【摘要】：微納結(jié)構(gòu)過渡金屬氧化物的應(yīng)用已經(jīng)成為開啟許多先進(jìn)功能材料和智能設(shè)備潛力的重要工具。由于其具有不同的價態(tài)和價電子構(gòu)型而擁有特殊的光、電、磁、力學(xué)性質(zhì),在變色、發(fā)光、催化、傳感等許多方面都有應(yīng)用。其中,一維過渡金屬氧化物納米材料因直接、快速的電子傳輸性能以及特殊的幾何構(gòu)型,有望成為未來納米級電子器件的基元之一。此外,基于一維納米結(jié)構(gòu)有序自組裝的多級微納結(jié)構(gòu)擁有獨(dú)特的立體空間構(gòu)架,其中許多具有大的可接觸表面積與較多的活性位點(diǎn)數(shù)目,這種特殊的構(gòu)效關(guān)系昭示了其應(yīng)用的廣闊前景。本論文以三氧化鎢一維材料以及基于三氧化鎢一維結(jié)構(gòu)自組裝的多級微納結(jié)構(gòu)材料為研究目標(biāo),利用水熱法通過篩選反應(yīng)體系,調(diào)整反應(yīng)體系中各種條件,制備出晶體結(jié)構(gòu)、微觀尺度以及形貌可調(diào)控的一維結(jié)構(gòu)三氧化鎢及其自組裝多級結(jié)構(gòu)體系。進(jìn)而對所合成的產(chǎn)物進(jìn)行性能探究,包括應(yīng)用于環(huán)己醇催化脫氫體系和環(huán)己烯催化氧化體系的催化性能,以及應(yīng)用于電化學(xué)超級電容器的相關(guān)電化學(xué)性能。本論文所研究的內(nèi)容主要涉及如下幾個方面:(1)以鎢酸鈉、硝酸為反應(yīng)物,檸檬酸、硫酸鈉為分散劑和結(jié)構(gòu)導(dǎo)向劑,通過水熱法制備出沿著[001]軸方向生長的h-WO3納米棒。值得一提的是,這些納米棒是由直徑、長度一致的h-WO3納米線自組裝而成。實驗研究了以這種納米棒結(jié)構(gòu)三氧化鎢作為催化劑,在無相轉(zhuǎn)移劑、無酸性配體的條件下,以雙氧水(H202)作為氧化劑催化氧化環(huán)己醇合成環(huán)己酮。結(jié)果表明,在溫和的反應(yīng)條件下(80℃,常壓),納米棒結(jié)構(gòu)三氧化鎢能夠有效地提高雙氧水的氧化能力,使得環(huán)己酮的產(chǎn)率由3.1%提高到78.6%,大大高于使用商業(yè)三氧化鎢時環(huán)己酮的產(chǎn)率(43.0%)。同時催化劑也顯示出較高的催化穩(wěn)定性,這為合成環(huán)己酮提供了一種以三氧化鎢納米棒為催化劑、過氧化氫為氧化劑的綠色路徑。(2)提出一種在不使用模板的條件下僅使用兩種常見反應(yīng)物合成一維結(jié)構(gòu)三氧化鎢及多級結(jié)構(gòu)三氧化鎢水合物的簡便水熱方法。僅依靠調(diào)節(jié)前驅(qū)溶液的pH值就可以得到納米線自組裝的三氧化鎢棒及由納米棒自組裝的微納多級結(jié)構(gòu)(球狀、盤狀)三氧化鎢水合物。與此同時,通過對比試驗探究了 pH值對于產(chǎn)物晶體結(jié)構(gòu)和形貌的影響機(jī)理。進(jìn)一步,以所制備的微納結(jié)構(gòu)三氧化鎢作為催化劑,以雙氧水(H202)為氧化劑氧化環(huán)己烯合成己二酸。結(jié)果表明,在溫和的反應(yīng)條件(90℃、常壓)下這種催化劑能夠有效地提高雙氧水催化氧化環(huán)己烯制備己二酸的產(chǎn)率。(3)以鎢酸鈉為鎢源,通過水熱法制備出基于一維結(jié)構(gòu)自組裝的三氧化鎢水合物(h-WO3·0.33H2O)多級結(jié)構(gòu)材料。該材料的結(jié)構(gòu)除具有h-W03的三元通道和六元通道特征外,還在六元通道中堆積了水分子。這使得質(zhì)子在晶體內(nèi)部得以快速嵌入、脫嵌。同時,組成多級結(jié)構(gòu)的h-WO3·0.33H2O納米棒也給電子的傳輸提供了大量直接、快速的傳輸路徑。正是由于穩(wěn)定的晶體通道結(jié)構(gòu)、h-WO3·0.33H2O材料的質(zhì)子、電子雙重導(dǎo)體作用以及特殊的多級結(jié)構(gòu)使得h-WO3·0.33H2O材料具有很好的超級電容性能,在電流密度為0.5 Ag-1時具有391 Fg-1的比容量。同時,在電流密度為10 A g-1時仍能在循環(huán)2000次后穩(wěn)定保持298 F g-1的比容量。
[Abstract]:The application of micro nanostructured transition metal oxides has become an important tool to open many advanced functional materials and intelligent devices. Because of their different valence and valence electron configurations, they have special light, electrical, magnetic and mechanical properties, and are applied in many aspects, such as discoloration, luminescence, catalysis, transmission and so on. Chemical nanomaterials are expected to be one of the basic elements of the future nanoscale electronic devices because of their direct, rapid electronic transmission properties and special geometric configurations. In addition, the multi-stage micro nanostructures based on the ordered self-assembled one-dimensional nanostructures have unique three-dimensional spatial structures, many of which have large contact surface area and more activity. The number of loci, this special structure-activity relationship shows the broad prospect of its application. In this paper, we use one dimensional tungsten trioxide material and multistage micro nano structure material based on one dimensional structure of tungsten oxide as the research target. By using the hydrothermal method, the various conditions in the reaction system are adjusted by screening the reaction system, and the crystal structure is prepared. The one-dimensional structure of tungsten trioxide and its self-assembled multistage structure system have been investigated, including the catalytic performance