Boosting activity and selectivity of glycerol oxidation over platinum–palladium–silver electrocatalysts via surface engineering

Abstract

A series of platinum–palladium–silver nanoparticles with tunable structures were synthesized for glycerol electro-oxidation in both alkaline and acidic solutions. Electrochemical results indicate that the catalysts show superior activity in alkaline solutions relative to acidic solutions. In alkaline solutions, the peak current densities of ammonia-etched samples are approximately twice those of saturated-NaCl-etched samples. Ammonia-etched platinum–palladium–silver (PtPd@Ag-NH₃) exhibits a peak current density of 9.16 mA cm⁻², which is 18.7 and 10 times those of the Pt/C and Pd/C, respectively. The product distribution was analyzed by high performance liquid chromatography. Seven products including oxalic acid, tartronic acid, glyoxylic acid, glyceric acid (GLA), glyceraldehyde (GALD), glycolic acid, and dihydroxyacetone (DHA) were detected. The NH₃·H₂O etched samples tend to generate more GALD, while the NaCl etched samples have a great potential to produce DHA. The addition of Pd atoms can facilitate glycerol oxidation pathway towards the direction of GALD generation. The Pt@Ag-NaCl possesses the largest DHA selectivity of 79.09% at 1.3 V, while the Pt@Ag-NH₃ exhibits the largest GLA selectivity of 45.01% at 0.5 V. The PtPd@Ag-NH₃ exhibits the largest C3/C2 ratio of 17.45. The selectivity and product distribution of glycerol electro-oxidation can be tuned by engineering the surface atoms of the as-synthesized catalysts.