本文選題：ZIF-8材料 + 核殼結(jié)構(gòu)��； 參考：《大連理工大學(xué)》2015年博士論文

【摘要】：核-殼結(jié)構(gòu)材料作為眾多形式復(fù)合材料中最為常見的一種,通常是由內(nèi)部的“核心”與外部的“殼層”組成,而且由于兩種不同性質(zhì)材料之間的結(jié)合,核殼結(jié)構(gòu)材料在一些領(lǐng)域的應(yīng)用過程中會展現(xiàn)出一些獨(dú)特的性能,使其在很多領(lǐng)域具有潛在應(yīng)用價值。以ZIF-8為代表的沸石咪唑酯骨架結(jié)構(gòu)材料由于其規(guī)則的孔道結(jié)構(gòu)、大的比表面積與孔容、良好的熱穩(wěn)定性與化學(xué)穩(wěn)定性,被廣泛應(yīng)用于催化、氣體吸附和氣體分離等方向的研究。本論文主要圍繞ZIF-8包覆的核-殼結(jié)構(gòu)粒子的設(shè)計、合成及其應(yīng)用展開,通過“核”材料與“ZIF-8殼”材料兩者性質(zhì)的結(jié)合,賦予該類核-殼粒子更多新穎的功能。主要內(nèi)容如下：(1)以Fe304磁性粒子為核、ZIF-8為殼層包覆形成Fe3O4@ZIF-8磁性核殼粒子。殼層成功包覆的關(guān)鍵是采用聚電解質(zhì)——聚苯乙烯磺酸鈉(PSS)對Fe304表面進(jìn)行修飾；然后考察了合成溫度、合成時間、Fe304與ZIF-8合成液固液比、合成次數(shù)對于ZIF-8殼層包覆的影響。通過外加磁場成功將Fe3O4@ZIF-8磁性核殼粒子固載至不銹鋼毛細(xì)管管壁組裝成了微反應(yīng)器,并應(yīng)用于催化苯甲醛與氰乙酸乙酯間的Knoevenagel縮合反應(yīng),表現(xiàn)出優(yōu)異的催化活性,而且具有磁性催化劑裝填／卸載的簡易操作性。(2)以水熱碳球(Collodial carbon sphere, CCS)負(fù)載鈀形成的Pd/CCS為核、ZIF-8膜為殼層制備了Pd/CCS@ZIF-8核殼結(jié)構(gòu)粒子。采用葡萄糖水熱法制備了粒徑均一的CCS,以其為載體通過自還原反應(yīng)進(jìn)行Pd納米粒子的負(fù)載在CCS表面形成Pd/CCS微球；利用Pd/CCS粒子豐富的表面官能團(tuán)及其表面較大的負(fù)電荷密度,使ZIF-8在Pd/CCS微球表面原位生長成膜得到完整包覆的Pd/CCS@ZIF-8核殼粒子。在催化液相烯烴加氫反應(yīng)時,Pd/CCS@ZIF-8核殼粒子表現(xiàn)出良好的抗Pd團(tuán)聚、防Pd流失功能,而且循環(huán)6次催化性能幾乎無降低。(3)以介孔二氧化硅微球形(Mesoporous silica sphere, MSS)為載體負(fù)載鈀形成的Pd/MSS為核、ZIF-8為殼層,結(jié)合聚電解質(zhì)表面修飾法與兩步變溫合成法成功制備了連續(xù)、完整ZIF-8殼層包覆的Pd/MSS@ZIF-8核殼粒子。聚電解質(zhì)(PDDA和PSS)修飾增加了Pd/MSS核粒子與ZIF-8殼層間的親和力和結(jié)合力；而采用低溫有利于成核、高溫有利于生長的兩步變溫ZIF-8殼層合成策略能有效減少殼層中的晶間縫隙和缺陷。該P(yáng)d/MSS@ZIF-8核殼催化劑應(yīng)用于烯烴液相加氫反應(yīng),不僅具有良好的防Pd流失功能：循環(huán)使用5次后該核殼催化劑依然保持良好的催化活性；而且完整的ZIF-8殼層還賦予了該核殼催化劑擇形催化和抗硫中毒功能。(4)結(jié)合聚電解質(zhì)表面修飾法與兩步變溫合成法合成了一種新型的Fe3O4@Pd/SiO2@ZIF-8磁性核／殼／殼結(jié)構(gòu)粒子。它綜合了Fe304核的磁性、Pd納米粒子的催化性能以及微孔ZIF-8殼層的固定和篩分功能,因此在烯烴液相加氫反應(yīng)中該核／殼／殼結(jié)構(gòu)粒子表現(xiàn)出良好的磁性回收、擇形催化、抗Pd團(tuán)聚、防Pd流失、抗硫中毒和多次重復(fù)使用功能。(5)探索了在非球型載體——ZSM-5分子篩粒子表面生長ZIF-8殼層的可行性,并合成了Pd/ZSM-5@ZIF-8核殼粒子。首先通過晶種誘導(dǎo)合成法成功合成出了粒徑均一、單分散好且具有典型六棱型形貌的ZSM-5分子篩；然后對ZSM-5分子篩進(jìn)行Pd納米粒子負(fù)載和聚電解質(zhì)表面修飾后,進(jìn)行ZIF-8殼層的包覆得到了具有擇形催化和可重復(fù)利用性的Pd/ZSM-5@ZIF-8核殼催化粒子。
[Abstract]:Core-shell structure materials as many forms in composite materials is one of the most common, usually is composed of internal and external "core" of "shell", but due to the combination of two different properties of materials, application of core shell structure material in some areas in the exhibition show some unique properties it has potential applications in many fields. With ZIF-8 as the representative of the zeolitic imidazolate frameworks as the pore structure of the rules, the specific surface area and pore volume, thermal stability and good chemical stability, widely used in catalysis, gas adsorption and separation of the design direction. This paper mainly focuses on the core-shell particles coated with ZIF-8, launches the synthesis and application, through the combination of nuclear materials and "ZIF-8" shell "to the nature of the material, giving the core-shell particles more novel main function. Contents are as follows: (1) with Fe304 magnetic particles as the core, ZIF-8 as shell coated Fe3O4@ZIF-8 magnetic core-shell particles. The key is the shell successfully coated by the polyelectrolyte -- sodium polystyrene sulfonate (PSS) was modified on the surface of Fe304; then the synthesis temperature, synthesis time and synthesis of ZIF-8 Fe304, the ratio of solid to liquid. The number of synthetic effects on ZIF-8 shell coated