發(fā)布時(shí)間：2018-07-13 11:40

【摘要】：隨著現(xiàn)代工業(yè)的發(fā)展,有機(jī)污染物的大量排放嚴(yán)重威脅到人類(lèi)健康和環(huán)境安全。如何高效、經(jīng)濟(jì)地處理這些環(huán)境問(wèn)題,已成為科研工作者面臨的重要課題。在現(xiàn)有的各種污染物處理技術(shù)中,作為新型高級(jí)氧化技術(shù)的光催化技術(shù),因其具備操作簡(jiǎn)單、效率高、綠色、安全等優(yōu)點(diǎn),可用于解決上述問(wèn)題。氧化鉍半導(dǎo)體催化材料,因其具有良好的介電、光學(xué)和離子導(dǎo)電性能,被認(rèn)為是極具應(yīng)用前景的可見(jiàn)光光催化材料。本論文以環(huán)境水污染治理為研究背景,重點(diǎn)對(duì)氧化鉍展開(kāi)改性研究以提高其可見(jiàn)光光催化活性。主要研究?jī)?nèi)容和結(jié)果包括:(1)采用第一性原理方法,研究了Bi_2O_3晶體結(jié)構(gòu)、電子結(jié)構(gòu)與其光催化性能之間的關(guān)系,探討了晶型與電子結(jié)構(gòu)間的協(xié)同效應(yīng)對(duì)氧化鉍可見(jiàn)光催化性能的影響。利用MS軟件的CASTEP模塊對(duì)α-Bi_2O_3、β-Bi_2O_3、γ-Bi_2O_3、δ-Bi_2O_3的幾何結(jié)構(gòu)、能帶結(jié)構(gòu)、電子態(tài)密度和光學(xué)性質(zhì)進(jìn)行了理論計(jì)算。結(jié)果表明α-Bi_2O_3和β-Bi_2O_3為層狀結(jié)構(gòu),γ-Bi_2O_3和δ-Bi_2O_3為網(wǎng)狀交聯(lián)結(jié)構(gòu),其中δ-Bi_2O_3交聯(lián)程度較高,呈現(xiàn)導(dǎo)體特性。各晶相的導(dǎo)帶主要由Bi 6p軌道構(gòu)成,價(jià)帶主要由O 2p軌道構(gòu)成。α-Bi_2O_3和β-Bi_2O_3的吸收帶邊均延伸到了可見(jiàn)光區(qū),因此它們具有可見(jiàn)光催化活性。γ-Bi_2O_3和δ-Bi_2O_3的吸收帶邊均延伸擴(kuò)展到了紅外光區(qū),因此它們具一定的紅外光激發(fā)特征。這些理論計(jì)算結(jié)果,為新型Bi_2O_3光催化材料的設(shè)計(jì)和應(yīng)用提供了重要的理論指導(dǎo)。(2)采用理論設(shè)計(jì)加實(shí)驗(yàn)驗(yàn)證的方法,通過(guò)聚丙烯酰胺溶膠凝膠法制備得到了鐠摻雜α-Bi_2O_3的新型可見(jiàn)光光催化材料。通過(guò)第一性原理方法對(duì)Pr摻雜α-Bi_2O_3體系進(jìn)行了理論計(jì)算研究。計(jì)算結(jié)果表明Pr摻雜α-Bi_2O_3后,Pr的4f軌道發(fā)生分裂,高能軌道進(jìn)入導(dǎo)帶并與O 2p、Bi 6p軌道發(fā)生作用,低能軌道進(jìn)入禁帶形成新的雜質(zhì)能級(jí),從而使得禁帶寬度減小,光吸收帶邊發(fā)生紅移,計(jì)算結(jié)果表明Pr摻雜可有效提高α-Bi_2O_3的可見(jiàn)光催化活性。以理論計(jì)算結(jié)果為設(shè)計(jì)指導(dǎo),制備得到α-Bi_2O_3和Pr摻雜α-Bi_2O_3的納米催化劑顆粒。通過(guò)可見(jiàn)光催化降解甲基橙對(duì)樣品的可見(jiàn)光催化活性進(jìn)行了評(píng)價(jià),實(shí)驗(yàn)結(jié)果與計(jì)算結(jié)果相一致,Pr摻雜α-Bi_2O_3表現(xiàn)出了更高的可見(jiàn)光催化活性,這為新型高效可見(jiàn)光催化材料的研發(fā)和改性設(shè)計(jì)提供了新的研究思路。(3)采用簡(jiǎn)易的揮發(fā)法制備得到β-Bi_2O_3/石墨烯復(fù)合材料,通過(guò)可見(jiàn)光催化降解亞甲基藍(lán)對(duì)樣品的可見(jiàn)光催化活性進(jìn)行了評(píng)價(jià)。結(jié)果表明與β-Bi_2O_3相比,β-Bi_2O_3/石墨烯復(fù)合材料表現(xiàn)出了更高的可見(jiàn)光催化活性。石墨烯的高效電子捕獲和傳導(dǎo)能力,可有效促進(jìn)光生電子-空穴對(duì)分離,將光生電子快速轉(zhuǎn)移至石墨烯片層的表面,使更多的光生電荷參與到光催化反應(yīng)中,從而提高光催化活性。(4)采用化學(xué)氧化聚合法在乙二醇溶液中,制備得到PANI/β-Bi_2O_3復(fù)合光催化材料,通過(guò)可見(jiàn)光催化降解酸性橙7對(duì)其光催化活性進(jìn)行了評(píng)價(jià)。結(jié)果表明,聚苯胺含量為5%時(shí),復(fù)合物的光催化活性最高。與β-Bi_2O_3納米顆粒相比,PANI/β-Bi_2O_3復(fù)合物表現(xiàn)出了更高的光催化性能,解釋了PANI/β-Bi_2O_3復(fù)合物的光催化機(jī)理。聚苯胺是優(yōu)良的空穴接受體,可有效分離光生電荷,降低光生電子-空穴對(duì)的復(fù)合,從而提高β-Bi_2O_3的光催化活性。(5)通過(guò)降解羅丹明B對(duì)β-Bi_2O_3納米顆粒的超聲催化活性及其超聲耦合光催化協(xié)同作用進(jìn)行了研究。結(jié)果表明β-Bi_2O_3納米顆粒具有良好的超聲催化活性。系統(tǒng)研究了超聲頻率(f),反應(yīng)溫度(T),催化劑投加量(Ccatalyst),羅丹明B初始濃度(CRh B)等實(shí)驗(yàn)參數(shù)對(duì)超聲催化性能的影響,結(jié)果發(fā)現(xiàn)其超聲催化降解羅丹明B的最佳實(shí)驗(yàn)條件為:f=60 k Hz,T=40 oC,Ccatalyst=3 g·L-1,and CRhB=5 mg·L-1,超聲催化反應(yīng)90 min,對(duì)羅丹明B的降解率為98.7%。由實(shí)驗(yàn)結(jié)果可知,·OH是起到超聲催化降解作用的主要活性基團(tuán)。超聲光催化活性結(jié)果表明超聲耦合光催化協(xié)同作用,能有效提高β-Bi_2O_3納米顆粒對(duì)有機(jī)染料的催化降解能力。
