A vesicle-aggregation-assembly approach to highly ordered mesoporous γ-alumina microspheres with shifted double-diamond networks

Abstract

Alumina materials have widely been used in industrial fields, such as catalysis and adsorption. However, due to the fast sol-gel process and complicated crystalline-phase transformation, the synthesis of alumina materials with both highly ordered mesostructures and crystallized frameworks remains a great challenge. Herein, we report a novel vesicle-aggregation-assembly strategy to prepare highly ordered mesoporous γ-alumina microspheres with unique shifted double-diamond networks for the first time, by using diblock copolymer poly(ethylene oxide)-<i>b</i>-poly(methyl methacrylate) (PEO-<i>b</i>-PMMA) as a template and aluminum isopropoxide as a precursor in a tetrahydrofuran (THF)/hydrochloric acid binary solvent. During the gradual evaporation of THF and H₂O, the as-made Al³⁺-based gel/PEO-<i>b</i>-PMMA composites can be obtained through a co-assembly process based on the hydrogen bonding interaction between hydroxyl groups of alumina oligomers and PEO segments of the diblock copolymers. The formed composites exhibit a spherical morphology with a wide size distribution (diameter size 1-12 μm). Furthermore, these composite microspheres possess an inverse bicontinuous cubic mesostructure (double diamond, <i>Pn</i>3[combining macron]<i>m</i>) with Al³⁺-based gel buried in the PEO-<i>b</i>-PMMA matrix in the form of two intertwined but disconnected networks. After a simple calcination at 900 °C in air, the structure of the resultant mesoporous alumina changes to a relatively low symmetry (shifted double diamond, <i>Fd</i>3[combining macron]<i>m</i>), ascribed to the shifting of the two alumina networks due to loss of the templates. Meanwhile, the unit cell size of the alumina mesostructure decreases from ∼131 to ∼95 nm. The obtained ordered mesoporous alumina products retain the spherical morphology and possess ultra-large mesopores (∼72.8 nm), columnar frameworks composed of γ-alumina nanocrystalline particles (crystal size of ∼15 nm) and high thermal stability (up to 900 °C). As a support of Au nanoparticles, the formed Au/mesoporous γ-alumina composite catalysts have been used in the catalytic reduction of 4-nitrophenol with a high kinetic constant <i>k</i> of 0.0888 min^-1, implying promising potential as a catalyst support.