Synthesis of Pt–Ni Octahedra in Continuous-Flow Droplet Reactors for the Scalable Production of Highly Active Catalysts toward Oxygen Reduction

A number of groups have reported the syntheses of nanosized Pt–Ni octahedra with remarkable activities toward the oxygen reduction reaction (ORR), a process key to the operation of proton-exchange membrane fuel cells. However, the throughputs of those batch-based syntheses are typically limited to a scale of 5–25 mg Pt per batch, which is far below the amount needed for commercial evaluation. Here we report the use of droplet reactors for the continuous and scalable production of Pt–Ni octahedra with high activities toward ORR. In a typical synthesis, Pt­(acac)₂, Ni­(acac)₂, and W­(CO)₆ were dissolved in a mixture of oleylamine, oleic acid, and benzyl ether, and then pumped into a polytetrafluoroethylene tube. When the solution entered the reaction zone at a temperature held in the range of 170–230 °C, W­(CO)₆ quickly decomposed to generate CO gas, naturally separating the reaction solution into discrete, uniform droplets. Each droplet then served as a reactor for the nucleation and growth of Pt–Ni octahedra whose size and composition could be controlled by changing the composition of the solvent and/or adjusting the amount of Ni­(acac)₂ added into the reaction solution. For a catalyst based on Pt_2.4Ni octahedra of 9 nm in edge length, it showed an ORR mass activity of 2.67 A mg_Pt^–1 at 0.9 V, representing an 11-fold improvement over a state-of-the-art commercial Pt/C catalyst (0.24 A mg_Pt^–1).