Influence of Pd and Au on electrochemical valorization of glycerol over Ni-rich surfaces

Herein we synthesized bi-metallic Pd@Ni and Au@Ni core-shell-like nanoparticles (NPs) for glycerol electrooxidation reaction (GEOR) in alkaline media. The morphological, structural and surface properties of the NPs were evaluated using a range of physicochemical techniques. The catalytic activity and stability were studied using the three-electrode electrochemical cell and 25 cm2- continuous electrolysis cell. Among different atomic ratios, Ni80Pd20 and Ni90Au10 nanoparticles showed the highest current densities which are ~4.5 and 4.2 times higher than spherical Ni, respectively. The addition of Pd and Au (<20 at.%) to Ni nanoparticles led to a remarkable glycerate selectivity of ~73.1% and 65.7% for Ni80Pd20 and Ni90Au10 catalysts at 1.3 V and 50 °C, respectively. Notably, after 6 h of electrolysis Pd@Ni and Au@Ni tend to suppress the C-C bond cleavage, compared to Ni at any applied potentials and temperatures. The DFT calculations predicted that the addition of Pd or Au to Ni reduces the work function of M@Ni NPs, which strengthens the OH adsorption and enhances the removal of GEOR intermediates.