【作者】 庄鑫；

【导师】 万颖；

【作者基本信息】 上海师范大学 ， 物理化学， 2010， 硕士

【摘要】 有序杂化介孔碳和聚合物材料由于具有高的比表面积,大的孔体积,均一可调的孔径,介观结构可控等优点,广泛的应用于催化、吸附、光学器件、电化学等科技领域。因此,本文以三嵌段共聚物F127为模板,多元体系共组装的方法,合成有序杂化介孔碳和聚合物材料,并应用于吸附和催化反应中。全文共分四章,第一章为文献综述,主要介绍了杂化介孔碳和介孔聚合物的发展以及研究现状。第二章介绍了以三嵌段共聚物模板,合成了具有二维六方结构的孔径分布均一,高比表面积,大的孔体积的有序介孔碳材料,并应用于吸附废水中的染料大分子。这几种碳材料具有不同的孔径(4.5 - 6.4 nm)、比表面积(398 - 2580 m2/g)和孔体积(0.51 - 2.16 cm3/g)。分别用于吸附染料亚甲基蓝、碱性品红、罗丹明B、灿烂黄、维多利亚蓝B、甲基橙和苏丹红。同时也考查了商业活性炭对上述染料的吸附性能。结果表明介孔碳材料(孔径6.4 nm、比表面积2580 m2/g、孔体积2.16 cm3/g)对染料的吸附量是商业活性炭的两倍,并且介孔碳对低浓度的染料有较高的吸附率,高达到99 %。无论是对碱性染料,酸性染料还是对偶氮染料都有很好的吸附行为。吸脱附后的介孔碳仍然很稳定,可以重复使用。值得一提的是,高比表面积,大的孔体积,双孔分布的介孔碳MPSC/C具有高的吸附性能。同时,本实验建立了吸附剂的孔尺寸大小与染料分子尺寸之间的关系,染料分子的空间尺寸在有序介孔碳的吸附过程中起了决定性的作用。当吸附小尺寸的染料分子时,孔径小、孔体积大、比表面积高的有序介孔碳吸附剂利于吸附,孔的利用率高;当吸附大尺寸的染料分子时,孔径大、孔体积大、比表面积高的有序介孔碳吸附剂利于吸附。以上的结果为有序介孔碳吸附水体中有机污染物提供了可能。第三章介绍了硫酸溶剂萃取脱除模板法来脱除由三元共组装制备的介孔聚合物-氧化硅复合材料的三嵌段共聚物模板。萃取后,纳米复合材料的孔道是开放的,得到的介孔聚合物-氧化硅复合材料具有有序的介观结构、高的比表面积(332 - 367 m2/g)、大的孔体积(0.66 - 0.78 cm3/g)、较大的孔径(~ 10.9 nm)。此方法与焙烧除表面活性剂的方法相比,骨架收缩较小,所得的材料具有较大的孔径。硫酸溶液萃取的方法在去除含有机官能团功能化的有机-无机复合材料的模板中有潜在的应用空间。第四章介绍了多元共组装的方法,由MPTMS、TEOS、酚醛树脂和三嵌段共聚物共组装制备有机功能化的介孔杂化材料,其中巯基的含量和酚醛树脂的量是可调节的。合成的巯基功能化的有机-无机纳米复合材料具有高度有序的介观结构、高的比表面积(198 - 466 m2/g)、大的孔体积(0.18 - 0.89 cm3/g)、均一的孔径(4.0 - 7.8 nm)和高的巯基含量(1.55 - 3.79 mmol/g)。巯基功能化的有机-无机纳米复合材料对水体中的银离子和铅离子具有高的吸附性能,材料本身非常稳定,可以重复使用。巯基功能化的有机-无机纳米复合材料可以通过双氧水氧化巯基组分而获得磺酸功能化的有机-无机纳米杂化材料。磺酸功能化的有机-无机纳米杂化材料具有高的比表面积、大的孔体积、均一的孔径和易接近的酸性位。该材料催化苯酚和丙酮的缩聚合成双酚A,具有高的催化活性。更多还原

