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Atmospheric‐Pressure, Liquid‐Phase, Selective Aerobic Oxidation of Alkanes Catalysed by Metal–Organic Frameworks
Author(s) -
Dhakshinamoorthy Amarajothi,
Alvaro Mercedes,
Garcia Hermenegildo
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002664
Subject(s) - cyclooctane , selectivity , chemistry , catalysis , ethylbenzene , hydrocarbon , oxide , atmospheric pressure , phase (matter) , product distribution , metal , metal organic framework , tetralin , inorganic chemistry , organic chemistry , photochemistry , chemical engineering , adsorption , oceanography , engineering , geology
Aerobic oxidation of cyclooctane to its corresponding ol/one mixture at atmospheric pressure and in the liquid phase is efficiently promoted by an Fe(BTC) (BTC=1,3,5‐benzenetricarboxylate) metal–organic framework, incorporating N ‐hydroxyphthalimide and in several cases reaches a selectivity over 90 % at 28 % conversion. This catalytic system is further extended to other hydrocarbons, such as ethylbenzene and 1,2,3,4‐tetrahydronaphthalene (tetralin), with high selectivity (>85 %). This high selectivity in the product distribution arises from a radical reaction mechanism that occurs inside a hydrophobic cavity that preferentially adsorbs hydrocarbons over their corresponding alcohols. The system can be reused although there is a gradual decrease in turnover frequency, caused by minor changes in the crystal structure due to the formation of iron oxide nanoparticles. Given the sustainable nature of the oxidant and the mild conditions used, this discovery could serve to develop a new catalyst generation for the oxyfunctionalisation of hydrocarbon feedstocks with the real possibility of finding industrial application.