摘要
无机层状化合物由于其离子交换能力和可溶胀性,可以使不同的客体分子(包括有机、无机和有机金属化合物等)进入层空间,而层板的基本结构不会被破坏。通过插层组装方式设计层状纳米复合材料,主要是基于将客体分子的化学、光学、电学、磁学等功能性质与无机主体材料的结构、机械和热稳定性等结合,被认为是制备纳米复合材料的最有前途的方法之一。层状纳米复合材料为构筑光电纳米器件、化学或生物传感器提供了新材料体系,在分子识别和催化等领域都有广阔的应用前景。
本文以阳离子型无机层状化合物(铌酸盐、钛酸盐、铌钛酸盐以及α-磷酸锆等)为主体,以水溶性金属卟啉衍生物、导电聚合物以及色素等为客体,制备了多种新型层状纳米复合材料,利用XRD、IR、元素分析、UV-vis等手段对制得的纳米复合材料进行结构、形貌和性质分析,并研究了这些复合材料在电催化、化学催化、发光、光催化等方面的应用。
以半导体层状化合物K4Nb6O17、K2Ti4O9和KTiNbO5为主体材料,采用客体-客体交换法成功地将水溶性金属卟啉衍生物阳离子MtTMPyP(Mt=Mn、Fe、Co)引入层间。根据XRD结果分析,并结合金属卟啉衍生物的分子尺寸,可以推测客体分子在主体材料层间均以单层倾斜方式紧密堆积。通过简单的滴涂法,制得了插层复合材料薄膜修饰玻碳电极。循环伏安测试表明修饰电极具有良好的电化学活性,在中性缓冲溶液中能够催化氧气还原。
以环烯烃环氧化为探针,考察了制得的系列金属卟啉衍生物插层纳米复合材料的催化性能。尽管与金属卟啉均相催化体系相比,非均相体系中底物的转化速度要慢一些,但选择性明显提高,这主要是由于主体层板提供的二维纳米反应器为底物的选择性氧化提供了理想的反应场。在九种层状复合材料中,MnTMPyP-Nb6O17和CoTMPyP-Nb6O17的催化活性最高,循环使用多次后催化活性未见降低。
采用原位聚合的方法成功地制备了聚苯胺插层铌钛酸盐(PANI-TiNbO5)和聚吡咯插层铌酸盐(PPy-Nb6O17)纳米复合材料。基于XRD分析结果,对单体在层间的排列方式和原位聚合机理进行了推测。在HCl溶液中,PANI-TiNbO5薄膜修饰玻碳电极的循环伏安曲线呈现两对氧化还原峰,分别对应于PANI的还原态形式向半氧化半还原态盐形式的转化以及半氧化半还原态盐形式向氧化态形式的转化。在LiClO4水溶液中,PPy-Nb6O17修饰电极的循环伏安曲线呈现一对可逆的氧化还原峰,对应于[PPy+,Cl04-]/PPy电对。而在聚苯胺/α-磷酸锆复合材料的制备过程中,尽管单体进入到了层间,但苯胺聚合可能发生α-ZrP的外层空间。
采用客体-客体交换法成功地制备了荧光染料罗丹明6G插层铌钛酸盐纳米复合材料。根据XRD结果,推测R6G在层间以单分子层方式排列,分子长轴垂直于层板。TG-DSC测试结果表明相比单一的客体分子,R6G在铌钛酸盐层间具有更高的热稳定性,这可能是由于纳米层板起到了一定的阻隔作用。荧光测试表明尽管插层复合材料中R6G的浓度很高(质量分率达到了约34.8%),复合材料薄膜依然展现出高的荧光效率。
制备了Fe203柱撑钛酸盐纳米复合材料,考察了该复合材料对甲基橙的光催化降解性能,结果表明复合材料的光催化活性比单一的主、客体材料要高,这可能是由于插层组装方式有利于主体层板与客体分子之间的电子转移,延长了瞬态电子的寿命,还可能与主客体之间形成新的能量匹配有关。
Inorganic layered compounds can accommodate a great diversity of guest molecules (including organic, inorganic and organometallic compounds) due to their ionic exchange capacity and the expandability of their interlayer spaces while maintaining other structural features unalterable. The design of layered nanocomposites by the intercalation techniques is based on the interconnection and compatibility between the chemical, optical, electrical and magnetic properties of the guest molecule with the structural, mechanical and thermal stability of the host material, which has been considered as one of the most promising methods for the fabrication of nanocomposites. Layered nanocomposites offered novel material systems for the design of optoelectronic nanodevices, chemical sensors and biosensors, with potential applications in the fields of molecular recognition and catalysis.
