Nanosheet Array-Like Palladium-Catalysts Pdx/rGO@CoAl-LDH via Lattice Atomic-Confined in Situ Reduction for Highly Efficient Heck Coupling Reaction

A series of novel nanosheet array-like catalysts Pdx/rGO@CoAl-LDH (x = 0.0098–1.9, refers to Pd loading in wt % on ICP, rGO: reduced graphene oxide, LDH: layered double hydroxide) were first prepared via a simple and green lattice atomic-confined in situ reduction of oxidative Pd precursors by the evenly atomic-dispersed reductive Co2+ sites on LDH layers of a nanohybrid rGO@CoAl-LDH with hexagonal LDH nanoplates (∼73 × 7 nm) interdigitated vertical to the surfaces of rGO layer in both sides, fabricated through a simple citric acid-assisted aqueous-phase coprecipitation method. The as-obtained Pd catalysts possess clean Pd nanoclusters (NCs) with tunable sizes in 1.3–1.8 nm on varied Pd loadings. All the Pdx/rGO@CoAl-LDH catalysts show excellent activities for the Heck reaction, and the Pd0.0098/rGO@CoAl-LDH with the ultrafine Pd NCs of 1.3 ± 0.2 nm yields a maximum turnover frequency of 160 000 h–1 over a heterogeneous catalyst so far. The excellent activities can be attributed to the ultrasmall Pd NCs with high dispersion and clean Pd surfaces, increased electron transfer capacity and surface area, and remarkable Pd–CoAl-LDH—rGO three-phase synergistic effect of the present unique nanosheet array-like Pd NCs catalysts. Moreover, the catalyst Pd0.33/rGO@CoAl-LDH shows a broad range of substrate applicability and can be reused more than five runs without obvious loss of activity, giving the present catalysts long-term stability. These findings make the rGO@CoAl-LDH hybrid prepared by a facile and scalable synthesis route a universal green platform to support other noble or nonprecious metal NCs via lattice atomic-confined in situ reduction strategy to construct more desired heterogeneous catalysts.