Density functional theory study on the selective oxidation of ethylene glycol to glycolic acid over Pt_n (n = 4–55) clusters

Abstract

The selective oxidation of ethylene glycol to glycolic acid on the Pt₄, Pt₁₃, Pt₃₈, and Pt₅₅ clusters was investigated by using density-functional theory calculations. The calculated results imply that glycolic acid is preferentially generated through the dehydrogenation of ethylene glycol by OH to form HOCH₂CH₂O on the Pt₄, Pt₁₃, and Pt₃₈ surfaces, but that this process occurs directly without OH participation on the Pt₅₅ surface. The observed effect likely arises from the addition of OH, which modulates the electron density in the O atom of ethylene glycol, thereby affecting the cleavage of the O−H bond. Furthermore, the glycolic acid formation on the Pt_n clusters is limited by the β−H elimination of HOCH₂CH₂O to HOCH₂CHO, which exhibits the lowest energy barrier on the Pt₁₃ surface. It is because the d-band center of the Pt₁₃ cluster is closer to the Fermi energy than that of other clusters, which then enhances the electronic density of Pt. This facilitates the adsorption of HOCH₂CH₂O at the Pt sites and the activation of the C−H bond in HOCH₂CH₂O and therefore results in superior catalytic performance. This paper offers theoretical insights into the influence of Pt size on the selective oxidation of ethylene glycol to glycolic acid.

Graphical abstract

Keywords

ethylene glycol / glycolic acid / selective oxidation / Pt_n clusters / particle size effect

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