本文關(guān)鍵詞： 纖維素 表面溶膠-凝膠法 自組裝 光電轉(zhuǎn)化 鋰離子電池　出處：《浙江大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：進(jìn)入二十一世紀(jì),工業(yè)的飛速發(fā)展伴隨著巨大的能源消耗,人類面臨著化石燃料等不可再生能源的日益枯竭,以及隨之而來的一系列嚴(yán)峻的環(huán)境問題。因此,開發(fā)新型清潔能源材料和充分利用太陽能等可再生能源迫在眉睫。自然界中存在著大量的生物質(zhì)資源,其中,天然纖維素物質(zhì)具有豐富的產(chǎn)量、良好的生物可降解性、生物相容性、柔韌性和機(jī)械強(qiáng)度,并且纖維素分子之間復(fù)雜的相互作用賦予其獨(dú)特的三維多層級(jí)結(jié)構(gòu)、多孔性和大比表面積。因此,天然纖維素物質(zhì)是優(yōu)良的生物模板,其表面豐富的活性羥基使多種客體材料在纖維素表面的自組裝成為可能。本文是基于天然纖維素物質(zhì)(無灰定量濾紙)為模板,在纖維素單根納米纖維表面進(jìn)行多種氧化物客體分子的自組裝,隨后以不同的方式進(jìn)行后處理,制備得到結(jié)合了天然纖維素模板獨(dú)特結(jié)構(gòu)和客體材料特異性功能的新型先進(jìn)功能納米材料,可用于光電轉(zhuǎn)化體系和鋰離子電池等領(lǐng)域的研究,主要內(nèi)容如下:1、光系統(tǒng)Ⅱ/多孔二氧化鈥納米管網(wǎng)絡(luò)光陽極體系:基于天然纖維素的表面羥基和鈦醇鹽的共價(jià)作用,在濾紙的納米纖維表面進(jìn)行二氧化鈦凝膠薄膜的層層自組裝,在空氣中煅燒除掉纖維素模板,得到精確復(fù)制了模板多層級(jí)多孔網(wǎng)絡(luò)結(jié)構(gòu)的銳鈦礦型二氧化鈥納米管材料。用該二氧化鈥材料對(duì)電極基底表面進(jìn)行修飾。隨后,將從菠菜葉片中提純出的具有光解水功能的光系統(tǒng)Ⅱ(PSⅡ)蛋白組裝在電極上,成功構(gòu)建了新型蛋白/半導(dǎo)體復(fù)合仿生光陽極體系。由于電極的平面結(jié)構(gòu)被二氧化鈦納米管材料優(yōu)化,蛋白在電極表面的負(fù)載量得以提高。此外,PSⅡ蛋白和二氧化鈦之間具有協(xié)同作用,在PSⅡ蛋白和二氧化鈦能級(jí)間的電子傳遞模擬了自然界光合作用中的電子傳遞"Z"型鏈。該復(fù)合光陽極體系具有良好的光電化學(xué)性能。將其用于太陽能的轉(zhuǎn)化和電能的產(chǎn)生,在模擬太陽光的白光照射下能產(chǎn)生較高的光電流,在一定外加條件下能夠驅(qū)動(dòng)LED燈泡發(fā)光。2、光系統(tǒng)Ⅱ/納米管狀氧化銦錫薄膜共組裝光陽極體系:基于天然纖維素的表面羥基和銦醇鹽、錫醇鹽的共價(jià)作用制備得到氧化銦錫(ITO)凝膠薄膜/纖維素復(fù)合材料,在空氣中煅燒除掉纖維素成分,即可得到精確復(fù)制了纖維素模板的多層級(jí)多孔網(wǎng)絡(luò)結(jié)構(gòu)的納米管狀I(lǐng)TO薄膜材料。該材料對(duì)可見光透過性良好,其銦錫比使材料具有較高的導(dǎo)電率。將納米管狀I(lǐng)TO薄膜材料用導(dǎo)電金膠粘附在電極基底上實(shí)現(xiàn)對(duì)平面電極的修飾,并將PSⅡ蛋白組裝在ITO薄膜材料的多孔網(wǎng)絡(luò)結(jié)構(gòu)中,構(gòu)建得到一個(gè)新型半人工PSⅡ/納米管狀I(lǐng)TO薄膜復(fù)合光陽極體系。納米管狀I(lǐng)TO薄膜材料在電極表面的修飾有效提高了 PSⅡ蛋白的負(fù)載量;ITO材料的納米管結(jié)構(gòu)及其優(yōu)越的光學(xué)和電學(xué)性能有效增強(qiáng)了電子在光陽極體系中的傳遞效率。將該復(fù)合光陽極體系用于太陽能的轉(zhuǎn)化和電能的產(chǎn)生,在模擬太陽光的白光照射下產(chǎn)生了較大的光電流響應(yīng),具有出色的光電轉(zhuǎn)化效率和光電化學(xué)性能。3、聚吡咯/硅納米纖維復(fù)合材料:基于天然纖維素表面的羥基和硅烷的共價(jià)作用,通過溶膠-凝膠法制備二氧化硅凝膠薄膜/纖維素復(fù)合材料,在空氣中煅燒得到二氧化硅納米管材料,再通過鎂熱還原反應(yīng)將二氧化硅納米管還原為硅晶體納米顆粒組成的硅納米纖維材料,隨后用原位化學(xué)聚合法將吸附在硅納米纖維表面的吡咯單體聚合,得到的聚吡咯納米顆粒均勻且完整包覆在硅納米纖維表面。聚吡咯/硅納米纖維復(fù)合材料復(fù)制了纖維素模板的三維多孔網(wǎng)絡(luò)結(jié)構(gòu)。將該復(fù)合材料用作鋰離子電池負(fù)極的活性材料,在充放電過程中材料結(jié)構(gòu)的完整性以及硅的晶體相得以很好保持,電池顯示了良好的可逆比容量、循環(huán)穩(wěn)定性和倍率性能。4、釩摻雜的二氧化鈥復(fù)合材料:基于天然纖維素表面的羥基和鈦醇鹽、釩醇鹽的共價(jià)作用,通過表面溶膠-凝膠的方法在濾紙納米纖維表面層層自組裝二氧化鈥/五氧化二釩復(fù)合凝膠薄膜,再置于空氣中分別通過火焰燃燒或煅燒的方法除去纖維素模板,得到一系列釩摻雜的二氧化鈦復(fù)合材料。其中,釩摻雜比例可以通過釩醇鹽和鈦醇鹽的摩爾比來控制。和煅燒法相比,火焰燃燒法能在一定程度上抑制二氧化鈦和五氧化二釩的相分離以及晶體顆粒在相轉(zhuǎn)變過程中的聚集和生長(zhǎng),促進(jìn)了釩離子在二氧化鈦晶格中的摻雜,制備得到精確復(fù)制了纖維素模板多層級(jí)結(jié)構(gòu)的釩摻雜金紅石型二氧化鈦復(fù)合納米纖維材料,組成纖維的納米顆粒尺寸較小且均勻。此外,進(jìn)一步研究了用煅燒法制備得到的二氧化鈦材料的相轉(zhuǎn)變,結(jié)果表明釩離子在二氧化鈦晶格中的摻雜以及基于天然纖維素為模板的層層自組裝制備方法能夠顯著降低二氧化鈦的相轉(zhuǎn)變溫度,在600℃的較低煅燒溫度下初始的銳鈦礦型二氧化鈦即可完全轉(zhuǎn)變?yōu)榻鸺t石型的二氧化鈦。
[Abstract]:In twenty-first Century, the rapid development of industry with huge energy consumption, mankind is faced with fossil fuels and other non renewable energy exhausting, followed by a series of serious environmental problems. Therefore, the development of new clean energy materials and make full use of solar energy and other renewable energy imminent. There are a lot of biomass resources in nature among them, the natural cellulose material with abundant yield, good biodegradability, biocompatibility, flexibility and mechanical strength, and cellulose