Nanoscale high-entropy surface engineering promotes selective glycerol electro-oxidation to glycerate at high current density.

Selective production of valuable glycerol chemicals, such as glycerate (which serves as an important chemical intermediate), poses a significant challenge due to the facile cleavage of C-C bonds and the presence of multiple reaction pathways. This challenge is more severe in the electro-oxidation of glycerol, which requires the development of desirable electrocatalysts. To facilitate the glycerol electro-oxidation reaction to glycerate, here we present an approach utilizing a high-entropy PtCuCoNiMn nanosurface. It exhibits exceptional activity (200 mA cm at 0.75 V versus a reversible hydrogen electrode) and selectivity (75.2%). In situ vibrational measurements and theoretical calculations reveal that the exceptional glycerol electro-oxidation selectivity and activity can be attributed to the unique characteristics of the high-entropy surface, which effectively modifies the electronic structure of the exposed Pt sites. The catalyst is successfully applied in an electrolyser for long-term glycerol electro-oxidation reaction, demonstrating excellent performance (200 mA cm at 1.2V) over 210 h. The present study highlights that tailoring the catalytic sites at the catalyst-electrolyte interface by constructing a high-entropy surface is an effective strategy for electrochemical catalysis.