本研究報告了一種簡單的方法，製備出由聚(苯乙烯-b-環氧乙烷)（PS-b-PEO）和多巴胺（DA）混合物組成之三維(3-D)多尺度孔隙。將混合物(BCP/DA)分別溶於不同的共溶劑中，THF/水和DMF/水。隨後HCl的添加不僅增強了PEO和DA之間的電荷?偶極相互作用、抑制了DA在溶液中的氧化反應，還可以提高混合物之間的有效Flory?Huggins參數，並在DMF/水之共溶劑系統中誘導3-D多尺度孔隙凝膠的形成。此溶液?凝膠的相轉變需要遵循兩步驟反應。首先，PS-b-PEO在共溶劑中形成微胞。接著，通過添加HCl獲得斑點狀微胞。作為物理性的交聯點，斑點狀微胞會自發的形成凝膠。此凝膠具有疏水性通道組成的3-D孔洞結構。將溶液或凝膠乾燥時，THF/水之共溶劑中的低分子量兩親性微胞會經歷快速的微胞融合過程，形成洋蔥狀囊胞。相比之下，DMF/水之共溶劑系統中的3-D多尺度孔隙凝膠能支撐自身的孔洞結構。接著在氨氣環境下引發DA的氧化聚合反應。發現由混合物(BCP/PDA)所構成之3-D多尺度孔隙結構仍保持不變。儘管在當前的製程中，高溫碳化後之3-D多尺度孔隙結構會塌陷，但此種具有高比表面積之3-D多尺度孔隙模板仍是非常具有應用價值。;Abstract Three-dimensional (3D) network templates show great potential and interest in the fabrication of electronic devices, electrocatalysis, and supercapacitors. The 3D-network templates provide favorable characteristics, such as high specific surface area, high mass, and diffusion transfer. In this work, we report a simple method to fabricate 3-D micelle networks through self-assembly of mixtures of polystyrene-block-poly(ethylene) (PS-b-PEO) and dopamine (DA) in solution. Mixtures are dissolved in two different co-solvents, THF/water, and DMF/water, respectively, followed by HCl addition HCl addition not only enhances charge?dipole interactions between PEO and DA but also prohibits the oxidation reaction of DA in solution. In addition, HCl can increase the effective Flory-Huggins parameter of PS-b-PEO for the mixtures and triggers formation of a gel-like structure in the DMF/water system. Two-steps are necessary to induce the sol?gel transition. First, low-molecular-weight (low-Mw) PS-b-PEO formed core-shell micelles in co-solvent. Second, deformed micelles were obtained by adding HCl. Patchy micelles were formed and acted as cross-linking points for gelling. The gel structure is a 3-D micellar network with hydrophobic channels. The network framework evolved from patchy micelles. Upon drying from THF/water co-solvent, micelles of low-Mw PS-b-PEO formed onion-like vesicles . In contrast, the 3-D gel structure could support the porous framework that had formed in DMF/water co-solvent. DA oxidative polymerization was induced by NH4OH vapor. It was found that 3-D porous structure of BCP/PDA mixtures remained unchanged after DA polymerization for the micelles in DMF/water. Nevertheless, 3-D porous networks could collapse after carbonization at a high temperature.