molecules between the complex interaction gives its unique three-dimensional multi-level structure, porous structure and large surface area. Therefore, natural cellulose is an excellent biological activity of hydroxyl groups on the surface of the template. Rich variety of object materials might self assemble into cellulose surface. This paper is based on natural cellulose substances ( No ash) quantitative filter paper as the template, the self-assembly of various guest molecules on the surface of oxide cellulose single nanofiber, followed by different ways to prepare postprocessing, combined with a new type of cellulose template structure and unique object material specific functions in functional nano materials, can be used in the research field of photoelectric transformation system and lithium ion batteries, the main contents are as follows: 1, photosystem II / two porous holmium oxide nanotube network light anode system: the covalent interaction of surface hydroxyl groups of cellulose and titanium alkoxide based on titanium dioxide gel film in the surface of nanometer fiber filter paper of self-assembly, calcined in air to get rid of the cellulose template obtained an exact copy of the anatase two holmium oxide nanotubes template multilayer porous network structure. The two holmium oxide materials on the surface of the electrode substrate Modified. Then, the purified from spinach leaves with water splitting function of photosystem II (PS II) protein assembled on the electrode, successfully constructed a novel protein / semiconductor composite anode system. Because the bionic planar electrode was titanium dioxide nanotube material optimization, protein can improve the loading capacity of the electrode surface. In addition, synergistic interaction between PS protein and titanium dioxide, transfer to simulate electron transfer in Photosynthesis "Z" chain in electronic PS II protein and titanium dioxide levels. The complex light anode system has good photoelectrochemical properties. It used for the conversion of solar energy and electric power generation, light current high white light under simulated sunlight, with a certain external to drive LED lights under the condition of.2, PS / nano tubular indium tin oxide film is light anode body assembly Department of surface hydroxyl cellulose and indium alkoxides based on covalent interactions for tin alkoxide preparing indium tin oxide (ITO) gel film / cellulose composite material, calcined in air to get rid of cellulose, can obtain nano tubular ITO thin film structure of multilayer porous network to accurately reproduce the cellulose template. The material of visible light transmittance, conductivity of the indium tin make material has high adhesion. The conductive colloidal gold achieve modification of planar electrode on the electrode substrate using nano tubular ITO film material, and the PS II protein assembled in the porous network structure of ITO thin film materials, construct a new semi manual PS II / ITO nano tubular composite optical anode system. Nano tubular ITO films can effectively improve the load capacity of PS II protein in the surface of the electrode; ITO nanotube structure material and its superior