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Nanostructured Rare Earth Catalysts Via Advanced Surface Grafting

  • Chapter
Nanostructured Catalysts

Part of the book series: Nanostructure Science and Technology ((NST))

Abstract

Mesoporous silicas of the M41S family are discussed as attractive host materials in catalysis and materials science. Their intrinsic zeolite-like pore architecture with tunable pore sizes and narrow pore size distributions provides a unique platform (model support) to study the grafting of highly reactive organometallic compounds. In contrast to their alkyl and alkoxide derivatives, silylamide complexes of oxophilic and electrophilic metal centers display favorable surface reactions featuring (i) mild reaction conditions, (ii) the formation of thermodynamically stable metal siloxide bonds, (iii) concomitant surface silylation, (iv) favorable atom economy, and (v) the absence of any insoluble by-products. Various conceptual approaches to this novel heterogeneously performed silylamine elimination are presented for the lanthanide elements, which are promising components of nanostructured catalysts. Particular emphasis is put on the application of conclusive methods of characterization of the hybrid materials, elaborating the importance of spectroscopic probe ligands and nitrogen physisorption measurements. It is shown that the Lewis acidity (i.e., cation size), pore diameter, surface silylation and confinement are critical parameters influencing the catalytic performance of lanthanide(III) surface species, for example, in the hetero Diels-Alder and Meerwein-Ponndorf-Verley reactions. Moreover, pore entrapment and surface confinement seem to be important factors which govern the stabilization and reactivity patterns of the surface species involved in the samarium(II)-mediated reduction of ketones.

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  1. Anorganisch-chemisches Institut, Technische Universität München, D-85747, Garching, Lichtenbergstraβe 4, Germany

    Reiner Anwander

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  1. University of Ottawa, Ottawa, Ontario, Canada

    Susannah L. Scott

  2. Queen’s University, Kingston, Ontario, Canada

    Cathleen M. Crudden

  3. Georgia Institute of Technology, Atlanta, Georgia

    Christopher W. Jones

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Anwander, R. (2005). Nanostructured Rare Earth Catalysts Via Advanced Surface Grafting. In: Scott, S.L., Crudden, C.M., Jones, C.W. (eds) Nanostructured Catalysts. Nanostructure Science and Technology. Springer, Boston, MA. https://doi.org/10.1007/978-0-387-30641-4_2

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