Hierarchical hollow nanostructured core@shell recyclable catalysts gamma-Fe2O3@LDH@Au-25-x for highly efficient alcohol oxidation

A series of honeycomb-like hierarchical hollow nanostructured magnetic catalysts, gamma-Fe2O3@M3Al-LDH@Au-25-x (x represents determined mass of gold in wt%), have been successfully fabricated by modified electrostatic adsorption of water-soluble captopril-capped Au-25 nanoclusters (Au(25)Capt(18)) on pre-prepared magnetic supports, Fe3O4@M3Al-LDH (M = Ni, Mg, or Cu/Mg (0.5/2.5), LDH: layered double hydroxide) followed by proper calcination. The characterization results show that the low Au-loading samples, gamma-Fe2O3@Ni3Al-LDH@Au-25-x (x = 0.053, 0.11), show nearly atomically precise Au-25 nanoclusters (Au25NCs) (similar to 1.4 +/- 0.3-1.9 +/- 0.6 nm) dispersed on the surface of the Ni3Al-LDH shell, while the catalysts, gamma-Fe2O3@M3Al-LDH@Au-25-x Au-25-x (x similar to 0.2), display slightly aggregated Au25NCs on the LDH shell with sizes of similar to 3.0 +/- 1.3, 3.3 +/- 1.2, and 4.2 +/- 1.5 nm for Ni-, Mg-, and CuMg-based catalysts, respectively, related to varied synergy between Au25NCs and magnetic LDH supports at slightly higher Au loadings. All the gamma-Fe2O3@M3Al-LDH@Au-25-x Au-25-x catalysts exhibit much higher catalytic activity for the oxidation of 1-phenylethanol under atmospheric O-2, without basic additives, in toluene than Fe3O4@Mg3Al-LDH@Au prepared by a traditional deposition-precipitation method. The catalyst, gamma-Fe2O3@Ni3Al-LDH@Au-25-x, presents even higher alcohol oxidation activity than gamma-Fe2O3@Mg3Al-LDH@Au-25-0.21 and gamma-Fe2O3@Cu0.5Mg2.5Al-LDH@Au-25-0.2 and, particularly, gamma-Fe2O3@Ni3Al-LDH@Au-25-0.053 exhibits the highest activity (TOF: 112 498 h(-1)) for the aerobic oxidation of 1-phenylethanol under solvent-free conditions and can be applied for a variety of alcohols, this being mainly attributed to its nearly atomically precise Au25NCs and remarkable Au25NCs-LDH-magnetic core three-phase synergistic interaction, along with its abundant Ni-OH sites. Moreover, gamma-Fe2O3@Ni3Al-LDH@Au-25-0.053 can be easily separated, by simply applying an external magnetic field, and reused for more than ten runs without significant loss of activity, giving the magnetic catalysts long-term stability. These observations make Fe3O4@LDH a universal green platform to support other noble or non-precious metal nanoparticles by using a metal nanocluster precursor method to construct desired metal-loaded ecofriendly catalysts that can be applied in a broad range of heterogeneous catalysis processes.