本文關(guān)鍵詞：新型鉍、鋅系可見光催化劑的制備及降解有機(jī)廢水性能研究　出處：《河南師范大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 可見光催化劑 棒狀Bi VO4 Bi OF/Bi2O3/RGO 棒狀Zn O 廢水處理

【摘要】：光催化氧化技術(shù)是一種去除水體中難降解有機(jī)污染物的有效手段,具有極大的開發(fā)與應(yīng)用前景。當(dāng)今,光催化氧化技術(shù)仍存在量子效率低,可見光利用效率差等缺陷,嚴(yán)重制約著該技術(shù)的工業(yè)化應(yīng)用和發(fā)展。因此,研究開發(fā)性能優(yōu)異的可見光催化劑,是國內(nèi)外水處理領(lǐng)域的重要前沿課題�；阡\、鉍系半導(dǎo)體材料具有良好的可見光催化活性,還原氧化石墨烯(RGO)具有優(yōu)異的吸附性能和高透光性。本研究采用水熱法、化學(xué)水解法,并通過優(yōu)化煅燒溫度、表面活性劑含量及RGO負(fù)載修飾手段制備具有高效可見光催化活性的新型鋅、鉍系光催化劑Bi VO4、Bi OF/Bi2O3/RGO和Zn O;利用X射線衍射(XRD)、掃描電子顯微鏡(SEM)、高分辨透射電子顯微鏡(HRTEM)、N2吸附、傅里葉變換紅外光譜(FT-IR)、紫外可見漫反射光譜(UV-vis DR)、光致發(fā)光光譜(PL)、循環(huán)伏安法(CV)等手段對其光催化劑的結(jié)晶、形態(tài)、吸附性能、能帶結(jié)構(gòu)、化學(xué)結(jié)構(gòu)、光化學(xué)性質(zhì)和電子轉(zhuǎn)移特性進(jìn)行表征;通過對目標(biāo)污染物羅丹明B(Rh B)、橙黃-IV(OG-IV)或甲硝唑(MNZ)模擬廢水在可見光或自然太陽光照射下的降解率,評價新型光催化劑的光催化活性,從而為新型鋅、鉍系可見光催化劑的制備和在難降解有機(jī)廢水處理中的應(yīng)用提供理論依據(jù)。主要研究結(jié)論如下:(1)水熱法制備棒狀Bi VO4光催化劑及其自然太陽光催化性能研究:以Bi(NO3)3·5H2O和NH4VO3為原料,采用水熱法制備出新型Bi VO4光催化劑。實(shí)驗(yàn)結(jié)果表明:煅燒溫度對Bi VO4光催化劑的性質(zhì)及光催化活性均有重要影響,300°C煅燒條件下制備得到的催化劑(Bi V-3)活性最優(yōu);通過表征發(fā)現(xiàn),Bi V-3具有均一的棒狀結(jié)構(gòu),屬于單斜白鎢礦型,可見光吸收限達(dá)到540 nm,禁帶寬度為2.44 e V,比表面積為3.4652m2/g;在自然太陽光下,以Rh B和OG-IV作為模擬廢水進(jìn)行光催化化活性研究,結(jié)果顯示:在進(jìn)水濃度分別為10 mg/L和7.5 mg/L,催化劑投加量分別為1.0 g/L和0.5 g/L條件下,兩者的降解率分別達(dá)到99%和75%;與未煅燒的相比,Rh B和OG-IV的降解率分別提升了45%和49%;且Bi V-3對Rh B和OG-IV的降解規(guī)律均符合一級動力學(xué)模型,其相應(yīng)的反應(yīng)速率常數(shù)分別為0.852 h-1和0.142 h-1;Bi V-3具有良好的循環(huán)性和穩(wěn)定性。(2)水解法制備Bi OF/Bi2O3/RGO光催化劑及其自然太陽光催化性能研究:以Bi(NO3)3·5H2O和Na F為原料,采用水解法制備出了Bi OF/Bi2O3納米光催化劑,通過水浴還原法將Bi OF/Bi2O3用RGO負(fù)載修飾,制備出性能優(yōu)異的Bi OF/Bi2O3/RGO復(fù)合光催化劑。研究結(jié)果表明:煅燒溫度對Bi OF/Bi2O3光催化劑具有顯著影響,在300°C煅燒溫度下,得到的光催化劑(BF-3)活性最高;石墨烯負(fù)載量對復(fù)合光催化劑的活性具有重要影響,當(dāng)負(fù)載量為1wt%時,樣品(BG-1)的光催化活性最高;在自然太陽光下,以Rh B為模擬廢水進(jìn)行光催化活性測試,結(jié)果顯示:在進(jìn)水濃度為15 mg/L,復(fù)合光催化劑BG-1的投加量為0.5 g/L條件下,Rh B降解率高達(dá)99%;與未負(fù)載BF-3光催化劑相比,BG-1樣品的催化活性提高了48%;并且發(fā)現(xiàn)該催化劑具有良好的穩(wěn)定性和循環(huán)性。(3)水熱法制備Zn O光催化劑中不同表面活性劑含量對光催化活性的影響:以Zn(CH3COO)2·2H2O和Na WO4·2H2O為原料,采用水熱法制備出Zn O光催化劑,并通過十二烷基苯磺酸鈉(SDBS)表面活性劑對Zn O光催化劑進(jìn)行修飾。研究結(jié)果顯示:當(dāng)SDBS添加量為0.75 g時,制備的光催化劑(ZO-0.75)活性最優(yōu);經(jīng)過表征發(fā)現(xiàn)SDBS的存在,改變了催化劑的形態(tài)、禁帶寬度等性質(zhì),修飾后的ZO-0.75為納米棒狀結(jié)構(gòu),禁帶寬度為3.17e V;通過羥基自由基捕獲實(shí)驗(yàn)驗(yàn)證出該催化劑的主要活性成分為·OH;在模擬可見光下,ZO-0.75光催化劑對甲硝唑的降解率達(dá)72%,比未修飾的Zn O活性高出56%。
[Abstract]:Photocatalytic oxidation technology is an effective means to remove the refractory organic pollutants in water, and has great prospects for development and application. Nowadays, photocatalytic oxidation still has some defects, such as low quantum efficiency and poor utilization of visible light, which seriously restrict the industrial application and development of this technology. Therefore, the research and development of excellent photocatalyst of visible light is an important frontier subject in the field of water treatment at home and abroad. Zinc and bismuth based semiconductors have good photocatalytic activity, and the reduction of graphene oxide (RGO) has excellent adsorption properties and high light transmittance. This study using the hydrothermal method and chemical hydrolysis method, and by optimizing the calcination temperature, surfactant content and RGO load model, modified zinc preparation methods with high visible light photocatalytic activity of bismuth based photocatalyst Bi VO4, Bi OF/Bi2O3/RGO and Zn O; using X ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), N2 adsorption, Fu Liye transform infrared spectroscopy (FT-IR), UV Vis diffuse reflectance spectroscopy (UV-vis DR), photoluminescence spectroscopy (PL), cyclic voltammetry (CV) and other means of crystallization, on the photocatalytic agent morphology, adsorption properties, energy band the structure, chemical structure, photochemical properties and electron transfer properties were characterized by B; the target pollutants Luo Danming (Rh B), orange -IV (OG-IV) or metronidazole (MNZ) simulated wastewater under visible light or natural sun light irradiation degradation rate, the evaluation model of light The photocatalytic activity of the catalyst provides a theoretical basis for the preparation of new zinc and bismuth visible light catalysts and the application of the photocatalyst in the treatment of refractory organic wastewater. The main conclusions are as follows: (1) hydrothermal synthesis of rod like Bi VO4 photocatalyst and its natural solar photocatalytic performance: Bi (NO3) 3. 