Synergistic interconnected quasi-spherical Pd-Ni nanoparticles on lignin-derived N, O-doped carbon promote selective glycerol oxidation

Selective electrochemical oxidation of glycerol presents an attractive route for producing value-added chemicals from biomass; however, achieving high C 3 product selectivity while suppressing over-oxidation remains challenging. Here, we report a supramolecule-assisted strategy to construct Pd 3 Ni 1 interconnected nanoparticles anchored on lignin-derived N, O-doped porous carbon (Pd 3 Ni 1 /LNOC). The engineered carbon framework provides abundant defects and strong metal-support interactions, enabling uniform Pd-Ni dispersion and optimized electronic structure. The synthesized Pd 3 Ni 1 /LNOC catalyst exhibits outstanding glycerol electrooxidation performance, delivering a high mass activity of 2330 mA mg −1 , 91.7 % glycerol conversion, and 70.2 % C 3 glycerate selectivity at 0.85 V versus RHE, significantly outperforming commercial Pd/C. Operando Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy combined with density functional theory (DFT) calculations reveal the potential-dependent evolution of reaction intermediates and demonstrate that Pd-Ni active sites regulate adsorption energetics, lowering the free-energy barriers toward selective C 3 formation. In addition, the catalyst maintains stable operation in an H-type flow cell with minimal current decay (≥65 mA cm −2 ) over 3 h. This work establishes a sustainable platform for the design of biomass-derived carbon-supported bimetallic catalysts for selective alcohol electrooxidation and renewable chemical production.