Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, PR China.
Langmuir. 2010 Jun 15;26(12):10277-86. doi: 10.1021/la100455w.
Fuctionalization of porous carbon materials through chemical methods orientates the development of new hybrid materials with specific functions. In this paper, a comprehensive study of pore evolution, mesostructural oxidation resistance, and simultaneous surface functionalization of ordered mesoporous carbon FDU-15 under various oxidation conditions is presented for the first time. The mesostructure and pore evolution with increasing oxidative strength are retrieved from XRD, TEM, and N(2) sorption techniques. The textural properties can be conveniently manipulated by changing the oxidation parameters, including different oxidative solution, temperature, and duration. It is revealed that the mesoporous carbon FDU-15 shows excellent structural stability under severe oxidation treatments by acidic (NH(4))(2)S(2)O(8), HNO(3), and H(2)O(2) solutions, much more stable than the mesostructural analogue CMK-3 carbon prepared by the nanocasting method. The surface area and porosity deteriorate to a large extent compared to the pristine carbon, with the micropores/small mesopores as the major contribution to the deterioration. The micropore/small mesopore can be blocked by the attached surface oxides under mild oxidation, while reopened with more carbon layer dissolution under more severe conditions. Simultaneously, high densities of surface oxygen complexes, especially carboxylic groups, can be generated. The contents and properties of the surface oxygen-containing groups are extensively studied by FTIR, TG, elemental analyses, and water and ammonia adsorption techniques. Such surface-functionalized mesoporous carbons can be used as a highly efficient adsorbent for immobilization of heavy metal ions as well as functional organic and biomolecules, with high capacities and excellent binding capabilities. Thus, we believe that the functionalized mesoporous carbon materials can be utilized as a promising solid and stable support for water treatment and organic/biomolecules immobilization and may be applicable in drug delivery, separation, adsorption technology, and columns for GC and HPLC systems in the near future.
通过化学方法对多孔碳材料进行功能化,定向开发具有特定功能的新型杂化材料。本文首次全面研究了有序介孔碳 FDU-15 在各种氧化条件下的孔演变、中孔结构抗氧化性以及表面同时功能化。通过 XRD、TEM 和 N2 吸附技术,从孔演变和中孔结构氧化还原强度的角度研究了介孔结构和孔演变。通过改变氧化参数,包括不同的氧化溶液、温度和时间,可以方便地操纵其结构特性。结果表明,介孔碳 FDU-15 在酸性(NH4)2S2O8、HNO3 和 H2O2 溶液等剧烈氧化处理下表现出优异的结构稳定性,比纳米铸模法制备的介孔结构类似物 CMK-3 碳稳定得多。与原始碳相比,表面积和孔隙度大大恶化,其中微孔/小中孔对恶化的贡献最大。在温和氧化条件下,附着的表面氧化物会堵塞微孔/小中孔,而在更剧烈的条件下,更多的碳层溶解会使微孔/小中孔重新打开。同时,可以生成高密度的表面氧络合物,特别是羧基。通过 FTIR、TG、元素分析以及水和氨吸附技术广泛研究了表面含氧基团的含量和性质。这种表面功能化的介孔碳可用作重金属离子固定化的高效吸附剂,也可用作功能有机和生物分子的固定化材料,具有高容量和优异的结合能力。因此,我们相信功能化介孔碳材料可用作水处理和有机/生物分子固定化的有前途的固体和稳定载体,并且在不久的将来可能适用于药物输送、分离、吸附技术以及 GC 和 HPLC 系统中的柱。