Magnetically Hollow Pt Nanocages with Ultrathin Walls as a Highly Integrated Nanoreactor for Catalytic Transfer Hydrogenation Reaction.

Abstract

Fabricating efficient and stable nanocatalysts for chemoselective hydrogenation of nitroaromatics is highly desirable because the amines hold tremendous promise for the synthesis of nitrogen containing chemicals. Here, a highly reactive and stable porous carbon nitride encapsulated magnetically hollow platinum nanocage is developed with subnanometer thick walls (Fe3O4@snPt@PCN) for this transformation. This well‐controlled nanoreactor is prepared via the following procedures: the preparation of core template, the deposition of platinum nanocage with subnanometer thick walls, oxidative etching, and calcination. This highly integrated catalyst demonstrates excellent performance for the catalytic transfer hydrogenation of various nitroaromatics and the reaction can reach >99% conversion and >99% selectivity. With the ultrathin wall structure, the atom utilization of platinum atoms is highly efficient. The X‐ray photoelectron spectroscopy results indicate that partial electrons transfer from the iron oxides to Pt nanowalls, and this increases the electron density of snPt nanoparticles, thus promoting the catalytic activity for the transfer hydrogenation of nitroaromatics. For the reduction of 4‐nitrophenol, the reaction rate constant K app is 0.23 min−1 and the turnover frequency (TOF) is up to 3062 h−1. Additional reaction results illustrate that this magnetic nanoreactor can be reused more than eight times and it is a promising catalytic nanoplatform in heterogeneous catalysis.