Mesoporous Pdx-Nix aerogels for electrocatalytic evaluation of urea-assisted electrolysis

Abstract

This work presents the synthesis and evaluation of Pd-Ni aerogels toward the urea oxidation reaction (UOR). The incorporation of Ni led to a 0.13 V reduction in the energy required for the oxidation and reduction of PdO compared to monometallic Pd, both in alkaline medium with and without urea. Varying the Ni ratios in Pd (Pd-Ni 4:1, Pd-Ni 1:1, and Pd-Ni 1:4) led to significant changes in the electrochemical behaviour. In alkaline medium without urea, PdNi 4:1 showed the formation of NiOOH at 1.35 V, which promoted oxygen diffusion on the electrode surface and increased the current density, confirming the increase in the active sites of NiOOH and NiPdOOH and enabling urea-based electrolysis at these sites. While palladium aerogels alone are ineffective for UOR, the presence of nickel plays a key role in enhancing the UOR efficiency. On the other hand, physicochemical characterisation revealed that PdNi 4:1 has a crystal size of 4.37 nm and a larger shift in the 2θ positions of the (111) and (200) planes, which favours electronic changes that were investigated by XPS. These changes affected the electrocatalytic activity, which is primarily related to electronic effects. The results of SEM and TEM studies and nitrogen adsorption-desorption isotherm confirmed that the aerogels are highly porous and have an effective surface area and abundant active sites for reactions that allow efficient mass transfer and low diffusion resistance. TEM observations revealed interconnected nanochains indicating optimal electrocatalytic activity for both ORR and UOR due to high mass transfer. These interconnected networks are crucial for improving electrocatalytic activity in the urea oxidation reaction.