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

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 PtSb 2 alloys by controlling the Pt:Sb atomic ratio (Pt 8.64 Sb 1.36 , Pt 7.01 Sb 2.99 , and Pt 5.59 Sb 4.41 ). Both experimental and computational methods were used to understand how and why the reaction performance and chemistry change with the PtSb and PtSb 2 alloy phases in the EGOR. The Pt 5.59 Sb 4.41 electrocatalyst, which has a large portion of PtSb and PtSb 2 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 Pt 5.59 Sb 4.41 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 PtSb 2 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. This work reports the synthesis of novel electrocatalytic material that includes both alloy phases of PtSb and PtSb 2 in a catalyst system. The prepared Pt-Sb hollow spherical electrocatalysts demonstrated high catalytic activity and dihydroxyacetone selectivity compared to the Pt catalyst for the electrocatalytic glycerol oxidation. The improved glycerol oxidation performances were related to the formed PtSb and PtSb 2 alloys at the surface structure of prepared Pt-Sb electrocatalysts. • Pt-Sb hollow spherical electrocatalysts including two PtSb and PtSb 2 alloys were prepared in this study. • The prepared Pt-Sb catalysts demonstrated excellent catalytic activity and dihydroxyacetone selectivity for electrocatalytic glycerol oxidation. • The enhanced catalytic performances were related to the formed PtSb and PtSb 2 alloys at the surface structure.