In this dissertation, the cationic inorganic layered compounds (niobate, titanate, titanoniobate and a-zirconium phosphate) were chosen as host materials. By using water-soluble metalloporphyrins, conducting polymers and pigments as guest molecules, several novel layered nanocomposites have been successfully prepared. The sturcture, morphology and properties of the obtained nanocomposites have been characterized by XRD, IR, elemental analysis, UV-vis, et al. Furthermore, the applications of these nanocomposites in the fields of electrocatalysis, chemical catalysis, luminescence and photocatalysis have been investigated.
The water-soluble metalloporphyrins cations MtTMPyP (Mt=Mn, Fe, Co) have been successfully inserted into the interlayer spacing of layered semiconductor compounds (K4Nb6O17, K2TiO9and KTiNbO5). Based on XRD analysis and the molecular dimension of metalloporphyrins, it has been speculated that the guest molecules are closely packed with the monolayer tilted against the host nanosheets. By simple dip-coating, the layered nanocomposited modified glassy carbon electrodes were prepared. The cyclic voltammetry tests revealed that the modified electrodes exhibit good electrochemical activity and can effectively electrocatalyze oxygen reduction in neutral buffer solution.
The catalytic performance of the as-prepared metalloporphyrins intercalated nanocomposites for the epoxidation of cyclohexene was studied. Although in heterogeneous systems the conversion rate of substrate was lower than that of homogeneous systems, the selectivity is obviously higher. The oxidation can proceed selectively by means of the unique two dimensional reaction field provided by the host layers. Among the nine layered nanocomposites, MnTMPyP-Nb6O17and CoTMPyP-Nb6O17exhibited the best catalytic performance. And both catalysts showed no appreciable decrease in activity after several reaction cycles.
Polyaniline intercalated titanoniobate (PANI-TiNbO5) and polypyrrole intercalated niobate (PPy-Nb6O17) nanocomposite have been successfully prepared by in-situ polymerization method. Accordingly to the XRD results, the arrangement of monomers in the interlayer spacing as well as the polymerization mechanism has been proposed. In HCl solution, the cyclic voltammetry curves of PANI-TiNbO5modified electrode showed two pairs of redox peaks, corresponding to the conversion of Leucoemeraldine state to Emeraldine salt and Emeraldine salt to Pernigraniline state, respectively. In LiClO4aqueous solution, the CV curves of PANI-TiNbO5modified electrode showed one reversible redox wave, corresponding to [PPy+,ClO4-]/PPy couples. In the preparation process of polyaniline/α-zirconium phosphate composite, monomer was inserted between the nanosheets, while the polyerization occurred in the outer space.
Rhodamine6G (R6G), a well-known fluorescent dye, has been intercalated into layered potassium titanoniobate through a guest-guest exchange method. It is postulated here that R6G forms monolayer coverage with its long molecular axis being oriented perpendicular with respect to titanoniobate nanosheets. TG-DSC analysis revealed that in comparison with pure dye, the intercalation of dye molecules in solid inorganic host material enhances thermostability of the dye. We are delight to find that R6G cations in thin film are highly fluorescent even at a high dye concentration (34.8wt%).
Finally, Fe2O3pillared titanate nanocomposite was fabricated. The photocatalytic degradation performance of the nanocomposite toward methyl orange was studied. It was found that the photocatalytic activity of the nanocomposite was higher than the single host and guest material. The intercalation assembly structure may favor the electron transfer between the host and the guest and increase the lifetime of transient electrons. And the enhanced photocatalytic acvitiy may also be related to the new energy match formed between the host and guest.
引文
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