PdCo Alloy Nanonetworks−Polyallylamine Inorganic–Organic Nanohybrids toward the Oxygen Reduction Reaction

Rationally controlling the morphology, chemical composition, and interfacial property of metal nanostructures can remarkably enhance their electrocatalytic performance, such as activity, selectivity, and durability. In this work, a facile functional molecule‐assisted cyanogel‐reduction method is developed to successfully synthesize the polyallylamine (PAA)‐functionalized PdCo alloy nanonetworks (PdCo‐NNW@PAA) inorganic–organic nanohybrids. The solid, double‐metal, and 3D backbone properties of jelly‐like K2PdCl4/K3Co(CN)6 cyanogel intermediate contribute to the high alloying degree and network structure of PdCo‐NNW@PAA nanohybrids. During the reduction, PAA molecules not only serve as surfactant to decrease the particle size but also act as functional molecule to modify the metal surface. The oxygen reduction reaction (ORR) polarization and chronoamperometry tests demonstrate that PdCo‐NNW@PAA nanohybrids have outstanding electrocatalytic activity, excellent resistance to alcohol crossover effect, and good durability toward the ORR in alkaline media. This work provides a new strategy for synthesizing the chemical functionalized multimetallic alloy nanonetworks at room temperature and reveals that the interfacial property of metal nanocrystals strongly affects their electrocatalytic activity and selectivity.