Hollow mesoporous atomically dispersed metal-nitrogen-carbon catalysts with enhanced diffusion for catalysis involving larger molecules.

Abstract

Single-atom catalysts (SACs) show great promise in various applications due to their maximal atom utilization efficiency. However, the controlled synthesis of SACs with appropriate porous structures remains a challenge that must be overcome to address the diffusion issues in catalysis. Resolving these diffusion issues has become increasingly important because the intrinsic activity of the catalysts is dramatically improved by spatially isolated single-atom sites. Herein, we develop a facile topo-conversion strategy for fabricating hollow mesoporous metal-nitrogen-carbon SACs with enhanced diffusion for catalysis. Several hollow mesoporous metal-nitrogen-carbon SACs, including Co, Ni, Mn and Cu, are successfully fabricated by this strategy. Taking hollow mesoporous cobalt-nitrogen-carbon SACs as a proof-of-concept, diffusion and kinetic experiments demonstrate the enhanced diffusion of hollow mesoporous structures compared to the solid ones, which alleviates the bottleneck of poor mass transport in catalysis, especially involving larger molecules. Impressively, the combination of superior intrinsic activity from Co-N₄ sites and the enhanced diffusion from the hollow mesoporous nanoarchitecture significantly improves the catalytic performance of the oxidative coupling of aniline and its derivatives.