The oxidation of glycerol under alkaline conditions in the presence of a heterogeneous catalyst can be tailored to the formation of lactic acid, an important commodity chemical. Despite recent advances in this area, the mechanism for its formation is still a subject of contention. In this study, we use a model 1 wt. % AuPt/TiO2 catalyst to probe this mechanism by conducting a series of isotopic labeling experiments with 1,3-13C glycerol. Optimization of the reaction conditions was first conducted to ensure high selectivity to lactic acid in the isotopic labeling experiments. Selectivity to lactic acid increased with temperature and concentration of NaOH, but increasing the O2 pressure appeared to influence only the rate of reaction. Using 1,3-13C glycerol, we demonstrate that conversion of pyruvaldehyde to lactic acid proceeds via a base-promoted 1,2-hydride shift. There was no evidence to suggest that this occurs via a 2,1-methide shift under the conditions used in this study.
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7 April 2020
Research Article|
April 07 2020
Enhancing the understanding of the glycerol to lactic acid reaction mechanism over AuPt/TiO2 under alkaline conditions
Special Collection:
Catalytic Properties of Model Supported Nanoparticles
Christopher D. Evans;
Christopher D. Evans
1
Cardiff Catalysis Institute, School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom
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Mark Douthwaite
;
Mark Douthwaite
1
Cardiff Catalysis Institute, School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom
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James H. Carter
;
James H. Carter
1
Cardiff Catalysis Institute, School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom
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Samuel Pattisson
;
Samuel Pattisson
1
Cardiff Catalysis Institute, School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom
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Simon A. Kondrat
;
Simon A. Kondrat
a)
1
Cardiff Catalysis Institute, School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom
2
Department of Chemistry, Loughborough University
, Loughborough, Leicestershire, LE11 3TU, United Kingdom
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Donald Bethell
;
Donald Bethell
1
Cardiff Catalysis Institute, School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom
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David W. Knight;
David W. Knight
1
Cardiff Catalysis Institute, School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom
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Stuart H. Taylor
;
Stuart H. Taylor
1
Cardiff Catalysis Institute, School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom
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Graham J. Hutchings
Graham J. Hutchings
a)
1
Cardiff Catalysis Institute, School of Chemistry, Cardiff University
, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom
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Note: This paper is part of the JCP Special Topic Collection on Catalytic Properties of Model Supported Nanoparticles.
J. Chem. Phys. 152, 134705 (2020)
Article history
Received:
September 21 2019
Accepted:
March 09 2020
Citation
Christopher D. Evans, Mark Douthwaite, James H. Carter, Samuel Pattisson, Simon A. Kondrat, Donald Bethell, David W. Knight, Stuart H. Taylor, Graham J. Hutchings; Enhancing the understanding of the glycerol to lactic acid reaction mechanism over AuPt/TiO2 under alkaline conditions. J. Chem. Phys. 7 April 2020; 152 (13): 134705. https://doi.org/10.1063/1.5128595
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