本文選題：煤炭 + 煤瀝青��； 參考：《大連理工大學(xué)》2015年博士論文

【摘要】：以熒光碳點為代表的零維納米材料是目前研究非常廣泛的一類新型功能材料,其可控制備是當(dāng)今納米材料研究領(lǐng)域的前沿和熱點之一。如何選用優(yōu)質(zhì)、廉價的碳源前驅(qū)體,并在制備過程中實現(xiàn)對熒光碳點結(jié)構(gòu)和組成的準確控制,進而調(diào)變其本征性能,對于深入理解物質(zhì)結(jié)構(gòu)與性質(zhì)的關(guān)聯(lián)、人工設(shè)計合成新型功能材料具有重要意義。本文以煤炭及其衍生產(chǎn)物為碳源,針對不同原料的結(jié)構(gòu)和性質(zhì),合理設(shè)計工藝路線,制備具有獨特?zé)晒庑阅艿拿夯键c,主要研究結(jié)果如下： 以煤炭為碳源前驅(qū)體,采用硝酸氧化法制備了具有藍色熒光的煤基碳點,系統(tǒng)研究了碳源種類、煤巖結(jié)構(gòu)、預(yù)炭化處理和氧化條件對煤基碳點收率、結(jié)構(gòu)和性質(zhì)的影響。結(jié)果表明高煤化度的煤炭和絲質(zhì)組分有利于提高煤基碳點的量子產(chǎn)率,通過控制預(yù)炭化溫度,可實現(xiàn)煤基碳點平均粒徑從1.9nm到3.1nm范圍內(nèi)的精確調(diào)變。煤基碳點表面含氧官能團的種類和數(shù)量可通過后續(xù)還原處理來調(diào)控,經(jīng)硼氫化鈉還原后的煤基碳點的量子產(chǎn)率從1.02%大幅增大到8.80%。還原后的煤基碳點對銅離子具有特異性的熒光響應(yīng),可作為熒光探針用來監(jiān)測水體中的銅離子,檢測限可達2.0nM。 以煤炭為碳源前驅(qū)體,采用電化學(xué)法制備了具有藍色熒光的煤基碳點,考察了碳源種類,以及在電解液體系中引入含氮助劑對煤基碳點收率、結(jié)構(gòu)和熒光性質(zhì)的影響,并詳細研究了煤基碳點在高濃度條件下的聚集狀態(tài)和熒光變化規(guī)律。結(jié)果顯示煤基碳點的收率遠大于石墨基碳點,電解液中引入含氮助劑可實現(xiàn)氮摻雜煤基碳點的制備,煤基碳點在高濃度條件下熒光光譜紅移。氮摻雜后的煤基碳點具有優(yōu)異的催化性能,在電催化氧還原反應(yīng)時表現(xiàn)出媲美商業(yè)Pt/C催化劑的催化活性,并且具有更好的穩(wěn)定性和更強的抵御甲醇穿透效應(yīng)的能力。 以煤瀝青為碳源前驅(qū)體,采用模板輔助法制備了具有藍綠色熒光的煤瀝青基碳點。碳點制備過程受到模板劑的納米反應(yīng)空間的限域效應(yīng)影響,所得熒光碳點粒徑非常均勻,平均尺寸為2.2nm。采用不同種類的有機修飾劑鍵連在瀝青基碳點表面,不但極大地提高了碳點的量子產(chǎn)率,而且也改善了碳點與周圍環(huán)境介質(zhì)之間的相親互溶性。乙二胺修飾后的碳點可均勻分散在有機玻璃固體介質(zhì)中,即使在很高的濃度條件下也不易產(chǎn)生團聚,造成熒光猝滅。用這種碳點復(fù)合物作為光轉(zhuǎn)化涂層,可成功將InGaN二極管的紫外光轉(zhuǎn)變成藍光。
[Abstract]:Zero-dimensional nanomaterials, represented by fluorescent carbon dots, are a new type of functional materials which are widely studied at present, and their controllable devices are one of the frontier and hot spots in the research field of nanomaterials. How to select the high quality and cheap carbon precursor, and how to control the structure and composition of the fluorescent carbon point accurately in the preparation process, and then adjust its intrinsic properties, which is helpful to understand the relationship between the structure and properties of the substance. It is of great significance to design and synthesize new functional materials. In this paper, coal and its derived products are used as carbon sources, according to the structure and properties of different raw materials, the technological route is designed rationally to prepare coal-based carbon points with unique fluorescence properties. The main results are as follows: coal is used as precursor of carbon source. Coal based carbon spots with blue fluorescence were prepared by nitric acid oxidation. The effects of carbon source types, coal rock structure, pre-carbonization treatment and oxidation conditions on the yield, structure and properties of coal based carbon points were systematically studied. The results show that the coal and silk components with high coalification degree can improve the quantum yield of coal-based carbon dots. By controlling the precarbonization temperature, the average particle size of coal-based carbon points can be accurately adjusted from 1.9nm to 3.1nm. The types and the number of oxygen-containing functional groups on the surface of coal-based carbon spots can be controlled by subsequent reduction treatment. The quantum yield of coal-based carbon dots reduced by sodium borohydride has been increased from 1.02% to 8.80%. The reduced coal-based carbon spots have a specific fluorescence response to copper ions and can be used as a fluorescence probe to monitor copper ions in water with a detection limit of up to 2.0 nm. Coal based carbon spots with blue fluorescence were prepared by electrochemical method using coal as carbon precursor. The effects of carbon sources and nitrogen-containing additives on the yield, structure and fluorescence properties of coal based carbon spots were investigated. The aggregation state and fluorescence variation of coal-based carbon point at high concentration were studied in detail. The results show that the yield of coal-based carbon point is much higher than that of graphite-based carbon point. The nitrogen-containing additive can be used to prepare the nitrogen-doped coal-based carbon point, and the fluorescence spectrum of coal-based carbon point can shift red under the condition of high concentration. The nitrogen-doped coal-based carbon spots have excellent catalytic performance and exhibit catalytic activity comparable to those of commercial Pt / C catalysts in the electrocatalytic oxygen reduction reaction. They also have better stability and stronger resistance to methanol penetration. Coal pitch based carbon spots with blue-green fluorescence were prepared by template assisted method using coal pitch as carbon precursor. The preparation process of carbon points is affected by the limiting effect of the nano-reaction space of the template. The size of the fluorescent carbon points is very uniform and the average size is 2.2 nm. Using different kinds of organic modifiers to bond on the surface of asphalten-based carbon points not only greatly improves the quantum yield of carbon dots, but also improves the compatibility and solubility between carbon points and surrounding media. The carbon points modified by ethylenediamine can be uniformly dispersed in the solid medium of plexiglass, and it is not easy to produce agglomeration even at very high concentration, which results in fluorescence quenching. The UV light of the InGaN diode can be converted into blue light successfully by using the carbon dot complex as the photoconversion coating.
【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】：TQ127.11;TQ536

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本文編號：2011338