Highly ordered, thermally/hydrothermally stable cubic Ia3d aluminosilica monoliths with low silica in frameworks

High order aluminosilica monoliths (Al/HOM-5) with cubic Ia3d structures were fabricated with low silica content (Si/Al = 1) by means of a simple, reproducible, and one-pot synthesis strategy. A realistic control over the cubic Ia3d geometry of aluminosilica monoliths was achieved by using microemulsion phases of copolymer P123 (EO20PO70EO20) as soft templates. The textural and geometrical pore structures and acidic properties of Al/HOM-5 were characterized by means of various tools of XRD, N2 isotherms, HRTEM, FTD, FESEM, 27Al and 29Si MAS NMR, EDX, and NH3-TPD. The incorporated amounts of Al species in Al/HOM-5 monoliths play a key determinant in the formation of the coordination state of the aluminum species in four (AlIV, AlO4)-, five (AlV, AlO4)-, and six (AlVI, AlO6)-coordinate environments. Results show evidence of the formation of aluminosilicas with disordered distribution of Si and Al sites in the frameworks. In addition, the increase of the aluminum contents enhanced the distortion in the pore uniformity of Al/HOM-5 monoliths. The large amount of acid sites was revealed with the high aluminum contents into the pore framework walls. With high-temperature treatments (⩾1073 K), the γ-Al2O3 phase with face-centered-cubic Fd3m symmetry can be formed in the monolithic aluminosilica matrices. This finding might indicate that the dealumination effect at high thermal treatment would be expected to generate many defect sites existing in the Al/HOM-5 frameworks. Accordingly, a large mass transport of aluminum from tetrahedral aluminum (framework) to octahedral aluminum (extra framework) was occurred, leading to form a separate aluminum species into the crystalline alumina matrices. Moreover, cubic Ia3d aluminosilica structures exhibit outstanding steam stability even with high Al content (Si/Al = 1). However, the mesostructured integrity of Al/HOM-5 can be retained under 100% steam treatments with N2 flow for 8 h at 1073 K, permitting their desirability in various applications such as catalysis, adsorption, and sensing technologies.

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► High order aluminosilica monoliths (Al/HOM-5) with cubic Ia3d structures were fabricated with low silica content (Si/Al = 1) using instant, one-pot synthesis (in the order of minutes) with simple composition domains.
► Control over the local aluminum structure in frameworks, structural integrity, and thermal/hydrothermal stability was successfully achieved with increasing the aluminum content in the mesopore frameworks.
► The 3D mesostructured geometry and the location and coordination of aluminum species play crucial clues in stabilizing the Al/HOM-5 frameworks against severe thermal/hydrothermal steam condition for longer contact time, permitting their desirability in various applications such as catalysis, adsorption, and sensing technologies.