本文選題：CdSe量子點(diǎn) + 雙金屬離子摻雜��； 參考：《江蘇大學(xué)》2017年博士論文

【摘要】：隨著工業(yè)化程度的日益提高,越來(lái)越多的有機(jī)物被投入到現(xiàn)代生產(chǎn)和生活中,造成水環(huán)境中出現(xiàn)大量有機(jī)物殘留,這些有機(jī)物殘留對(duì)環(huán)境造成的污染日益加劇。近年來(lái),利用太陽(yáng)能光降解有機(jī)污染物的綠色光催化技術(shù)引起了科研工作者的廣泛關(guān)注,如何獲得高性能低成本的半導(dǎo)體光催化材料已然是光催化技術(shù)發(fā)展的關(guān)鍵問(wèn)題。量子點(diǎn)材料由于具有尺寸小、比表面積大、光響應(yīng)能力強(qiáng)、獨(dú)特的電子態(tài)和光學(xué)吸收性能等優(yōu)勢(shì),已成為光催化領(lǐng)域新興的研究熱點(diǎn)。同時(shí),硒化鎘(CdSe)半導(dǎo)體光催化材料具有合適的禁帶寬度,獨(dú)特的晶體結(jié)構(gòu)特征以及在可見(jiàn)光下顯示出優(yōu)異的光降解有機(jī)污染物性能的優(yōu)勢(shì),具有較高的研究?jī)r(jià)值。因此,結(jié)合量子點(diǎn)材料和CdSe半導(dǎo)體的多重優(yōu)勢(shì),選擇CdSe量子點(diǎn)作為光催化材料來(lái)降解環(huán)境廢水中有機(jī)污染物具有很好的應(yīng)用前景。但是由于單一 CdSe量子點(diǎn)材料存在著一些缺陷嚴(yán)重制約了其應(yīng)用范圍,例如:易于團(tuán)聚,抗光腐蝕性差,穩(wěn)定性較低等。為了克服CdSe量子點(diǎn)材料的這些缺點(diǎn),本論文采取多種修飾技術(shù)對(duì)其進(jìn)行改性,如離子摻雜技術(shù)對(duì)其進(jìn)行修飾,克服CdSe量子點(diǎn)光生電子和空穴易復(fù)合的問(wèn)題;結(jié)合貴金屬納米粒子等離子體共振效應(yīng),在提高光生電子與空穴的分離效率的同時(shí)還提高了光能利用率;選擇合適載體制備負(fù)載-復(fù)合型多組分光催化材料,解決CdSe量子點(diǎn)材料吸附能力差、穩(wěn)定性不高等問(wèn)題。同時(shí),通過(guò)多種分析測(cè)試方法,系統(tǒng)地研究了改性CdSe量子點(diǎn)光催化材料的物化特性以及光降解環(huán)境中有機(jī)污染物的反應(yīng)機(jī)理。具體研究工作如下:(1)采用軟模板法合成方案,以十六烷基三甲基氯化銨為表面活性劑,經(jīng)過(guò)簡(jiǎn)單水浴回流過(guò)程,合成了 CdSe量子點(diǎn)囊泡狀分級(jí)結(jié)構(gòu)光催化材料。根據(jù)TEM等測(cè)試手段分析了囊泡狀結(jié)構(gòu)的成型機(jī)制。經(jīng)過(guò)XRD、TEM、TGA等分析測(cè)試手段對(duì)量子點(diǎn)光催化材料的物化性質(zhì)進(jìn)行表征。相對(duì)于粒子結(jié)構(gòu)CdSe量子點(diǎn)材料,該結(jié)構(gòu)具有較大的比表面積和豐富的孔道結(jié)構(gòu)。降解實(shí)驗(yàn)結(jié)果表明,CdSe量子點(diǎn)囊泡狀分級(jí)結(jié)構(gòu)光催化材料對(duì)鹽酸四環(huán)素(Tetracycline hydrochloride,TC·HCl)展現(xiàn)出優(yōu)異的光催化降解活性。通過(guò)活性物種捕獲實(shí)驗(yàn),分析其光催化降解反應(yīng)機(jī)理。通過(guò)循環(huán)降解實(shí)驗(yàn),考察催化劑的循環(huán)利用率。(2)采用簡(jiǎn)單的一步水熱法,以3-巰基丙酸為修飾劑,合成了雙離子共摻雜CdSe量子點(diǎn)光催化材料。通過(guò)調(diào)節(jié)離子摻雜種類(lèi)以及摻雜比例,制備不同的金屬離子摻雜CdSe量子點(diǎn)光催化材料。TEM研究發(fā)現(xiàn),制備的金屬離子摻雜CdSe量子點(diǎn)材料,納米粒子尺寸均一,呈球狀分布,納米粒子平均尺寸約為8 nm。UV-vis DRS表明制備的所有離子摻雜CdSe量子點(diǎn)樣品在可見(jiàn)光范圍內(nèi)均具有很強(qiáng)的光響應(yīng)能力,相比于單一 CdSe量子點(diǎn)材料,金屬離子摻雜CdSe量子點(diǎn)材料帶隙值降低。同時(shí),以TC·HCl溶液為目標(biāo)物廢水、詳細(xì)探討了光催化降解機(jī)理并研究不同條件對(duì)光催化降解性能的影響。通過(guò)考察摻雜金屬離子的種類(lèi)及比例,得出3%Co-4%K/CdSe量子點(diǎn)材料具有最佳的光催化性能。在30min內(nèi),其對(duì)TC·HCl的降解率達(dá)到78.4%。通過(guò)對(duì)降解不同時(shí)間的溶液質(zhì)譜進(jìn)行測(cè)定,分析了 TC·HCl降解的中間過(guò)程。(3)采用簡(jiǎn)單的水熱法,將Al2Ti05陶瓷材料與CdSe量子點(diǎn)復(fù)合,構(gòu)建異質(zhì)結(jié)復(fù)合材料。在此基礎(chǔ)上,制備了納米Ag粒子修飾CdSe量子點(diǎn)負(fù)載Al2Ti05復(fù)合光催化劑。利用XRD、TEM、電化學(xué)等多種分析測(cè)試手段對(duì)光催化劑進(jìn)行物化性質(zhì)表征。以典型的亞甲基藍(lán)染料(Methylene blue,MB)溶液為降解目標(biāo)物驗(yàn)證制備的復(fù)合光催化劑的光催化活性�？疾炝� Al2Ti05的引入比例對(duì)復(fù)合材料光催化性能的影響。通過(guò)活性物種捕獲實(shí)驗(yàn),分析了光催化降解過(guò)程中起主要作用的活性因子并詳細(xì)探討了光催化降解有機(jī)染料的機(jī)理。(4)以箭竹葉為生物原材料,采用無(wú)氧炭化法制備蜂窩管狀竹葉生物炭。通過(guò)XRD、SEM、N2吸脫附等多種不同分析測(cè)試手段對(duì)竹葉生物炭的物化性能進(jìn)行表征。以竹葉生物炭為載體,可溶性金屬鹽溶液為金屬源,硼氫化鈉為還原劑,原位生長(zhǎng)法與水熱法相結(jié)合,成功制備了金屬離子摻雜CdSe量子點(diǎn)負(fù)載竹葉生物炭復(fù)合光催化劑。通過(guò)光催化降解TC·HCl溶液驗(yàn)證其光催化活性�？疾焐锾考尤肓繉�(duì)所制備的復(fù)合材料性能的影響規(guī)律;探究了金屬離子摻雜比例對(duì)所制備的材料性能的影響規(guī)律。最終得出結(jié)論,生物炭加入量為35 wt%、Co離子摻雜比例為3%-7%時(shí)最佳。另外,通過(guò)多種實(shí)驗(yàn)手段相結(jié)合探討了光催化降解抗生素廢水的反應(yīng)機(jī)理,揭示了其提高光催化性能的本質(zhì)原因。
