Original Synthesis of Molybdenum Nitrides Using Metal Cluster Compounds as Precursors: Applications in Heterogeneous Catalysis
Kévin GuyFranck TessierHelena KaperFabien GrassetNoée DumaitValérie DemangeMitsuaki NishioYoshitaka MatsushitaYoshio MatsuiToshiaki TakeiDavid LechevalierCaroline TardivatTetsuo UchikoshiNaoki OhashiStéphane Cordier
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Abstract:
Transition metal nitrides (TMN) form a class of materials with unique physical and chemical properties. Among them, molybdenum nitrides are mainly used as high-performance magnets or catalysts for a wide range of reactions. This work aims at developing innovative syntheses to prepare nanostructured TMN from metallic clusters for heterogeneous catalysis. The use of a nanoscale precursor such as (TBA)2Mo6Br14 (TBA = tetrabutylammonium = (C4H9)4N+) enables us to reach different molybdenum nitride compositions (Mo2N, Mo5N6) by thermal reaction under ammonia at relatively low temperatures. Such a novel synthetic approach highlights the prime importance of the starting material to stabilize specific stoichiometries. The impact of this new synthetic route is characterized by several techniques including electron probe microanalysis and high-resolution transmission microscopy. Moreover, catalytic properties of these potential cost-effective catalysts are investigated for the Water–Gas Shift Reaction.Keywords:
Stoichiometry
Microanalysis
Molybdenum disulfide
For pure molybdenum nitrided at 1373 K in NH 3 gas, microstructural observations of a molybdenum nitride layer were conducted through a transmission electron microscope. The molybdenum nitride layer consisted of two molybdenum nitrides: an outer one of γ‐Mo 2 N and an inner one of β‐Mo 2 N. A great number of (011)[01] type twins were observed in the β‐Mo 2 N phase, whereas the microstructure of the γ‐Mo 2 N phase was almost free from lattice defects except for slightly observed {111}〈112〉 type twin.
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The syntheses, crystallographic structures, magnetic properties, and theoretical studies of two heptacoordinated molybdenum complexes with N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine (H4N2O2) are reported. A formally molybdenum(VI) complex [Mo(N2O2)Cl2(dmf)] (1) was synthesized by the reaction between [MoO2Cl2(dmf)2] and H4N2O2, whereas the other molybdenum(VI) complex [Mo(N2O2)(HN2O2)] (2) was formed when [MoO2(acac)2] was used as a molybdenum source. Both complexes represent a rare case of the MoVI ion without any multiply bonded terminal ligands. In addition, molecular structures, magnetic measurements, ESR spectroscopy, and density functional theory calculations indicate that complex 2 is the first stable molybdenum(VI) amidophenoxide radical.
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ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTUse of .eta.6-arylphosphine complexes of molybdenum(0) for the synthesis of complexes containing molybdenum-molybdenum and molybdenum-tungsten quadruple bondsRudy L. Luck and Robert H. MorrisCite this: J. Am. Chem. Soc. 1984, 106, 25, 7978–7979Publication Date (Print):December 1, 1984Publication History Published online1 May 2002Published inissue 1 December 1984https://pubs.acs.org/doi/10.1021/ja00337a058https://doi.org/10.1021/ja00337a058research-articleACS PublicationsRequest reuse permissionsArticle Views123Altmetric-Citations13LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts
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Protein induced ultrathin MoS2 flakes were successfully exfoliated, and they were used as additives for water-based lubricating systems, which indicated that they could improve the friction performance and anti-wear abilities at a low concentration.
Molybdenum disulfide
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Abstract Die Reaktion des Mo(O)‐Komplexes (I), in dem ein Phosphin über einen der Pheny1‐Substituenten koordiniert ist, mit MoCl 4 (TH F); oder WCl 4 (PPh 3 ) 2 ergibt den homo‐ bzw. heterozweikernigen Komplex (II) und (IV) mit einer Vierfachbindung zwischen beiden Metallen ohne unterstützende Brückenliganden.
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Molybdenum disulfide
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Molybdenum disulfide (MoS2) has long been known as a low- friction material. Low, ultralow and superlow friction properties of MoS2 are shown in this section.
Molybdenum disulfide
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Abstract Als mögliche Modelle für die Koordination von Mo durch ungesättigte Thiolat‐Jfhioether‐Liganden in dem Mo‐Pterin‐Cofaktor von Molybdänenzymen wurden die Titelkomplexe (III), (Va) und (VI) dargestellt (siehe Schema).
Molybdenum oxide
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Abstract Durch Zugabe von tBuNC zu einer Lösung von (I) erhält man den Komplex (II), der durch Daten des Elektronenund 1 H‐ und ÜC‐NMR‐Spektrums sowie eine Kristallstrukturbestimmung (Raumgruppe I5") P2 1 /c, Z=4) charakterisiert wurde.
Molybdenum oxide
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