[Abstract]:With the development of modern industry, the mass emission of organic pollutants seriously threatens human health and environmental safety. How to deal with these environmental problems efficiently and economically has become an important issue for researchers. In the existing various pollutants treatment technologies, photocatalytic technology, as a new advanced oxidation technology, has been used as a result of it. Simple operation, high efficiency, green, safety and so on, can be used to solve the above problems. Bismuth oxide semiconductor catalytic material is considered to be a promising visible light photocatalytic material because of its good dielectric, optical and ionic conductivity. This paper focuses on the modification of bismuth oxide in the environment of environmental water pollution treatment. The main research contents and results are as follows: (1) the relationship between the structure of Bi_2O_3 crystal, the electronic structure and the photocatalytic properties of the crystal was studied by the first principle method, and the effect of the synergistic effect between the crystal and the electronic structure on the visible photocatalytic activity of bismuth oxide was investigated. The CASTE of the MS software was used. The P module has a theoretical calculation of the geometric structure, band structure, electron density and optical properties of alpha -Bi_2O_3, beta -Bi_2O_3, gamma -Bi_2O_3, and delta -Bi_2O_3. The results show that alpha -Bi_2O_3 and beta -Bi_2O_3 are layered structure, gamma -Bi_2O_3 and delta -Bi_2O_3 are network crosslinking structures, and delta -Bi_2O_3 has high crosslinking degree, showing conductor properties. The band is mainly composed of Bi 6p orbitals. The valence band is mainly composed of O 2p orbitals. The absorption band edges of alpha and beta -Bi_2O_3 are extended to the visible light region, so they have visible photocatalytic activity. The absorption band edges of the gamma and delta -Bi_2O_3 are extended to the infrared light region, so they have certain infrared excitation characteristics. These theories The calculation results provide important theoretical guidance for the design and application of the new Bi_2O_3 photocatalyst. (2) a new visible light photocatalytic material with praseodymium doped alpha -Bi_2O_3 was prepared by the method of theoretical design and experimental verification by the method of polyacrylamide sol gel. The first principle method was used for the Pr doped alpha -Bi_2O_3 system. Theoretical calculation is carried out. The results show that after the Pr doping of alpha -Bi_2O_3, the 4f orbit of Pr occurs split, the high energy orbit enters the guide band and acts with the O 2p, Bi 6p orbit, and the low energy orbit enters the forbidden band to form a new impurity level, which makes the band gap decrease and the light absorption band edge occurs red shift. The calculation results show that Pr doping can be effectively proposed. The visible photocatalytic activity of high alpha -Bi_2O_3 was observed. Based on the theoretical calculation, the nano catalyst particles of alpha -Bi_2O_3 and Pr doped alpha -Bi_2O_3 were prepared. The visible photocatalytic activity of the methyl orange was evaluated by visible light catalytic degradation of methyl orange. The experimental results were in accordance with the calculated results, and the Pr doping of the alpha -Bi_2O_3 showed a better performance. High visible photocatalytic activity has provided new research ideas for the development and modification of new efficient visible photocatalytic materials. (3) a simple volatilization method was used to prepare beta -Bi_2O_3/ graphene composite. The visible photocatalytic activity of methylene blue was evaluated by visible light catalytic degradation of methylene blue. Compared with _2O_3, the beta -Bi_2O_3/ graphene composite exhibits higher visible photocatalytic activity. The high efficient electron capture and conduction ability of graphene can effectively promote the separation of photoelectron hole pair and transfer the photoelectron to the surface of the graphene layer, so that more photoelectric charges are involved in the photocatalytic reaction, thus increasing the light. (4) PANI/ beta -Bi_2O_3 composite photocatalyst was prepared by chemical oxidation polymerization in glycol solution. The photocatalytic activity of Acid Orange 7 was evaluated by photocatalytic degradation by visible light. The results showed that the photocatalytic activity of the compound was the highest when the content of polyaniline was 5%. Compared with the beta -Bi_2O_3 nanoparticles, PANI/ beta - Bi_2O_3 complexes exhibit higher photocatalytic properties and explain the photocatalytic mechanism of PANI/ beta -Bi_2O_3 complexes. Polyaniline is a good cavity acceptor, which can effectively separate light generated charge, reduce the recombination of photoelectron hole pair and improve the photocatalytic activity of beta -Bi_2O_3. (5) by degradation of Luo Danming B to beta -Bi_2O_3 nanoparticles The ultrasonic catalytic activity and the synergistic effect of ultrasonic coupling photocatalysis have been studied. The results show that the ultrasonic catalytic activity of the beta -Bi_2O_3 nanoparticles has good ultrasonic catalytic activity. The effects of ultrasonic frequency (f), reaction temperature (T), catalyst dosage (Ccatalyst), Luo Danming B initial concentration (CRh B) and other experimental parameters on ultrasonic catalytic performance are systematically studied. The best experimental conditions for the ultrasonic catalytic degradation of rhodamine B are: f=60 K Hz, T=40 oC, Ccatalyst=3 G. L-1, and CRhB=5 mg. The degradation rate of rhodamine is 90, and the degradation rate of rhodamine is known as the main active group for ultrasonic catalytic degradation. The synergistic effect of acoustic coupling photocatalysis can effectively improve the catalytic degradation ability of -Bi_2O_3 nanoparticles to organic dyes.
【學(xué)位授予單位】：蘭州理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O614.532;O643.36