[Abstract]:With the increasing degree of industrialization, more and more organic compounds have been put into modern production and life, resulting in a large number of organic residues in the water environment, and the pollution of these organic residues to the environment is aggravated. In recent years, the green photocatalytic technology for the use of solar energy to degrade organic contaminants has caused scientific research workers. Widely concerned, how to obtain high performance and low cost semiconductor photocatalytic materials has been the key problem in the development of photocatalytic technology. Quantum dots have become a new research hotspot in the field of photocatalysis because of their advantages of small size, large specific surface area, strong light response ability, unique electronic state and optical absorption properties. Cadmium (CdSe) semiconductor photocatalyst has a suitable band gap, unique crystal structure characteristics and excellent advantages of showing excellent photocatalytic degradation of organic pollutants in visible light. Therefore, combining quantum dots and CdSe semiconductors, CdSe quantum dots are selected as photocatalytic materials. The degradation of organic pollutants in environmental wastewater has a good application prospect. However, there are some defects in the single CdSe quantum dot material which seriously restrict its application, such as easy reunion, poor anti light corrosion and low stability. In order to overcome these shortcomings of CdSe quantum dots, this paper adopts a variety of modification techniques to it Modification, such as the modification of ion doping technology, overcomes the problem that the photoelectrons and holes of the CdSe quantum dots are easily compound, and the efficiency of optical electron and hole separation is enhanced with the plasma resonance effect of noble metal nanoparticles. Catalytic materials can solve the problem of poor adsorption capacity and low stability of CdSe quantum dots. At the same time, the physicochemical properties of the modified CdSe quantum dots photocatalytic materials and the reaction mechanism of organic pollutants in the photodegradation environment are systematically studied by a variety of analytical testing methods. The specific research work is as follows: (1) a soft template synthesis scheme is used. With sixteen alkyl three methyl ammonium chloride as surface active agent, a CdSe quantum dot vesicular structured photocatalytic material was synthesized through a simple water bath reflux process. The forming mechanism of the vesicular structure was analyzed by TEM and other testing methods. The physicochemical properties of the quantum dots photocatalyst were characterized by XRD, TEM, TGA and other analytical methods. Compared with the particle structure CdSe quantum dots, the structure has a large specific surface area and rich pore structure. The results of degradation experiments show that the photocatalytic activity of CdSe quantum dots vesicular graded structure photocatalytic materials to Tetracycline hydrochloride (TC. HCl) is superior to the photocatalytic degradation activity. The reaction mechanism of photocatalytic degradation was analyzed. The cyclic utilization rate of the catalyst was investigated by cyclic degradation. (2) a simple one step hydrothermal method was used to synthesize a double ion Co doped CdSe quantum dot photocatalyst with 3- mercapto propionic acid as the modifier. The study of CdSe quantum dots photocatalytic