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Integrated In?Situ Characterization of a Molten Salt Catalyst Surface: Evidence of Sodium Peroxide and Hydroxyl Radical Formation.

ABSTRACT: Sodium-based catalysts (such as Na₂ WO₄ ) were proposed to selectively catalyze OH radical formation from H₂ O and O₂ at high temperatures. This reaction may proceed on molten salt state surfaces owing to the lower melting point of the used Na salts compared to the reaction temperature. This study provides direct evidence of the molten salt state of Na₂ WO₄ , which can form OH radicals, using in?situ techniques including X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), laser induced fluorescence (LIF) spectrometry, and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). As a result, Na₂ O₂ species, which were hypothesized to be responsible for the formation of OH radicals, have been identified on the outer surfaces at temperatures of ?800?°C, and these species are useful for various gas-phase hydrocarbon reactions, including the selective transformation of methane to ethane.

SUBMITTER: Takanabe K

PROVIDER: S-EPMC5601248 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Integrated In Situ Characterization of a Molten Salt Catalyst Surface: Evidence of Sodium Peroxide and Hydroxyl Radical Formation.

Takanabe Kazuhiro K Khan Abdulaziz M AM Tang Yu Y Nguyen Luan L Ziani Ahmed A Jacobs Benjamin W BW Elbaz Ayman M AM Sarathy S Mani SM Tao Franklin Feng FF

Angewandte Chemie (International ed. in English) 20170724 35

Sodium-based catalysts (such as Na2 WO4 ) were proposed to selectively catalyze OH radical formation from H2 O and O2 at high temperatures. This reaction may proceed on molten salt state surfaces owing to the lower melting point of the used Na salts compared to the reaction temperature. This study provides direct evidence of the molten salt state of Na2 WO4 , which can form OH radicals, using in situ techniques including X-ray dif ...[more]

PMID: 28650565

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Project description:BackgroundFibrous chrysotile has been the most commonly applied asbestos mineral in a range of technical applications. However, it is toxic and carcinogenic upon inhalation. The chemical reactivity of chrysotile fiber surfaces contributes to its adverse health effects by catalyzing the formation of highly reactive hydroxyl radicals (HO•) from H2O2. In this Haber-Weiss cycle, Fe on the fiber surface acts as a catalyst: Fe3+ decomposes H2O2 to reductants that reduce surface Fe3+ to Fe2+, which is back-oxidized by H2O2 (Fenton-oxidation) to yield HO•. Chrysotile contains three structural Fe species: ferrous and ferric octahedral Fe and ferric tetrahedral Fe (Fe3+tet). Also, external Fe may adsorb or precipitate onto fiber surfaces. The goal of this study was to identify the Fe species on chrysotile surfaces that catalyze H2O2 decomposition and HO• generation.ResultsWe demonstrate that at the physiological pH 7.4 Fe3+tet on chrysotile surfaces substantially contributes to H2O2 decomposition and is the key structural Fe species catalyzing HO• generation. After depleting Fe from fiber surfaces, a remnant fiber-related H2O2 decomposition mode was identified, which may involve magnetite impurities, remnant Fe or substituted redox-active transition metals other than Fe. Fe (hydr)oxide precipitates on chrysotile surfaces also contributed to H2O2 decomposition, but were per mole Fe substantially less efficient than surface Fe3+tet. Fe added to chrysotile fibers increased HO• generation only when it became incorporated and tetrahedrally coordinated into vacancy sites in the Si layer.ConclusionsOur results suggest that at the physiological pH 7.4, oxidative stress caused by chrysotile fibers largely results from radicals produced in the Haber-Weiss cycle that is catalyzed by Fe3+tet. The catalytic role of Fe3+tet in radical generation may also apply to other pathogenic silicates in which Fe3+tet is substituted, e.g. quartz, amphiboles and zeolites. However, even if these pathogenic minerals do not contain Fe, our results suggest that the mere presence of vacancy sites may pose a risk, as incorporation of external Fe into a tetrahedral coordination environment can lead to HO• generation.

Dataset Information

Integrated In?Situ Characterization of a Molten Salt Catalyst Surface: Evidence of Sodium Peroxide and Hydroxyl Radical Formation.

Publications

Integrated In Situ Characterization of a Molten Salt Catalyst Surface: Evidence of Sodium Peroxide and Hydroxyl Radical Formation.

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