Microgel-stabilized gold nanoclusters: Powerful “quasi-homogeneous” catalysts for the aerobic oxidation of alcohols in water
作者:A BIFFIS、S CUNIAL、P SPONTONI、L PRATI
DOI:10.1016/j.jcat.2007.07.024
日期:2007.10.1
Gold nanoclusters of small size (2.5 nm) and narrow size distribution were synthesized in solution using tailor-made soluble cross-linked polymers (microgels) as exotemplates and stabilizers. The resulting microgel-stabilized nanoclusters could be conveniently isolated by precipitation, stored in the solid state, and redispersed in water and polar organic solvents. They were found to exhibit remarkable catalytic activity (average TOF up to 960 h(-1)) in the aerobic oxidation of benzylic and aliphatic alcohols and also of polyols in water under mild conditions (50-70 degrees C, 1-3 atm O-2). (c) 2007 Elsevier Inc. All rights reserved.
Bismuth as a modifier of Au–Pd catalyst: Enhancing selectivity in alcohol oxidation by suppressing parallel reaction
作者:Alberto Villa、Di Wang、Gabriel M. Veith、Laura Prati
DOI:10.1016/j.jcat.2012.04.021
日期:2012.8
Bi has been widely employed as a modifier for Pd and Pt based catalyst mainly in order to improve selectivity. We found that when Bi was added to the bimetallic system AuPd, the effect on activity in alcohol oxidation mainly depends on the amount of Bi regardless its position, being negligible when Bi was 0.1 wt% and detectably negative when the amount was increased to 3 wt%. However, the selectivity of the reactions notably varied only when Bi was deposited on the surface of metal nanoparticles suppressing parallel reaction in both benzyl alcohol and glycerol oxidation. After a careful characterization of all the catalysts and additional catalytic tests, we concluded that the Bi influence on the activity of the catalysts could be ascribed to electronic effect whereas the one on selectivity mainly to a geometric modification. moreover, the Bi-modified AuPd/AC catalyst showed possible application in the production of tartronic acid, a useful intermediate, from glycerol. (C) 2012 Elsevier Inc. All rights reserved.
Chemometric approaches on glycerol oxidation with H2O2 over supported gold nanoparticles
作者:Cleiton A. Nunes、Mário C. Guerreiro
DOI:10.1016/j.molcata.2013.01.006
日期:2013.4
This paper reports a chemometric study of effects of the catalyst preparation method and reaction conditions on the efficiency of glycerol oxidation catalyzed by gold nanoparticles supported on activated carbon using H2O2 as oxidant. Factorial designs and principal component analysis were used for the evaluation of experimental conditions and reaction performance. Evaluating catalyst preparation conditions we found that larger Au nanoparticles are obtained using HAuCl4 in higher concentration. Glycerol conversion and production of glycerate and tartronate were higher using catalysts prepared with low polyvinyl alcohol (PVA) to Au ratio and low Au content. Higher HAuCl4 concentrations resulted in larger Au nanoparticles, which contributed to higher glycolate production. Evaluating reaction conditions we found that the influence of H2O2 to glycerol ratio was insignificant. Glycerol conversion and production of glycerate and tartronate were higher at lower temperature. Increasing H2O2 to glycerol ratio contributed to higher glycolate production. Glycerol to Au ratio has a smaller influence on the reaction course. (C) 2013 Elsevier B.V. All rights reserved.