Atomically Dispersed Pd-N₁C₃ Sites on a Nitrogen-Doped Carbon Nanosphere for Semi-hydrogenation of Acetylene.

Abstract

Rationally designing efficient catalysts for semi-hydrogenation of acetylene is significant but challenging. Herein, Pd isolated single-atom sites (ISAS) on a covalent-organic-framework (COF)-derived nanosphere (Pd-ISAS/CN) are synthesized by a COF-absorption-pyrolysis strategy. This synthetic strategy is also applicable for Pt and Ru ISAS catalysts, demonstrating that it is a general method to synthesize noble-metal ISAS on COF-derived carbon materials. Pd-ISAS/CN exhibits outstanding reactivity and high selectivity for semi-hydrogenation of acetylene, with 92% conversion of acetylene, 80% selectivity toward ethylene at 100 °C, and corresponding activity is as high as 712 mol_acetylene mol_metal^-1 h^-1. Extended X-ray absorption fine structure (EXAFS) measurement and density functional theory (DFT) calculation reveal the Pd-N₁C₃ sites from Pd-ISAS/CN efficiently boost the reactivity for semi-hydrogenation of acetylene. This work will bring inspiration to rationally design noble-metal-based ISAS catalysts derived from COF materials and boost catalytic performance by optimizing the coordination environment of catalytic sites.