Assembly of Silicalite-1 Crystals Like Toy Lego Bricks into One-, Two-, and Three-Dimensional Architectures for Enhancing Its Adsorptive Separation and Catalytic Performances

Many researchers have contributed to the assembly of zeolitic nanosheets and nanocrystallites into three-dimensional (3D) networks as it can remarkably improve the catalytic and/or adsorptive performances of zeolites. However, the applications of these synthesized materials are seriously limited because of low hydrothermal stability. A highly interesting strategy, but a great challenge, is the alignment of well-crystallized zeolite crystals into desirable architectures. Here, well-crystallized silicalite-1 crystals are assembled like toy Lego bricks into one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) architectures, and the assembly mechanism is investigated by combining elaborate experiments, in situ spectroscopy, and theoretical calculations. A 1D architecture was formed by stacking crystals along the b axis with the assistance of ethanol that is selectively adsorbed on (100) and (001) crystal facets. Such adsorption increases the condensation energy barriers along a and c axes, but facilitates the condensation between (010) facets. The assembly of the crystals into well-arrayed 2D architectures is achieved using both ethanol and benzaldehyde because of their preferable adsorption on the (001) facet. When an amphiphilic copolymer (P123) was further added in the gel along with the substitution of ethanol by 1-propanol, a 3D network was fabricated by the agglomeration and self-pillaring of the 2D Lego bricks possibly with P123 aggregates as the substrate matrix. Excitingly, upon alignment of crystals into 2D architectures, the adsorptive selectivity of 1-butanol (2 wt %) to water of silicalite-1 increases by 45.3 times, while into 3D networks, the catalytic activity for the Beckmann rearrangement of cyclohexanone oxime elevates by 79% along with a great enhancement of catalytic stability.