Selective production of market-valued dihydroxyacetone on two alloy phase surfaces by electrocatalytic oxidation of biomass-derived glycerol

Abstract

Dihydroxyacetone (DHA) is recognized as a valuable chemical in cosmetic and pharmaceutical industries. Recently, electrocatalytic glycerol oxidation reaction (EGOR) technology has been attractive for selective DHA production. However, one fundamental question needs to be answered: Which catalytic active site affects the reaction chemistry and mechanism for the selective DHA production from EGOR. In this study, Pt-Sb hollow spherical electrocatalysts were prepared by a simple chemical synthesis method, which includes different catalytic phases, namely, PtSb and PtSb2 alloys by controlling the Pt:Sb atomic ratio (Pt8.64Sb1.36, Pt7.01Sb2.99, and Pt5.59Sb4.41). Both experimental and computational methods were used to understand how and why the reaction performance and chemistry change with the PtSb and PtSb2 alloy phases in the EGOR. The Pt5.59Sb4.41 electrocatalyst, which has a large portion of PtSb and PtSb2 alloys, demonstrated superior EGOR activity over those of other ratios of Pt-Sb electrocatalysts, with a lower onset potential and higher Pt mass activity in the different pH conditions (acid, neutral, and base). Interestingly, in the EGOR, the Pt5.59Sb4.41 catalyst produced DHA with high selectivity of over 90 % in both acid and neutral conditions. The enhanced EGOR performances were related to the formed PtSb and PtSb2 alloys at the surface structure of prepared Pt-Sb electrocatalysts. Density functional theory (DFT) calculations revealed that the Sb atoms changed the electronic properties of the Pt atoms and thus modulated the interaction between Pt atoms and adsorbates, which affected both the catalytic activity and DHA selectivity for the EGOR. © 2025 The Authors