The optical and electrical properties and enhance the transmission efficiency in the electronic light anode system. The composite light anode system for solar energy conversion and power generation, in the light irradiation of simulated sunlight caused by the photocurrent response is larger, with excellent photoelectric conversion efficiency and photoelectrochemical properties of PPy /.3. Silicon nano fiber composite materials: covalent interactions of natural cellulose based on surface hydroxyl groups and silane, was prepared by sol-gel silica gel film / cellulose composite material, calcined in air to obtain silica nanotubes, by magnesiothermic reduction reaction of silica nanotubes reduced to silicon nano crystal silicon nano fiber material particles, then the adsorption on the surface of silicon nano fiber polymerization of pyrrole monomer in situ chemical polymerization of polypyrrole nanoparticles to obtain uniform and complete package Coating on the surface of the fibers. The silicon nano polypyrrole / silicon nano fiber composite material copied cellulose template three-dimensional porous network structure. The composite material is used as the active material of lithium ion battery cathode material structure, in the process of charge and discharge and the integrity of the silicon crystal phase can be maintained, the battery showed good reversible capacity, cycle stability and rate performance of.4 two, holmium oxide composite vanadium doping: natural cellulose hydroxyl on the surface of titanium alkoxide and based on covalent effects of vanadium alkoxide, by surface sol-gel nano fiber filter in surface layer by layer self-assembly of two / five of two vanadium holmium oxide composite gel film, then in the air by flame method or calcined to remove the cellulose template, obtained a series of vanadium doped TiO2 composite materials. Among them, the proportion of vanadium doped by vanadium alkoxide And the mole ratio of titanium alkoxide control. Compared with the calcination method, phase separation flame combustion method can to some extent inhibit the oxidation of two titanium dioxide and five vanadium and crystal particles in the phase transition and aggregation in the process of growth, promoted vanadium doping ions in TiO2 lattice, prepared to accurately reproduce vanadium doping rutile TiO2 composite nano fiber material structure of multi grade cellulose fiber template, nano particle size is small and uniform. In addition, further study of the phase transformation of calcined TiO2 materials were prepared, the results showed that the doped vanadium ion in TiO2 lattice and layers based on natural cellulose template self-assembly preparation method can significantly reduce the phase transition temperature of TiO2 anatase TiO2 can be calcined at low initial temperature of 600 DEG C under complete turn It turns into rutile titanium dioxide.

【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O636.11;TM912

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 ;Fast Isolation of Highly Active Photosystem II Core Complexes from Spinach[J];Journal of Integrative Plant Biology;2010年09期

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本文編號(hào)：1490246