Synthesis And Application Of Ordered Hybrid Mesoporous Carbon And Polymer

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.