by the external magnetic field. The success of the Fe3O4@ZIF-8 magnetic core-shell particles immobilized to the stainless steel capillary wall assembled into a micro reactor, and applied to the Knoevenagel condensation reaction of benzaldehyde and ethyl cyanoacetate in between, showed excellent catalytic activity, easy to operate and has a magnetic catalyst uninstall /. (2) by hydrothermal carbon spheres (Collodial carbon sphere, CCS) supported palladium formed Pd/CCS as core and ZIF-8 films prepared Pd/CCS@ZIF-8 core-shell particles as shell. Preparation of uniform size CCS by glucose hydrothermal method, with its carrier to load Pd nanoparticles by self reduction reaction in CCS formed on the surface of Pd/CCS microspheres; using Pd/CCS particle rich surface functional groups and surface negative charge density, the ZIF-8 in the Pd/CCS in situ surface ball film Pd/CCS@ZIF-8 core-shell particles complete coating. In liquid phase catalytic hydrogenation of olefin, Pd/CCS@ZIF-8 core-shell particles showed good anti Pd aggregation, anti Pd loss function, and 6 cycles of catalytic performance almost no decrease. (3) using mesoporous silica microspheres (two - Mesoporous silica sphere, MSS) supported palladium the formation of Pd/MSS core and ZIF-8 shell, were prepared with continuous polyelectrolyte surface modification method and two step temperature synthesis method successfully, Pd/MSS@ZIF-8 core-shell particles ZIF-8 shell coated. Polyelectrolyte (PDDA and PSS) Modified increased Pd/MSS core particles and ZIF-8 shell between the affinity and binding force; and the low temperature nucleation, high temperature is in favor of the two step temperature ZIF-8 shell synthesis strategy can effectively reduce the growth in the shell of intergranular cracks and defects. The Pd/MSS@ZIF-8 core shell catalyst used in olefin hydrogenation reaction, not only can prevent Pd loss function good: after 5 recycles the nuclear shell catalyst still maintain good catalytic activity; and the complete ZIF-8 shell also gives the core-shell catalyst bedfor catalytic function and resistance to sulfur poisoning. (4) a new type of Fe3O4@Pd/SiO2@ZIF-8 magnetic core / shell / shell particles synthesized by synthetic method polyelectrolyte surface modification method and two step temperature. It combines the magnetic core of Fe304, the catalytic properties of Pd nanoparticles and porous ZIF-8 shell fixed and screening function, so in olefin liquid phase The core / shell / shell particles in hydrogenation reactions showed good magnetic recovery, selective catalysis, anti Pd aggregation, anti Pd loss, resistance to sulfur poisoning and used repeatedly. (5) explored in the non spherical carrier - ZSM-5 molecular sieve particles grown on the surface of feasibility of ZIF-8 shell, and synthesized. Pd/ZSM-5@ZIF-8 core-shell particles. Firstly through seed mediated synthesis method was successfully synthesized with uniform size and monodisperse ZSM-5 molecules and six typical prismatic morphology screen; then the ZSM-5 molecular sieve Pd nanoparticles and polyelectrolyte surface modified by ZIF-8 shell coating is obtained and shape selective catalysis reusable Pd/ZSM-5@ZIF-8 core shell catalyst particle.

【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TB33;O643.36

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