Ultra-high loading single CoN3 sites in N-doped graphene-like carbon for efficient transfer hydrogenation of nitroaromatics

Abstract

Atomically dispersed non-noble metal single-site catalysts (SSCs) provide a promising approach to meet the catalytic requirements that traditional nanoparticles cannot accomplish. However, they often suffer from formidable challenges of cumbersome route, unmanageable loading, inevitable burial of active site and insufficient stability. Herein, we present a facile and hard template-assisted spatial confinement strategy to prepare Co SSCs embedded in N-doped graphene-like carbon (NG) with ultra-high loading of 10.26 wt%, which is close to the parent CoPc (10.31 wt%). Furthermore, the microstructure, surface area and Co loading in the titled catalysts can be easily manipulated via altering the synthesis parameters. The optimized Co SSCs@NG-800-50 catalyst shows excellent transfer hydrogenation of nitrobenzene with > 99% conversion and 96.3% aniline selectivity as well as good universality for various nitroaromatics in the presence of HCOOH. DFT calculations in combination with elaborate experiments unveil that the active H is firstly generated by the dissociation of C-H bond rather than the recognized O-H bond in HCOOH, then it is used for the hydrogenation of nitroaromatics on CoN3 site in Co SSCs@NG-800-50 catalyst, revealing the reaction mechanism of the tandem catalysis. This report paves a novel route to design and construct efficient and high-loading non-noble metal SSCs.