本文關鍵詞：有機—無機納米復合微球在催化和相變儲能方面的應用研究　出處：《北京科技大學》2017年博士論文　論文類型：學位論文

  更多相關文章： 納米復合微球 過渡金屬催化劑 金屬有機框架材料 介孔SiO_2空心微球 相變材料

【摘要】：由于具有良好獨特的綜合性能,有機-無機納米復合微球近幾年受到了廣泛的關注,在催化、能量存儲和轉換、傳感器、光電器件及納米生物技術等方面都有著很重要的科學和工業(yè)應用價值。有機-無機納米復合微球中納米尺度的復合組分不僅可以實現材料間功能性的集成,而且有可能產生出復合前納米材料本身所不具備的特殊性質。本論文從有機-無機納米復合微球的控制合成入手,制備了一系列具有特殊形貌、新穎結構的有機-無機納米復合微球,探索了其在催化和儲能領域的應用,并研究了材料結構與性能之間的構效關系,為有機-無機納米復合微球的結構設計、性能調控及其在相關領域的實際應用提供了理論和實驗依據。本論文的研究包括三類新型有機-無機納米復合微球的設計制備及其在催化與儲能方面應用,主要結論為:(1)以磁性納米粒子(Cu-CuFe2O4)作為核,在有機配體均苯三甲酸(H3BTC)溶液的刻蝕下,Cu-CuFe2O4的Cu(O)組分的釋放金屬銅離子,原位轉化為八面體微孔晶體HKUST-1,即在Cu-CuFe2O4外層形成了 HKUST-1的包覆層,制備得到core-shell結構的Cu-CuFe2O4@HKUST-1納米復合微球,克服了傳統的層層自組裝法存在的反應條件苛刻、周期長且后處理復雜等缺點。將其用于催化劑時,實現了金屬有機骨架化合物MOFs(Metal Organic Framework)優(yōu)異的結構特性(超大的比表面積,均勻的孔徑分布,可控的拓撲結構及可調的孔徑)和微納米粒子Cu-CuFe2O4催化特性的優(yōu)勢集成,該催化劑在低溫以及以分子氧為綠色氧源的條件下,可以高效催化芐基類有機分子的氧化反應;此外,Cu-CuFe2O4磁性核心還賦予了催化劑的快速分離回收的功能;另一方面,具有微孔結構的HKUST-1殼層可保護Cu-CuFe2O4,避免催化活性組分在反應中的流失。(2)以單分散的聚乙烯吡啶微球(P4VP)為載體,通過N原子的孤對電子與Fe(Ⅲ)進行配位,實現對均相鐵催化材料的固載,得到負載型鐵系催化材料。通過調控單分散的聚乙烯吡啶微球的交聯度,利用不同交聯度的聚乙烯吡啶微球功能固載三價鐵離子能力的不同,探討了聚乙烯吡啶微球不同交聯度對負載型催化材料中Fe(Ⅲ)含量的影響,獲得一系列不同P4VPDVB2.5-40%-Fe(Ⅲ)催化劑;以4,4'-二氟二苯甲烷的氧化反應為探針反應,探索了不同催化劑的交聯度和含鐵量對催化性能的影響規(guī)律,實驗結果顯示,當交聯劑二乙烯基苯(DVB)的含量為10%時,催化劑P4VPDVB10%-Fe(Ⅲ)展現了優(yōu)良的催化性能;該催化劑具有很好的穩(wěn)定性,對于芐基類底物的氧化反應具有普適性;此外,合成的催化劑的吡啶部分是能夠作為一種有機堿,從而顯著減少了在系統中的有機堿吡啶的用量。(3)以磺化的聚苯乙烯微球(PS)為核,通過水熱法將在外層包覆介孔二氧化硅殼層,利用高溫煅燒,獲得介孔SiO2空心微球,并以其為載體,通過物理吸附法將相變材料十八酸(SA)固載于載體中,最終制備得到SA/介孔SiO2空心微球復合相變材料。介孔SiO2空心微球由介孔殼和空心空腔組成,具有較強毛細管力的介孔殼可以吸收十八酸到空心空腔,絕大部分的相變材料存在于空腔中,有利于十八酸的分子鏈自由結晶,從而導致復合相變材料的高儲能效率;存在于SA與介孔SiO2空心微球的界面處的氫鍵及孔道的毛細作用力,對熔融的SA起到有效的定形作用;介孔SiO2空心微球提升了 SA的熱導率,提升幅度在56%;且復合相變材料50次循環(huán)后仍然保持良好的相變性能。
[Abstract]:With a good overall performance unique, organic-inorganic nano composite microspheres have attracted much attention in recent years, catalysis, energy storage and conversion, sensor, photoelectric devices and nano biotechnology and other aspects have a very important application of scientific and industrial value. Composite nano scale organic-inorganic nanocomposite microspheres the points can not only realize the integration between the functional materials, and can produce specific properties of the composite materials are not available before. This paper from the controlled synthesis of organic inorganic nanocomposite microspheres with the preparation of a series of special morphology, organic inorganic nanocomposite microspheres with novel structure, explore the application in the field of catalysis and storage, and to study the structure-activity relationship between the structure and properties of materials, structural design of organic-inorganic nanocomposite microspheres, and its performance in the phase control Provides a theoretical and experimental basis for practical application in related fields. The research of this paper includes three kinds of novel organic-inorganic nano composite microsphere preparation and design in catalysis and energy storage applications, the main conclusions are as follows: (1) the magnetic nanoparticles (Cu-CuFe2O4) as the core, in the organic ligands were three Formic acid (H3BTC the etching solution), Cu-CuFe2O4 Cu (O) release of metal ion component of copper, in situ into eight surface microporous crystal HKUST-1, which formed the outer coating layer in Cu-CuFe2O4 HKUST-1, prepared by Cu-CuFe2O4@ HKUST-1 nano composite microspheres of core-shell structure, overcome the reaction conditions of