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 張向華,李文釗,徐恒泳,劉鴻;分子篩在光催化中的應(yīng)用[J];化學(xué)進(jìn)展;2004年05期

2 阮新潮;王文靜;曾慶福;艾銳;;氟硅摻雜二氧化鈦催化劑的制備及光催化性能研究[J];湖北農(nóng)業(yè)科學(xué);2011年11期

3 馮潔,祝春蘭;納米ZnO的光催化性能及軟化學(xué)合成研究進(jìn)展[J];江西化工;2004年01期

4 安太成,顧浩飛,陳衛(wèi)國(guó),熊亞,朱錫海,劉國(guó)光;超聲協(xié)同納米TiO_2光催化降解活性染科的初步研究[J];中山大學(xué)學(xué)報(bào)(自然科學(xué)版);2001年05期

5 趙彥巧,張繼炎,陳吉祥;光催化反應(yīng)與應(yīng)用研究進(jìn)展[J];化學(xué)工業(yè)與工程;2004年03期

6 梁文俊;馬琳;李堅(jiān);;低溫等離子體-光催化聯(lián)合技術(shù)處理空氣污染物的研究進(jìn)展[J];工業(yè)催化;2011年12期

7 高甲友;納米二氧化鈦薄膜光催化降解性能的研究[J];安徽工業(yè)大學(xué)學(xué)報(bào)(自然科學(xué)版);2003年04期

8 張浩;任寶山;宋寶俊;牟興瑞;;空氣中微量苯的光催化降解研究[J];河北工業(yè)大學(xué)學(xué)報(bào);2006年05期

9 蔡乃才,王亞平,王鄂鳳,彭正合;光催化與光化學(xué)聯(lián)合降解苯胺[J];應(yīng)用化學(xué);1999年02期

10 尹飛;納米TiO_2光催化原理及其在環(huán)保領(lǐng)域的應(yīng)用[J];天津城市建設(shè)學(xué)院學(xué)報(bào);2002年04期

相關(guān)會(huì)議論文 前10條

1 黃建輝;陳建琴;吳丹丹;;納米鍺酸鎘的合成及其液相光催化性能研究[A];第六屆全國(guó)環(huán)境化學(xué)大會(huì)暨環(huán)境科學(xué)儀器與分析儀器展覽會(huì)摘要集[C];2011年

2 劉立明;何燕;黃應(yīng)平;;水體異味物質(zhì)2-MIB光催化降解機(jī)理研究[A];第十三屆全國(guó)太陽(yáng)能光化學(xué)與光催化學(xué)術(shù)會(huì)議學(xué)術(shù)論文集[C];2012年

3 陳春城;李?lèi)?趙玉寶;籍宏偉;馬萬(wàn)紅;趙進(jìn)才;;有機(jī)污染物光催化降解機(jī)理的同位素標(biāo)記研究[A];第十三屆全國(guó)太陽(yáng)能光化學(xué)與光催化學(xué)術(shù)會(huì)議學(xué)術(shù)論文集[C];2012年

4 何春;付鳳連;查長(zhǎng)虹;朱錫海;熊亞;;兼有光催化和非光催化雙重活性的Pt-TiO_2薄膜[A];第二屆全國(guó)環(huán)境化學(xué)學(xué)術(shù)報(bào)告會(huì)論文集[C];2004年

5 王建春;劉平;王世銘;韓煒;王占義;莊建東;付賢智;;Nation薄膜中ZnS單分散納米晶的水熱合成及其光催化性質(zhì)[A];第十三屆全國(guó)催化學(xué)術(shù)會(huì)議論文集[C];2006年

6 馬萬(wàn)紅;籍宏偉;陳春城;趙進(jìn)才;;光催化在有機(jī)物選擇性氧化中的應(yīng)用[A];中國(guó)化學(xué)會(huì)第28屆學(xué)術(shù)年會(huì)第11分會(huì)場(chǎng)摘要集[C];2012年

7 馬萬(wàn)紅;張苗;王齊;陳春城;趙進(jìn)才;;TiO_2光催化氧化醇過(guò)程中的氧轉(zhuǎn)移機(jī)理:氧同位素研究[A];中國(guó)化學(xué)會(huì)第27屆學(xué)術(shù)年會(huì)第12分會(huì)場(chǎng)摘要集[C];2010年

8 張丹;楊秋昕;余江;;體相光催化反應(yīng)降解有機(jī)污染物研究[A];第五屆全國(guó)環(huán)境化學(xué)大會(huì)摘要集[C];2009年

