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Understanding the Reaction Mechanism of Glycerol Hydrogenolysis over a CuCr 2 O 4 Catalyst
Author(s) -
Yun Yang Sik,
Kim Tae Yong,
Yun Danim,
Lee Kyung Rok,
Han Jeong Woo,
Yi Jongheop
Publication year - 2017
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.201601269
Subject(s) - hydrogenolysis , catalysis , adsorption , reaction mechanism , spinel , exothermic reaction , chemistry , reaction intermediate , glycerol , inorganic chemistry , materials science , organic chemistry , metallurgy
The reaction mechanism of glycerol hydrogenolysis to 1,2‐propanediol over a spinel CuCr 2 O 4 catalyst was investigated by using DFT calculations. Theoretical models were developed from the results of experimental characterization. Adsorption configurations and energetics of the reactant, intermediates, final product, and transition states were calculated on Cu(1 1 1) and CuCr 2 O 4 (1 0 0). Based on our DFT results, we found that the formation of acetol is preferred to that of 3‐hydroxypropionaldehyde thermodynamically and kinetically on both surfaces. For glycerol hydrogenolysis to 1,2‐propanediol, the CuCr 2 O 4 surface is less exothermic but more kinetically favorable than the Cu surface. The low activation barrier during the reaction on the CuCr 2 O 4 surface is attributed to the unique surface structure; the cubic spinel structure provides a stable adsorption site on which reactants are allowed to be dehydrated and hydrogenated easily with the characteristic adsorption configuration. The role of the Cu and Cr atoms in a CuCr 2 O 4 surface were revealed. The results of reaction tests supported our theoretical calculations.