of cyclohexanol catalytic dehydrogenation system and cyclohexene catalytic oxidation system, as well as the related electrochemical properties of electrochemical supercapacitors. The main contents of this study are as follows: (1) the h-WO3 nanorods which grow along the [001] axis are prepared by sodium tungstate and nitric acid as reactant, citric acid, sodium sulfate as dispersant and structural guide. It is worth mentioning that these nanorods are self assembled by the diameter, uniform length of h-WO3 nanowires. The synthesis of cyclohexanone by the catalytic oxidation of cyclohexanol with hydrogen peroxide (H202) as an oxidizing agent under the condition of no phase transfer agent and no acidic ligand is investigated. The results show that the nanorod structure of tungsten oxide can effectively improve oxygen oxygen in hydrogen peroxide under mild reaction conditions (80 degrees C, atmospheric pressure). The yield of cyclohexanone increased from 3.1% to 78.6%, greatly higher than the yield of cyclohexanone (43%) when using commercial tungsten trioxide (43%). The catalyst also showed high catalytic stability. This provides a green path for synthesis of cyclohexanone with a tungsten trioxide nanorod as the catalyst and hydrogen peroxide as a oxidant. (2) A simple and convenient hydrothermal method is used to synthesize tungsten trioxide and multistage tungsten trioxide hydrate with only two kinds of common reactants without the use of the template. The self-assembled tungsten trioxide rod and the nanorod self assembled micro nano structure (spherical, disk) can be obtained by adjusting the pH value of the precursor solution only by adjusting the value of the precursor solution. At the same time, the influence mechanism of pH value on the crystal structure and morphology of the product was investigated by comparison test. Further, the synthesized tungsten oxide tungsten oxide was used as the catalyst to oxidize cyclohexene to adipic acid with hydrogen peroxide (H202) as the oxidizing agent. The results showed that under mild reaction conditions (90 degrees, atmospheric pressure) The catalyst can effectively improve the yield of hexandiacid prepared by hydrogen peroxide catalyzed oxidation of cyclohexene. (3) a tungsten trioxide hydrate (h-WO3. 0.33H2O) multistage structure based on one dimensional self assembly was prepared by hydrothermal method using sodium tungstate as the tungsten source. The structure of this material has the characteristics of three yuan channel and six element channel of h-W03. Water molecules are stacked in the six element channel. This allows protons to be embedded quickly and inlaid in the crystal. At the same time, the multistage structure of the h-WO3. 0.33H2O nanorods also provides a large number of direct and rapid transmission paths for the transmission of electrons. It is due to stable crystal channel structure, proton and electronic dual conduction of h-WO3. 0.33H2O materials The body effect and the special multistage structure make the h-WO3 0.33H2O material have good supercapacitor performance and have a specific capacity of 391 Fg-1 when the current density is 0.5 Ag-1. At the same time, the specific capacity of 298 F g-1 can still be maintained at the current density of 10 A g-1.
【學(xué)位授予單位】：合肥工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TQ136.13

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