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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Strong Impact of Platinum Surface Structure on Primary and Secondary Alcohol Oxidation during Electro-Oxidation of Glycerol

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Author(s):
Garcia, Amanda C. [1, 2] ; Kolb, Manuel J. [1] ; van Nierop y Sanchez, Chris [1] ; Vos, Jan [1] ; Birdja, Yuvraj Y. [1] ; Kwon, Youngkook [1] ; Tremiliosi-Filho, Germano [2] ; Koper, Marc T. M. [1]
Total Authors: 8
Affiliation:
[1] Leiden Univ, Leiden Inst Chem, POB 9502, NL-2300 RA Leiden - Netherlands
[2] Univ Sao Paulo, Inst Quim Sao Carlos, Ave Trabalhador Sao Carlense 400, BR-13569590 Sao Paulo - Brazil
Total Affiliations: 2
Document type: Journal article
Source: ACS CATALYSIS; v. 6, n. 7, p. 4491-4500, JUL 2016.
Web of Science Citations: 38
Abstract

Herein we describe a combined experimental and computational study of electrochemical glycerol oxidation in acidic media on Pt(111) and Pt(100) electrodes. Our results show that glycerol oxidation is a very structure-sensitive reaction in terms of activity and, more surprisingly, in terms of selectivity. Using a combination of online HPLC and online electrochemical mass spectrometry, we show that on the Pt(111) electrode, glyceraldehyde, glyceric acid, and dihydroxyacetone are products of glycerol oxidation, while on the Pt(100) electrode, only glyceraldehyde was detected as the main product of the reaction. Density functional theory calculations show that this difference in selectivity is explained by different binding modes of dehydrogenated glycerol to the two surfaces. On Pt(111), the dehydrogenated glycerol intermediate binds to the surface through two single Pt-C bonds, yielding an enediol-like intermediate, which serves as a precursor to both glyceraldehyde and dihydroxyacetone. On Pt(100), the dehydrogenated glycerol intermediate binds to the surface through one double Pt=C bond, yielding glyceraldehyde as the only product. Stripping and in situ FTIR measurements show that CO is not the only strongly bound adsorbed intermediate of the oxidation of glycerol, glyceraldehyde, and dihydroxyacetone. Although the nature of this adsorbate is still unclear, this intermediate is highly resistant to oxidation and can only be removed from the Pt surface after multiple scans. (AU)

FAPESP's process: 14/24438-8 - Conversion of alcohol into added-value products. a mechanistic study on single crystal electrodes
Grantee:Amanda Cristina Garcia
Support Opportunities: Scholarships abroad - Research Internship - Post-doctor