5H2O and NH4VO3 are used as raw materials, and new Bi VO4 photocatalyst is prepared by hydrothermal method. The experimental results show that the calcination temperature has on the Bi VO4 photocatalyst properties and photocatalytic activity of the important effect of catalyst prepared by 300 DEG C under calcination conditions (Bi V-3) activity was optimal; characterized by Bi V-3 found that the rod like structure with uniform, which belongs to the monoclinic, visible light absorption limit reached 540 nm. The band gap is 2.44 e V, the specific surface area of 3.4652m2/g; in the natural sunlight, with Rh B and OG-IV as simulated wastewater was studied. The results showed that the photocatalytic activity of the influent concentration were 10 mg/L and 7.5 mg/L, catalyst dosage were 1 g/L and 0.5 g/L, both the degradation rate reached 99% and 75% respectively; compared with the method, the degradation of Rh B and OG-IV respectively increased by 45% and 49%; and Bi V-3 of Rh B and OG-IV degradation were accorded with the first-order kinetics model, the corresponding reaction rate constants were 0.852 H-1 And 0.142 H-1; Bi V-3 has good circulatory and stability. (2) the preparation of Bi OF/Bi2O3/RGO photocatalyst and its photocatalytic properties of natural sun hydrolysis method: Bi (NO3) 3 - 5H2O Na and F as raw materials, was prepared by hydrolysis of Bi OF/Bi2O3 nano photocatalyst, Bi OF/Bi2O3 with RGO modified by water bath load reduction method, the preparation of Bi OF/Bi2O3/RGO composite photocatalyst excellent performance. The results showed that the calcination temperature has significant effect on Bi OF/Bi2O3 photocatalyst in the calcination temperature of 300 DEG C, the obtained Photocatalyst (BF-3) was the highest; has an important influence on graphene load on the activity of composite photocatalyst, when the load is 1wt%, the sample (BG-1) the highest photocatalytic activity; in natural sunlight, photocatalytic activity test, using Rh B as the simulation results show that: in the wastewater influent concentration was 15 mg/L, the composite photocatalyst dosage of BG-1 is 0.5 g/L, Rh degradation rate of B was 99%; compared with non immobilized BF-3 catalyst, the catalytic activity of BG-1 were increased 48%; and found that the catalyst has good stability and cycle. (3) prepared by hydrothermal method Zn O photocatalyst with different surfactant content on photocatalytic activity: Zn (CH3COO) 2 - 2H2O Na and WO4 2H2O as raw material, prepared by hydrothermal method Zn O photocatalyst, and by twelve sulfonate (SDBS) surfactants modified Zn O photocatalyst. The results showed that when the amount of SDBS is 0.75 g, the prepared Photocatalyst (ZO-0.75) characterized by optimal activity; found that the presence of SDBS, change the morphology of the catalysts and the band gap properties of modified ZO-0.75 nano rod structure, the band gap is 3.17e V; through hydroxyl radical capture experiments the main active component of the catalyst is OH; in the simulation under visible light, ZO-0.75 photocatalytic degradation of metronidazole rate reached 72%, 56% higher than the unmodified Zn O activity.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TQ426;X703

【共引文獻(xiàn)】

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本文編號：1341112