs) chemisorbed on silica to produce acetic acid under soft conditions. Specially, when chemisorbed on silica, H 4SiW12O40, H3PW12O 40, H4SiMo12O40, and H 3PMo12O40 activate the primary C-H bond of methane at room temperature and atmospheric pressure. With these systems, acetic acid is produced directly from methane, in a single step, in the absence of Pd and without adding CO. Extensive surface characterization by solid-state NMR spectroscopy, IR spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy suggests that C-H activation of methane is triggered by the protons in the HPA-silica interface with concerted reduction of the Keggin cage, leading to water formation and hydration of the interface. This is the simplest and mildest way reported to date to functionalize methane. © 2012 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division; Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society
Journal:
Journal of the American Chemical Society
Issue Date:
16-Jan-2013
DOI:
10.1021/ja309966j
Type:
Article
ISSN:
00027863
Sponsors:
The authors acknowledge KAUST Nuclear Magnetic Resonance Core Lab and technical assistance of Dr. Kazuo Yamauchi (NMR). The authors also wish to thank Dr. Aram Amassian, Mr. Ahmed E. Mansour, and Mr. Guy Olivier NGONGANG NDJAWA for their kind help in XPS measurements. M.S. acknowledges support from Dr. Xin Liu in HPA structure drawing. A.J.R acknowledges support from an EU Marie-Curie IIF fellowship (PIIF-GA-2010-274574). This work was supported by funds from King Abdullah University of Science and Technology and SABIC (Saudi Basic Industries Corporation) company.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorSun, Miaoen
dc.contributor.authorAbou-Hamad, Edyen
dc.contributor.authorRossini, Aaron J.en
dc.contributor.authorZhang, Jizheen
dc.contributor.authorLesage, Anneen
dc.contributor.authorZhu, Haiboen
dc.contributor.authorPelletier, Jeremieen
dc.contributor.authorEmsley, Lyndonen
dc.contributor.authorCaps, Valerieen
dc.contributor.authorBasset, Jean-Marieen
dc.date.accessioned2015-08-03T10:58:25Zen
dc.date.available2015-08-03T10:58:25Zen
dc.date.issued2013-01-16en
dc.identifier.issn00027863en
dc.identifier.doi10.1021/ja309966jen
dc.identifier.urihttp://hdl.handle.net/10754/562614en
dc.description.abstractSelective functionalization of methane at moderate temperature is of crucial economic, environmental, and scientific importance. Here, we report that methane reacts with heteropolyacids (HPAs) chemisorbed on silica to produce acetic acid under soft conditions. Specially, when chemisorbed on silica, H 4SiW12O40, H3PW12O 40, H4SiMo12O40, and H 3PMo12O40 activate the primary C-H bond of methane at room temperature and atmospheric pressure. With these systems, acetic acid is produced directly from methane, in a single step, in the absence of Pd and without adding CO. Extensive surface characterization by solid-state NMR spectroscopy, IR spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy suggests that C-H activation of methane is triggered by the protons in the HPA-silica interface with concerted reduction of the Keggin cage, leading to water formation and hydration of the interface. This is the simplest and mildest way reported to date to functionalize methane. © 2012 American Chemical Society.en
dc.description.sponsorshipThe authors acknowledge KAUST Nuclear Magnetic Resonance Core Lab and technical assistance of Dr. Kazuo Yamauchi (NMR). The authors also wish to thank Dr. Aram Amassian, Mr. Ahmed E. Mansour, and Mr. Guy Olivier NGONGANG NDJAWA for their kind help in XPS measurements. M.S. acknowledges support from Dr. Xin Liu in HPA structure drawing. A.J.R acknowledges support from an EU Marie-Curie IIF fellowship (PIIF-GA-2010-274574). This work was supported by funds from King Abdullah University of Science and Technology and SABIC (Saudi Basic Industries Corporation) company.en
dc.publisherAmerican Chemical Societyen
dc.titleMethane reacts with heteropolyacids chemisorbed on silica to produce acetic acid under soft conditionsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalJournal of the American Chemical Societyen
dc.contributor.institutionUniversité de Lyon, CNRS/ENS-Lyon/UCB Lyon 1, Centre de RMN AÌ TreÌs Hauts Champs, 5 rue de la Doua, 69100 Villeurbanne, Franceen
dc.contributor.institutionLaboratoire des Matériaux, Surfaces et Procédés Pour la Catalyse (LMSPC), UMR 7515, CNRS/ECPM/Université de Strasbourg, 25 rue Becquerel, 67087 Strasbourg Cedex 2, Franceen
kaust.authorSun, Miaoen
kaust.authorAbou-Hamad, Edyen
kaust.authorZhang, Jizheen
kaust.authorZhu, Haiboen
kaust.authorPelletier, Jeremieen
kaust.authorCaps, Valerieen
kaust.authorBasset, Jean-Marieen
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