Stable Glycerol Electrooxidation to Glycerate Over 1000 Hours on a Hydroxyl-Modulated PdNiMo Alloy.
basic_science · Level V
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- Record sourced from PubMed, PMID 41645848.
- Also identified by DOI 10.1002/adma.202523353.
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Abstract
The electrochemical upgrading of glycerol into a single, valuable C<sub>3</sub> product remains a long-standing challenge, constrained by the limitations of insufficient activity, low selectivity, and poor stability. Here, we report a ternary PdNiMo alloy catalyst that synergistically modulates the electronic structure and optimizes the surface *OH coverage for efficient and stable glycerol-to-glycerate conversion. Combined experimental and theoretical studies reveal that Mo incorporation downshifts the d-band center and weakens *OH binding, while Ni introduction optimizes the balance between *OH-covered and free Pd sites. The resulting PdNiMo catalyst exhibits exceptional GEOR performance, achieving a high current density of 171 mA cm<sup>-2</sup> at 0.8 V vs. RHE and a superior glycerate selectivity of 67.5%. More impressively, in a membrane electrode assembly electrolyzer, the catalyst demonstrates outstanding durability, maintaining a current density of over 50 mA cm<sup>-2</sup> for more than 1000 h at a cell voltage of 1.2 V<sub>cell</sub>. This work elucidates the critical role of tailored hydroxyl coverage in selective oxidation and provides a design principle for advanced electrocatalysts in renewable energy-powered electrosynthesis.