9 林燕燕;王瓊生;王世銘;;Zn_xCd_(1-x)S-CDP雜化材料的制備與光催化性能研究[A];第六屆全國(guó)工業(yè)催化技術(shù)及應(yīng)用年會(huì)論文集[C];2009年

10 萬(wàn)良會(huì);許宜銘;;Fe~(3+)/WO_3光催化體系研究[A];第六屆全國(guó)環(huán)境化學(xué)大會(huì)暨環(huán)境科學(xué)儀器與分析儀器展覽會(huì)摘要集[C];2011年

相關(guān)重要報(bào)紙文章 前2條

1 記者 李大慶　通訊員 張帆;全球能源研究高手大連“論劍”[N];科技日?qǐng)?bào);2011年

2 李宏乾;可見(jiàn)光同樣能實(shí)現(xiàn)光催化降解反應(yīng)[N];中國(guó)環(huán)境報(bào);2006年

相關(guān)博士學(xué)位論文 前10條

1 陳學(xué)福;氧化鉍可見(jiàn)光光催化性能的增效改性研究[D];蘭州理工大學(xué);2017年

2 王芳霄;超臨界CO_2合成介孔碳/氧（硫）化物復(fù)合材料及光催化性能研究[D];哈爾濱工業(yè)大學(xué);2017年

3 梁軍;鍺酸鋅基微納米晶體組成結(jié)構(gòu)控制及光催化性能研究[D];福州大學(xué);2014年

4 陳志鴻;新型具可見(jiàn)光活性光催化體系的設(shè)計(jì)、制備及其光催化性能與機(jī)理研究[D];華南理工大學(xué);2016年

5 霍景沛;聯(lián)噻唑類(lèi)金屬配合物制備與光催化水制氫研究[D];華南理工大學(xué);2016年

6 王可欣;鹵氧化鉍基復(fù)合納米纖維的制備及其光催化性能研究[D];東北師范大學(xué);2016年

7 劉學(xué)琴;貴金屬及石墨烯負(fù)載金屬氧化物的制備與光催化性能研究[D];中國(guó)地質(zhì)大學(xué);2016年

8 王根;半導(dǎo)體材料的固定化及其對(duì)雨水消毒性能的研究[D];中國(guó)地質(zhì)大學(xué)(北京);2016年

9 劉玉良;光催化偶聯(lián)—加氧氧化串聯(lián)反應(yīng)構(gòu)建環(huán)狀化合物的研究[D];山東大學(xué);2017年

10 李燕瑞;基于半導(dǎo)體異質(zhì)結(jié)構(gòu)的光催化劑設(shè)計(jì)、合成及性質(zhì)研究[D];中國(guó)科學(xué)技術(shù)大學(xué);2017年

相關(guān)碩士學(xué)位論文 前10條

1 景煥平;新型金屬—有機(jī)骨架材料的合成及光催化性能研究[D];北京建筑大學(xué);2015年

2 劉振興;ZnFe_20_4基空心納米球的制備及其光催化性能研究[D];陜西科技大學(xué);2015年

3 魏小靜;可見(jiàn)光催化下五元環(huán)內(nèi)酯及二氟吲哚酮的合成反應(yīng)研究[D];蘭州大學(xué);2015年

4 鄒憶倫;TiO_2基光催化劑的制備及其光催化制氫性能[D];上海應(yīng)用技術(shù)學(xué)院;2015年

5 王琳;貴金屬-ZnO-RGO光催化劑的制備及性能研究[D];哈爾濱工業(yè)大學(xué);2015年

6 葛遠(yuǎn)幸;改性鎢酸鉍的制備及其光催化性能研究[D];廣西大學(xué);2015年

7 馮祝嘉;光催化與親核性催化結(jié)合實(shí)現(xiàn)氦鄰位C-H鍵官能化反應(yīng)研究[D];華中師范大學(xué);2015年

8 扈彬;水滑石/纖維復(fù)合結(jié)構(gòu)材料的制備及其吸附光催化性能[D];齊魯工業(yè)大學(xué);2015年

9 吳瑜鵬;TiO_2光催化乙醇一步直接合成乙縮醛[D];山西大學(xué);2015年

10 吳夢(mèng)霞;基于CdSe和石墨相C_3N_4納米結(jié)構(gòu)材料的制備及光催化性能研究[D];大連理工大學(xué);2015年

，

本文編號(hào)：2119240