Exploring the synergistic effect of palladium nanoparticles and highly dispersed transition metals on carbon nitride/super-activated carbon composites for boosting electrocatalytic activity

Abstract

In the present work, multifunctional electrocatalysts formed by palladium nanoparticles (Pd NPs) loaded on Fe or Cu-containing composite supports, based on carbon nitride (C3N4) and super-activated carbon with a high porosity development (SBET 3180 m2/g, VDR 1.57 cm3/g, and VT 1.65 cm3/g), were synthesised. The presence of Fe or Cu sites favoured the formation of Pd NPs with small average particle size and a very narrow size distribution, which agreed with Density Functional Theory (DFT) calculations showing that the interaction of Pd clusters with C3N4 flakes is weaker than with Cu- or Fe-C3N4 sites. The electroactivity was also dependent on the composition and, as suggested by preliminary DFT calculations, the Pd-Cu catalyst showed lower overpotential for hydrogen evolution reaction (HER) while bifunctional oxygen reduction reaction/ oxygen evolution reaction (ORR/OER) behaviour was superior in Pd-Fe sample. The Pd-Fe electrocatalyst was studied in a zinc-air battery (ZAB) for 10 h, showing a performance similar to a commercial Pt/C + RuO2 catalyst with a high content of precious metal. This study demonstrates the synergistic effect between Pd species and transition metals and shows that transition metals anchored on C3N4-based composite materials promote the electroactivity of Pd NPs in HER, ORR and OER due to the interaction between both species.