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三维有序大孔碳球的合成、修饰和催化性质

Synthesis and Modification of Highly Ordered Three Dimensionally Macroporous Carbon Spheres and Their Catalytic Properties

【作者】 张建明

【导师】 康振辉;

【作者基本信息】 苏州大学 , 有机化学, 2012, 硕士

【摘要】 近年来,基于三维有序多孔碳材料规整均一的孔道、可控的纳米结构、较高的比表面积、良好的导电性和优良物理性质,因此在光、电、磁、催化、生物医学、传感和纳米工程等领域展取得良好的应用前景,已受到材料和催化领域的普遍关注。随着多孔碳材料应用领域的不断延伸,众多孔径可调,孔道形状不一,形貌多样的多孔材料被不断合成出来,成为当前碳材料研究的热点课题之一。但是多孔材料的研究过程中仍然有许多未知和不足需要我们探索解决之道,如孔碳形貌可控,孔道均一并且长程有序。三维有序多孔规整碳材料的合成及其应用仍是一重大的挑战与机遇,以致大量工作需要我们去做。在本论文中,我们以葡萄糖为碳源,二氧化硅光子晶体球为模板,制备了三维有序大孔碳球(MPCS)。采用粉末X射线衍射(XRD)、低温N2吸附,扫描电镜(SEM)、投射电镜等对三维有序大孔碳球的结构进行了综合的表征。结果表明,三维有序大孔(250nm)彼此相连接成大的碳球(50μm)。以MPCS为催化剂载体,在其孔道负载Pt(PtNPs/MPCS),通过循环伏安法研究了PtNPs/MPCS的电催化甲醇氧化特性。结果表明,PtNPs/MPCS具有很好甲醇催化氧化性质并且具有很强的抗CO中毒的能力,是优良的催化剂载体。用半胱酰胺修饰MPCS的孔道(MPCS-CO-Cys),以其作电极材料检测(阳极溶出伏安法)重金属离子。结果表面,MPCS-CO-Cys具有很强的重金属离子响应能力,同时也研究了同时检测多种重金属离子的能力。证明MPCS-CO-Cys是很好的快速准确检测重金属离子的材料。用二氧化硅光子晶体作模板在低温下不完全碳化葡萄糖制备了MPCS,并在其孔道表面回流浓硫酸接上磺酸基,作为新型固体酸—MPCS-SO3H。通过催化乙酸乙酯酯化反应能力研究了MPCS-SO3H催化活性。结果表明,这种具有三维有序的大孔的固体酸(MPCS-SO3H)具有很好的酸催化能力和稳定性。

【Abstract】 In recent years, ordered porous carbon nanomaterials received much attention dueto their ordered pores, tailorable textural properties, large surface area, highconductivities and excellent physical property. These outstanding structural propertiesmake porous carbon materials exhibit potential applications in catalysis,optics,electrics,magnetism,nanotechnology, and sensors, eta. With the development ofapplication of porous carbon nanomaterials, numerous porous nanomaterials withdifferent pore sizes and pore shapes have been prepared, which become a hot topic ofthe present carbon materials. However, there are lots of shortages and unknownremaining to explore and solve, for example, how to shape the porous carbon and howto control the pore and size of porous carbon. Preparing and applications of orderedthree dimensionally uniformed porous carbon materials with regular configuration arestill a opportunity and challenge, which need a lot of work to do. In this paper, highlyordered three dimensionally macroporous carbon spheres (MPCS) were successfullyprepared against removable colloidal silica crystal bead templates by carbonization ofglucose. The unique structural characteristics of the well-developed three dimensionallyinterconnected macropores were characterized by X-ray diffraction scanning (XRD),nitrogen adsorption, electron microscopy (SEM), transmission electron microscopy(TEM). The3DMPCS have diameter about50μm and the size of uniform large porestructures composing of MPCS is about250nm.MPCS were used as catalyst support and Pt nanoparticles were supported on thethree dimensionally interconnected macropores. It was found that the MPCS supportedPt exhibited high electrocatalytic activity for methanol oxidation.MPCS were covalently modified by cysteine (MPCS-CO-Cys). High sensitivitywas exhibited when this material was used as electrode material in electrochemical detection (square wave anodic stripping voltammetry) of heavy metal ions.Simultaneous detection of heavy metal ions was also investigated. All these show thatMPCS-CO-Cys were a god-given material for rapidly detecting heavy metal ions withhigh accuracy.Highly ordered three dimensional macroporous carbon spheres bearing sulfonicacid groups (MPCS-SO3H) were prepared by incomplete carbonization of glucose insilica crystal bead template at low temperature, followed by sulfonation and removal ofthe template. The catalytic properties of the MPCS-SO3H were evaluated byesterification of ethanol with acetic acid, indicating that MPCS-SO3H possessremarkable catalytic performance (high stability and acid catalytic ability) for theesterification.

  • 【网络出版投稿人】 苏州大学
  • 【网络出版年期】2012年 10期
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