Two-Step Carbothermal Welding To Access Atomically Dispersed Pd_1 on Three-Dimensional Zirconia Nanonet for Direct Indole Synthesis

摘要

Herein, we report a novel carbothermal welding strategy to prepare atomically dispersed Pd sites anchored on a three-dimensional (3D) ZrO2 nanonet (Pd-1@ZrO2) via two-step pyrolysis, which were evolved from isolated Pd sites anchored on linker-derived nitrogen-doped carbon (Pd-1@NC/ZrO2). First, the NH2-H2BDC linkers and Zr-6-based [Zr-6(mu(3)-O)(4)(mu(3)-OH)(4)](12+) nodes of UiO-66-NH2 were transformed into amorphous N-doped carbon skeletons (NC) and ZrO2 nanoclusters under an argon atmosphere, respectively. The NC supports can simultaneously reduce and anchor the Pd sites, forming isolated Pd-1-N/C sites. Then, switching the argon to air, the carbonaceous skeletons are gasified and the ZrO2 nanoclusters are welded into a rigid and porous nanonet. Moreover, the reductive carbon will result in abundant oxygen (O*) defects, which could help to capture the migratory Pd-1 species, leaving a sintering-resistant Pd-1@ZrO2 catalyst via atom trapping. This Pd-1@ZrO2 nanonet can act as a semi-homogeneous catalyst to boost the direct synthesis of indole through hydrogenation and intramolecular condensation processes, with an excellent turnover frequency (1109.2 h(-1)) and 94% selectivity.