【Abstract】 Hybrid mesoporous carbon and polymer materials have high surface areas, large pore volumes, uniform and tunable pore sizes and well-controlled pore structures which open up many potential applications in catalysis, adsorption, optics and electrical chemistry, etc. This thesis fouces on synthesis of ordered hybrid mesoporous polymers and carbons and their application as adsorbents and catalysts.The thesis is composed of four chapters. The first chapter is a detailed review on the development and research status of (hybrid) mesoporous carbons, polymers and organic-inorganic composites.Chapter 2 described highly efficient adsorption of bulky dyes in waste water has been demonstrated on ordered mesoporous carbon adsorbents prepared from the surfactant-templating approach. Our results show that ordered mesoporous carbon adsorbents have high adsorption rates (> 99.9%) for low-concentration dyes, good performance in decoloration regardless of the dye nature, including basic, acidic or azo dyes, and high stability after dye elution. In particular, the ordered mesoporous carbon MPSC/C adsorbent which has interpenetrated bimodal pores (6.4 and 1.7 nm), an extremely high surface area (2580 m2/g) and a large pore volume (2.16 cm3/g) exhibits higher capacities about twice) in adsorbing bulky dyes than activated carbon. To establish the relationship between the size of adsorbate and pore size of adsorbent, ordered mesoporous carbons with the same 2-D hexagonal mesostructure but different pore textural properties are synthesized by using phenolic resins as carbon sources and triblock copolymer F127 as a template. The spatial effect of dye molecules is the determinative factor for the adsorption in ordered mesoporous carbons. When adsorbing small-size dye molecules, the mesoporous adsorbent with a small pore size, a large pore volume and a high surface area is efficient. The pore utilization is high. In the cases of adsorption of large-molecule-size dyes, the adsorbent with a large pore size, a large pore volume and a high surface area is a good candidate. These behaviors offer good opportunities for mesoporous carbons in adsorption of organic pollutants.In Chapter 3, Triblock copolymer templates in mesoporous polymer-silica nanocomposites with a polymer content lower than 51 wt% have been extracted by sulfuric acid (48 wt%) under reflux. A double extracted is adopted to almost eliminate templates. The extracted mesoporous polymer-silica composites possess high surface areas (332 - 367 m2/g) and large pore volumes (0.66 - 0.78 cm3/g). On comparison with the calcination method, the extraction method is mild and reduces framework shrinkage due to the lack of heating treatment at high temperatures. Correspondingly, the pore sizes of extracted composites (about 10.7 nm) are larger than those of calcined materials. The extraction method also has the advantage in maintenance of organic groups, showing potentials in removing templates from nanocomposites containing functional moieties, which are easily eliminated during heating treatment.In Chapter 4, The organic-group functionalized mesoporous hybrid materials have been synthesized by the multi-constituent co-assembly route which involves the organosilane such as MPTMS as an organic functional group source, TEOS as an inorganic matrix source, resols as organic matrix sources, and triblock copolymer F127 as a structure directing agent. Both the thiol and polymeric resins contents can be tuned.The thiol-containing organic-inorganic composites have the ordered mesostructure, high surface areas (198 - 466 m2/g), large pore volumes (0.18 - 0.89 cm3/g), large pore diameters (4.0 - 7.8 nm) and high-content, chemically accesible thiol groups (1.55 - 3.79 mmol/g). Mesoporous thiol-functionalized hybrid materials are stable and show high adsorption efficiency in adsorbing heavy metal ions. Mesoporous organic-inorganic composites containing sulfonic acid groups can be further obtained by oxidation of mercapto-modified composites with hydrogen peroxide. The mesoporous sulfonic-acid-modified composites possess high surface areas, large pore volumes, uniform pore sizes, and accessible acidic sites, showing high catalytic activity in condensation of phenol and acetone.更多还原