material.TEM found that the prepared metal ions doped CdSe quantum dots were uniform in size and spherical distribution. The average size of the nanoparticles was about 8 nm.UV-vis DRS, indicating that all the ions doped CdSe quantum dots have strong light response ability in the range of visible light, compared with those in the visible light range. The band gap value of metal ions doped CdSe quantum dots is reduced by single CdSe quantum dots. At the same time, the photocatalytic degradation mechanism and the effect of different conditions on photocatalytic degradation are investigated in detail with TC / HCl solution as target wastewater. By investigating the species and proportion of doped metal ions, the 3%Co-4%K/CdSe quantum dots materials are obtained. With the best photocatalytic performance. In 30min, the degradation rate of TC HCl was reached to 78.4%. by the determination of the solution mass spectra at different time. The intermediate process of TC HCl degradation was analyzed. (3) a simple hydrothermal method was used to combine the Al2Ti05 ceramics with the CdSe quantum dots to construct the heterojunction composite. On this basis, the preparation was made. Nano Ag particles modified CdSe quantum dots loaded with Al2Ti05 composite photocatalyst. The physicochemical properties of photocatalyst were characterized by XRD, TEM, electrochemistry and other analytical testing methods. The photocatalytic activity of the composite photocatalyst prepared with the typical methylene blue (Methylene blue, MB) solution as the degradation target was investigated. The effect of the introduction ratio on the photocatalytic properties of composite materials. Through the experiment of active species capture, the active factors which play the main role in the process of photocatalytic degradation were analyzed and the mechanism of photocatalytic degradation of organic dyes was discussed in detail. (4) honeycomb shaped bamboo leaf biological charcoal was prepared by oxygen free carbonization by using arrows bamboo leaves as biological raw materials. The physicochemical properties of bamboo leaf biological carbon were characterized by XRD, SEM and N2 desorption. The bamboo leaf biological charcoal was used as the carrier, the soluble metal salt solution was used as the metal source, the sodium borohydride was the reductant, and the in situ growth method was combined with the hydrothermal method to prepare the gold ion doped CdSe quantum dots loaded bamboo leaf bio carbon composite successfully. Photocatalyst. The photocatalytic activity was verified by photocatalytic degradation of TC / HCl solution. The effects of carbon content on the properties of the composites were investigated, and the influence of the proportion of metal ions on the properties of the prepared materials was explored. Finally, it was concluded that the amount of bio carbon added to 35 wt% and the proportion of Co ion doping at 3%-7% was 3%-7%. In addition, the reaction mechanism of photocatalytic degradation of antibiotic wastewater was discussed through a variety of experimental methods, and the essential reasons for improving the photocatalytic performance were revealed.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：X703;O643.36;O644.1

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