Full Gamut Wall Tunability from Persistent Micelle Templates via Ex Situ Hydrolysis
Full Gamut Wall Tunability from Persistent Micelle Templates via Ex Situ Hydrolysis
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通过异位水解实现持久性胶束模板的全色域壁可调性
DOI：
10.1002/smll.201900393
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发表时间：
2019
期刊：
影响因子：
13.3
通讯作者：
Stefik, Morgan
中科院分区：
文献类型：
--
作者：
Lantz, Kayla A.;Clamp, Nicholas Blake;van den Bergh, Wessel;Sarkar, Amrita;Stefik, Morgan
可调纳米结构的预测性自组装对于广泛的纳米材料研究和应用具有很大的实用性。然而，基于平衡的方法的使用阻止了独立的特征尺寸控制。动力学控制方法如持久性胶束模板（PMT）克服了这一限制，并通过对链交换施加较大的热力学屏障来保持恒定的孔径。因此，通过向PMT添加材料前体来独立地调节壁厚。之前的PMT演示将水反应性材料前体直接添加到胶束水溶液中。这种方法消耗了链交换的热力学屏障，从而限制了PMT控制下添加的材料量。在这里，一个异位水解的方法是开发二氧化钛，减轻这种消耗的水和几乎replicles材料化学从胶束控制。这实现了最宽的PMT范围（M：T = 1.6-4.0），从稀疏的壁到几乎孤立的孔，具有1.2 μ m的精度调节。这种高分辨率纳米材料系列表现出单调的趋势，其中壁厚增加导致PMT限制在更大的微晶和锂化程度增加，达到Li0.66TiO 2。锂化程度随着微晶尺寸的增加而增加，这归因于青铜和青铜多晶型物混合物的尺寸依赖性应变失配。
The predictive self‐assembly of tunable nanostructures is of great utility for broad nanomaterial investigations and applications. The use of equilibrium‐based approaches however prevents independent feature size control. Kinetic‐controlled methods such as persistent micelle templates (PMTs) overcome this limitation and maintain constant pore size by imposing a large thermodynamic barrier to chain exchange. Thus, the wall thickness is independently adjusted via addition of material precursors to PMTs. Prior PMT demonstrations added water‐reactive material precursors directly to aqueous micelle solutions. That approach depletes the thermodynamic barrier to chain exchange and thus limits the amount of material added under PMT‐control. Here, an ex situ hydrolysis method is developed for TiO2that mitigates this depletion of water and nearly decouples materials chemistry from micelle control. This enables the widest reported PMT range (M:T = 1.6–4.0), spanning the gamut from sparse walls to nearly isolated pores with ≈2 Å precision adjustment. This high‐resolution nanomaterial series exhibits monotonic trends where PMT confinement within increasing wall‐thickness leads to larger crystallites and an increasing extent of lithiation, reaching Li0.66TiO2. The increasing extent of lithiation with increasing anatase crystallite dimensions is attributed to the size‐dependent strain mismatch of anatase and bronze polymorph mixtures.