Lan Kun, Liu Lu, Yu Jiayu, Ma Yuzhu, Zhang Jun-Ye, Lv Zirui, Yin Sixing, Wei Qiulong, Zhao Dongyuan
College of Energy Materials and Chemistry, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010070, P. R. China.
Laboratory of Advanced Materials, Department of Chemistry, College of Chemistry and Materials, Fudan University, Shanghai 200433, P. R. China.
JACS Au. 2023 Mar 13;3(4):1141-1150. doi: 10.1021/jacsau.3c00007. eCollection 2023 Apr 24.
Mesoporous materials with crystalline frameworks have been acknowledged as very attractive materials in various applications. Nevertheless, due to the cracking issue during crystallization and incompatible hydrolysis and assembly, the precise control for crystalline mesoscale membranes is quite infertile. Herein, we presented an ingenious stepwise monomicelle assembly route for the syntheses of highly ordered mesoporous crystalline TiO membranes with delicately controlled mesophase, mesoporosity, and thickness. Such a process involves the preparation of monomicelle hydrogels and follows self-assembly by stepwise solvent evaporation, which enables the sensitive hydrolysis of TiO oligomers and dilatory micelle assembly to be united. In consequence, the fabricated mesoporous TiO membranes exhibit a broad flexibility, including tunable ordered mesophases (worm-like, hexagonal to body-centered cubic ), controlled mesopore sizes (3.0-8.0 nm), and anatase grain sizes (2.3-8.4 nm). Besides, such mesostructured crystalline TiO membranes can be extended to diverse substrates (Ti, Ag, Si, FTO) with tailored thickness. The great mesoporosity of the fabricated mesoscopic membranes also affords excellent pseudocapacitive behavior for sodium ion storage. This study underscores a novel pathway for balancing the interaction of precursors and micelles, which could have implications for synthesizing crystalline mesostructures in higher controllability.
具有晶体骨架的介孔材料在各种应用中被认为是非常有吸引力的材料。然而，由于结晶过程中的开裂问题以及不相容的水解和组装，对晶体介观膜的精确控制相当困难。在此，我们提出了一种巧妙的逐步单胶束组装路线，用于合成具有精细控制的中间相、介孔率和厚度的高度有序介孔晶体TiO膜。这样的过程包括制备单胶束水凝胶，并通过逐步溶剂蒸发进行自组装，这使得TiO低聚物的灵敏水解和缓慢的胶束组装得以结合。结果，制备的介孔TiO膜表现出广泛的灵活性，包括可调谐的有序中间相（蠕虫状、六方到体心立方）、可控的介孔尺寸（3.0 - 8.0纳米）和锐钛矿晶粒尺寸（2.3 - 8.4纳米）。此外，这种介观结构的晶体TiO膜可以扩展到具有定制厚度的各种基底（Ti、Ag、Si、FTO）上。制备的介观膜的大介孔率也为钠离子存储提供了优异的赝电容行为。这项研究强调了一种平衡前驱体和胶束相互作用的新途径，这可能对以更高的可控性合成晶体介观结构有启示意义。
