Electro‐Oxidation of Polyols on Bi‐Modified Pt in Acidic Media (HClO4). Understanding Activity and Selectivity Trends

Author:

Soffiati Gabriela1,Yukuhiro Victor Y.12,Raju Swathi P.12,De Souza Matheus B. C.12,Marquezini Leonardo12,da Silva Edison Z.3,Fernández Pablo S.12ORCID,San‐Miguel Miguel A.1

Affiliation:

1. Institute of Chemistry Department of Physical Chemistry State University of Campinas R. Josué de Castro, s/n 13083-970 Campinas Brazil

2. Center for Innovation on New Energies (CINE) R. Michel Debrun, s/n, Prédio Amarelo 13083-841 Campinas Brazil

3. Institute of Physics “Gleb Wataghin” (IFGW) State University of Campinas R. Sérgio Buarque de Holanda, 777 13083-859 Campinas Brazil

Abstract

AbstractHerein we show that Pt(111) and Pt(100) can produce the ketone through the oxidation of the secondary carbon of the polyols. After the Bi modification, the selectivity for the ketone formation increases. On the other hand, we observe that pure and Bi‐modified Pt(110) only produced the C3 molecules oxidized in the primary carbon, and it is the only facet that shows an enhancement in the activity due to the modification. In line with these findings, small Pt nanoparticles are not selective for ketone formation. Finally, based on data obtained through DFT calculations, we suggest that positively charged Bi adatoms interact with the OH‐ groups of the enediol‐like intermediate (believed to be the precursor for the ketone/aldehyde production), facilitating the oxidation of the secondary carbon to produce DHA.

Publisher

Wiley

Subject

Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Catalysis

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