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

摘要

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 ORE. 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 degrees 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 Pt24Ni 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)).