Stable Glycerol Electrooxidation to Glycerate Over 1000 Hours on a Hydroxyl-Modulated PdNiMo Alloy

Area of Science:

• Electrochemistry
• Materials Science
• Catalysis

Background:

• Electrochemical upgrading of glycerol to valuable C3 products faces challenges in activity, selectivity, and stability.
• Developing efficient catalysts is crucial for sustainable chemical synthesis.

Purpose of the Study:

• To develop a novel electrocatalyst for efficient and stable glycerol-to-glycerate conversion.
• To elucidate the role of catalyst composition in optimizing reaction pathways.

Main Methods:

• Synthesis and characterization of a ternary PdNiMo alloy catalyst.
• Electrochemical experiments including cyclic voltammetry and chronoamperometry.
• Density Functional Theory (DFT) calculations to understand reaction mechanisms.

Main Results:

• The PdNiMo catalyst achieved a high current density of 171 mA cm⁻² at 0.8 V vs. RHE.
• Superior glycerate selectivity of 67.5% was obtained.
• The catalyst demonstrated excellent durability, maintaining >50 mA cm⁻² for over 1000 h in a membrane electrode assembly electrolyzer.

Conclusions:

• Ternary PdNiMo alloy synergistically modulates electronic structure and optimizes surface hydroxyl coverage for efficient glycerol electrooxidation.
• Tailored hydroxyl coverage is critical for selective oxidation, providing a design principle for advanced electrocatalysts.
• This work advances electrosynthesis powered by renewable energy.