Distance controlled graphyne-like binuclear palladium catalyst for accelerating nitrobenzene reduction

Abstract

The diatomic catalyst synthesized by high-temperature thermal cracking usually undergoes structural reorganization of raw materials, increasing the difficulty in studying the structure-activity relationship of the catalysts. Herein, starting from the synthesis methodology, we adjust the atomic spacing of dual-Pd-site catalysts to 0.4 and 0.8 nm by regulating the monomer structure of graphyne. The model experiment of nitrobenzene reduction shows that graphyne catalyst (TEGY-Pd) with closer palladium atom spacing (0.4 nm) show a faster reaction rate (1.57 min−1), good universality and cyclic stability in catalytic process than that of graphdiyne catalyst (TEGDY-Pd) which has longer palladium atom spacing. Moreover, the theoretical calculation shows that the excellent catalytic performance of TEGY-Pd is original from the synergetic catalysis of the closer diatomic palladium to the nitro group in adsorption and electron transport process. This work provided a new idea to precisely control the metal atomic spacing and revealed the structure activity relationship of binuclear catalysts.