Water Deficient Environment Accelerates Proton Exchange: Acetone-Water Reaction Catalyzed by Calix 4 hydroquinone Nanotubes

    Authors

    M. Zakharov; A. E. Masunov;A. Dreuw

    Abbreviated Journal Title

    J. Phys. Chem. C

    Keywords

    ORGANIC NANOTUBES; ELECTRONIC-STRUCTURE; WAVE-FUNCTIONS; BASIS-SETS; GAS-PHASE; HYDROGEN; ENERGIES; ENOL; NMR; Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, ; Multidisciplinary

    Abstract

    Calix[4]hydroquinone nanotubes possess the unique property to catalyze proton exchange between water and acetone. Since concerted proton transfer mechanisms could be excluded previously, stepwise proton transfer via ionic intermediates created by predissociation of CHQ OH groups is studied using state-of-the-art quantum chemical methodology. In fact, the presence of charged species, protonated acetone or deprotonated hydroquinone, leads to a substantial decrease of the proton transfer energy barrier and to calculated reaction rates that provide an explanation for the experimentally observed proton exchange. Furthermore, our quantum chemical investigation demonstrates that the catalytic activity of CHQ aggregates is not based on a reduction of the energy barrier connected with proton transfer but on the desolvation of acetone and prevention of solvent water cluster formation.

    Journal Title

    Journal of Physical Chemistry C

    Volume

    113

    Issue/Number

    24

    Publication Date

    1-1-2009

    Document Type

    Article

    Language

    English

    First Page

    10395

    Last Page

    10401

    WOS Identifier

    WOS:000266930400016

    ISSN

    1932-7447

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