Hydrogen andHigh-Value-Added Chemicals from GlycerolElectroreforming Using a Highly Efficient and Selective Ligand-StabilizedPdCu Catalyst

PdCu alloy nanoparticles stabilized by a secondary diamine ligand (<b>L</b>) bearing C16-alkyl chains at the nitrogen atoms were successfully synthesized. The <b>PdCuL</b> supported on Vulcan XC-72 (<b>C</b>^<b>v</b>) with a very low metal loading (1 wt %) was applied in alkaline glycerol electroreforming experiments for both hydrogen generation and chemicals. The <b>PdCuL/C</b>^<b>v</b> electrocatalyst exhibited excellent activity as an anode material for glycerol oxidation with a specific activity of 6 A mg_Pd^–1 at 1 V and a notable selectivity (up to 95%) for high-value C3 oxidation products (glycerate and tartronate). Sterically demanding <b>L</b> allows the obtaining of small and stable size-controlled nanoparticles (<i>d</i>_m 1.9 ± 0.7 nm) observed through high-resolution transmission electron microscopy (TEM) analysis before and after catalysis testing. The catalyst was also thoroughly investigated by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) techniques. The Pd–Cu synergistic effect on alcohol oxidation catalysis was verified through electrochemical experiments, which highlight the superior catalytic activity of <b>PdCuL/C</b>^<b>v</b> (up to 3 times) compared to a monometallic catalyst.