Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Fudan University, Shanghai, People's Republic of China.
J Am Chem Soc. 2011 Sep 28;133(38):15148-56. doi: 10.1021/ja2056227. Epub 2011 Sep 6.
We report for the first time the synthesis of free-standing mesoporous carbon films with highly ordered pore architecture by a simple coating-etching approach, which have an intact morphology with variable sizes as large as several square centimeters and a controllable thickness of 90 nm to ∼3 μm. The mesoporous carbon films were first synthesized by coating a resol precursors/Pluronic copolymer solution on a preoxidized silicon wafer and forming highly ordered polymeric mesostructures based on organic-organic self-assembly, followed by carbonizing at 600 °C and finally etching of the native oxide layer between the carbon film and the silicon substrate. The mesostructure of this free-standing carbon film is confirmed to be an ordered face-centered orthorhombic Fmmm structure, distorted from the (110) oriented body-centered cubic Im3̅m symmetry. The mesoporosity of the carbon films has been evaluated by nitrogen sorption, which shows a high specific BET surface area of 700 m(2)/g and large uniform mesopores of ∼4.3 nm. Both mesostructures and pore sizes can be tuned by changing the block copolymer templates or the ratio of resol to template. These free-standing mesoporous carbon films with cracking-free uniform morphology can be transferred or bent on different surfaces, especially with the aid of the soft polymer layer transfer technique, thus allowing for a variety of potential applications in electrochemistry and biomolecule separation. As a proof of concept, an electrochemical supercapacitor device directly made by the mesoporous carbon thin films shows a capacitance of 136 F/g at 0.5 A/g. Moreover, a nanofilter based on the carbon films has shown an excellent size-selective filtration of cytochrome c and bovine serum albumin.
我们首次通过简单的涂层-刻蚀方法合成了具有高度有序孔结构的独立式介孔碳膜,该碳膜具有完整的形态,尺寸可达数平方厘米,厚度可控,为 90nm 至 3μm。介孔碳膜首先通过在预氧化硅片上涂覆酚醛树脂前体/Pluronic 嵌段共聚物溶液,并基于有机-有机自组装形成高度有序的聚合物介观结构,然后在 600°C 下碳化,最后刻蚀碳膜和硅基底之间的本征氧化层。该独立式碳膜的介观结构被确认为有序的面心正交 Fmmm 结构,从(110)取向的体心立方 Im3̅m 对称性发生了扭曲。通过氮气吸附对碳膜的介孔性进行了评估,结果表明其具有 700m²/g 的高比表面积和~4.3nm 的均匀大介孔。通过改变嵌段共聚物模板或酚醛树脂与模板的比例,可以调整介观结构和孔径大小。这些具有无开裂均匀形态的独立式介孔碳膜可以转移或弯曲到不同的表面上,特别是在软聚合物层转移技术的辅助下,从而可以在电化学和生物分子分离等多种潜在应用中发挥作用。作为概念验证,由介孔碳薄膜直接制成的电化学超级电容器装置在 0.5A/g 时表现出 136F/g 的电容。此外,基于碳膜的纳米滤器已显示出对细胞色素 c 和牛血清白蛋白的出色尺寸选择性过滤。