traditional self-assembly method the harsh, disadvantage of long period and postprocessing is complex. For the catalyst, the metal organic framework compound MOFs (Metal Organic Framework) structure excellent characteristics (ultra large surface area, uniform The pore size distribution, pore topology controllable and adjustable) integration and catalytic properties of micro nanoparticles the advantages of Cu-CuFe2O4, the catalyst at low temperature and with molecular oxygen as the oxygen source green conditions could catalyze the oxidation reaction of benzyl base organic molecules; in addition, the rapid separation and recovery of Cu-CuFe2O4 magnetic core with the catalyst function; on the other hand, the microporous structure of HKUST-1 shell can protect Cu-CuFe2O4, avoid the catalytic active components in the reaction loss. (2) with polyvinyl pyridine microsphere (P4VP) as the carrier, through the N atom lone pair electrons with Fe (III) for coordination, to achieve homogeneous iron the supported catalytic material, supported iron catalysts. The regulation of polyvinyl pyridine microspheres monodisperse crosslinked, with different degree of crosslinking of polyvinyl pyridine microspheres supported functional ability of ferric ion is not At the same time, discussed the different degree of crosslinking of polyvinyl pyridine microspheres supported catalytic materials in Fe (III) on the content of a series of different P4VPDVB2.5-40%-Fe catalysts; (III) by oxidation of 4,4'- two fluorine two benzene methane as probe reaction to investigate the effects of different catalysts and the cross-linking degree of catalytic iron the performance, the experimental results show that when the crosslinking agent two divinyl benzene (DVB) content is 10%, the catalyst of P4VPDVB10%-Fe (III) showed excellent catalytic performance; the catalyst has good stability and universality for the oxidation of benzyl base substrate; in addition, the catalyst is part of pyridine synthesis can be used as an organic base, which greatly reduces the organic alkali pyridine in the system used. (3) with sulfonated polystyrene microspheres (PS) as the core, through the hydrothermal method in the outer cladding of mesoporous silica shell, the use of high Calcining temperature, obtained mesoporous SiO2 hollow microspheres, and takes it as the carrier, the phase change material eighteen acid through physical adsorption (SA) immobilized on the carrier, then prepared mesoporous SA/ SiO2 hollow microspheres composite phase change materials. Mesoporous SiO2 hollow microspheres by mesoporous shell and hollow cavity composed of dielectric shell has a strong capillary force can absorb eighteen acid into a hollow cavity, most of the phase change material in the cavity, is conducive to the crystallization of eighteen acid free molecular chain, which leads to high efficiency of energy storage phase change composite material; capillary force and hydrogen bond at the interface in SA and pore mesoporous SiO2 hollow micro spheres the effect of melt into amorphous SA; mesoporous SiO2 hollow microspheres enhance the thermal conductivity of SA, increase in 56%; and the composite phase change material after 50 cycles of phase change still maintain good performance.

【學位授予單位】：北京科技大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TB383.1

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本文編號：1425515