Zn Single Atoms/Clusters/Nanoparticles Embedded in the Hybrid Carbon Aerogels for High-Performance ORR Electrocatalysis

Carbon-supported zinc single-atom catalysts have received considerable attention in the electrocatalytic oxygen reduction reaction (ORR) owing to the strong reduction capacity of zinc atoms and the abundant reserves of zinc elements. The common preparation method has been limited to the high-temperature pyrolysis of nitrogen-rich organic molecules and zinc ions, which makes it difficult to further improve the ORR performance. Herein, we first prepared ZnO/PNT/rGO aerogels as precursors via a simple hydrothermal method combined with freeze-drying, in which reduced graphene oxides (rGO) and polypyrrole nanotubes (PNT) together assembled into three-dimensional frames and numerous ZnO nanoparticles were anchored in the three-dimensional skeletons. Then, ZnO/PNT/rGO aerogels were calcined at 800 °C in the argon atmosphere, in which PNT/rGO were derived carbon aerogels, ZnO nanoparticles were reduced to Zn0 by carbon, and generating zinc single atoms were captured by the surrounding nitrogen atoms or aggregated into Zn clusters/nanoparticles in the carbon substrates. The obtained products were Zn single atoms/clusters/nanoparticles embedded into PNT/rGO-derived carbon aerogels, named Zn/NC catalysts. Zn/NC catalysts display a much higher half-wave potential and a larger limiting current density than pure rGO aerogels, NC, and Zn/C catalysts, indicating the synergy of excellent electronic transportation, high mass efficiency from outstanding porosity, and several active centers. Tailoring the quantity of zinc acetate can provide the optimal ORR performance with the Eonset of 0.96 V, the E1/2 of 0.845 V, and remarkable durability. This work exploits a novel strategy of carbon thermal reduction to construct high-performance Zn-based low-dimensional ORR catalysts.