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On the Chemistry of Ethanol on Basic Oxides: Revising Mechanisms and Intermediates in the Lebedev and Guerbet reactions
Author(s) -
Chieregato Alessandro,
Velasquez Ochoa Juliana,
Bandinelli Claudia,
Fornasari Giuseppe,
Cavani Fabrizio,
Mella Massimo
Publication year - 2015
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201402632
Subject(s) - chemistry , catalysis , reactivity (psychology) , computational chemistry , reaction intermediate , reactive intermediate , reaction mechanism , organic chemistry , green chemistry , combinatorial chemistry , biochemical engineering , medicine , alternative medicine , pathology , engineering
A common way to convert ethanol into chemicals is by upgrading it over oxide catalysts with basic features; this method makes it possible to obtain important chemicals such as 1‐butanol (Guerbet reaction) and 1,3‐butadiene (Lebedev reaction). Despite their long history in chemistry, the details of the close inter‐relationship of these reactions have yet to be discussed properly. Our present study focuses on reactivity tests, in situ diffuse reflectance infrared Fourier transform spectroscopy, MS analysis, and theoretical modeling. We used MgO as a reference catalyst with pure basic features to explore ethanol conversion from its very early stages. Based on the obtained results, we formulate a new mechanistic theory able to explain not only our results but also most of the scientific literature on Lebedev and Guerbet chemistry. This provides a rational description of the intermediates shared by the two reaction pathways as well as an innovative perspective on the catalyst requirements to direct the reaction pathway toward 1‐butanol or butadiene.