Methane reacts with heteropolyacids chemisorbed on silica to produce acetic acid under soft conditions
Rossini, Aaron J.
KAUST DepartmentAdvanced Membranes and Porous Materials Research Center
Biological and Environmental Sciences and Engineering (BESE) Division
Chemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Online Publication Date2013-01-03
Print Publication Date2013-01-16
Permanent link to this recordhttp://hdl.handle.net/10754/562614
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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.
CitationSun, M., Abou-Hamad, E., Rossini, A. J., Zhang, J., Lesage, A., Zhu, H., … Basset, J.-M. (2013). Methane Reacts with Heteropolyacids Chemisorbed on Silica to Produce Acetic Acid under Soft Conditions. Journal of the American Chemical Society, 135(2), 804–810. doi:10.1021/ja309966j
SponsorsThe 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.
PublisherAmerican Chemical Society (ACS)
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