Pd–Pd/PdO as active sites on intercalated graphene oxide modified by diaminobenzene: fabrication, catalysis properties, synergistic effects, and catalytic mechanism

Abstract

Pd–Pd/PdO nanoclusters well dispersed on intercalated graphene oxide (GO) (denoted as GO@PPD–Pd) were prepared and characterized. GO@PPD–Pd exhibited high catalytic activity (a TOF value of 60 705 h⁻¹) during the Suzuki coupling reaction, and it could be reused at least 6 times. The real active centre was Pd(200)–Pd(200)/PdO(110, 102). A change in the Pd facets on the surface of PdO was a key factor leading to deactivation, and the aggregation and loss of active centres was also another important reason. The catalytic mechanism involved heterogeneous catalysis, showing that the catalytic processes occurred at the interface, including substrate adsorption, intermediate formation, and product desorption. The real active centres showed enhanced negative charge due to the transfer of electrons from the carrier and ligands, which could effectively promote the oxidative addition reaction, and Pd(200) and the heteroconjugated Pd/PdO interface generated in situ also participated in the coupling process, synergistically boosting activity. Developed GO@PPD–Pd was a viable heterogeneous catalyst that may have practical applications owing to its easy synthesis and stability, and this synergistic approach can be utilized to develop other transition-metal catalysts.