【摘要】：有機(jī)物污染是目前我國(guó)面臨的最大環(huán)境保護(hù)問題之一,染料廢水作為高分子聚合物,其濃度大、色度高、可生化性差,缺乏有效的處理方法,成為了水處理領(lǐng)域的難點(diǎn),對(duì)人類和環(huán)境造成了極大的危害。光催化技術(shù)作為高級(jí)氧化技術(shù)的一種,為我們提供了高效治理有機(jī)廢水的途徑。此技術(shù)常采用納米二氧化鈦?zhàn)鳛榇呋瘎?這是因?yàn)槠浠瘜W(xué)性質(zhì)穩(wěn)定、無毒,并且材料成本低。然而納米材料存在回收難度大、可重復(fù)利用率低。因此本論文研究了新型TiO_2碳布電極和3D-TiO_2納米管電極的制備及其改性,分析材料形成機(jī)理、物理化學(xué)性能和光電催化性能,并分析光電催化降解甲基橙的各個(gè)影響因素,為光電催化去除有機(jī)污染物技術(shù)的實(shí)際應(yīng)用提供理論依據(jù),主要研究成果如下:(1)水熱法合成以碳布為基底的TiO_2電極:①通過比較光電流初步推斷光電催化活性,調(diào)節(jié)溫度、時(shí)間、鈦源等參數(shù)優(yōu)化電極性能。確定合成電極最佳實(shí)驗(yàn)條件為:前驅(qū)液濃度分別為0.6mL鈦酸異丙酯、10mL鹽酸溶液、0.2 g十六烷基三甲基溴化銨、0.34mL乙二醇;水熱溫度150℃;反應(yīng)時(shí)間5h。②所合成的材料為金紅石型TiO_2納米簇顆粒電極,其物理化學(xué)性能穩(wěn)定,導(dǎo)電性優(yōu)越,在紫外光下施加+0.7 V的偏壓,2 h光電降解5 mg/L甲基橙去除率為98%,且重復(fù)實(shí)驗(yàn)7次時(shí)2 h降解率仍然大于85%。(2)采用電化學(xué)陽極氧化法,以鈦絲網(wǎng)作為基底材料合成3D-TiO_2納米管陣列(3D-TNAs)電極。①最佳陽極氧化實(shí)驗(yàn)條件為:溶劑為V乙二醇：V 水=1:1,0.5wt%NH4F,陽極氧化電壓20V,超聲振蕩傳質(zhì)氧化90min。制得TiO_2納米管,與同一實(shí)驗(yàn)條件下以鈦板為基底陽極氧化電極比較,電化學(xué)活性面積、光電流、光電催化降解反應(yīng)速率常數(shù)分別提高了2倍、1倍和2倍。②通過連續(xù)離子層吸附反應(yīng),將合成出的3D-TNAs電極分別浸漬于乙醇:H_2O=1:1為溶劑的乙酸鋅、乙酸鎘、Na2S溶液,獲得異質(zhì)節(jié)負(fù)載改性電極。最佳實(shí)驗(yàn)條件是:濃度分別為0.01 mol/L,負(fù)載次數(shù)12次,煅燒條件是氮?dú)鈿夥找?℃/min升溫至500℃保持2h。在負(fù)載硫化物前,陽極氧化電極浸漬于1 mg/L氧化石墨烯(GO),再負(fù)載硫化物,氧化石墨烯的存在使體系形成Z形模型,明顯提高了光電催化性能。③硫化物改性電極在實(shí)際廢水降解測(cè)試效果不理想,穩(wěn)定性有待提高。(3)采用溶液蒸發(fā)自組裝法(EISA),制備金紅石-銳鈦礦混相二氧化鈦3D-TNAs電極材料,①最佳實(shí)驗(yàn)條件為:P123為模板劑,陳化2d,在陽極氧化后直接浸到溶膠凝膠中一起陳化干燥,以5℃/min升溫速率升到500℃,煅燒2h合成出3D-TNAs/TiO_2(EISA)電極,光電流較3D-TNAs電極提高2.5倍,光電耦合性能在+0.8 V最佳。②對(duì)5 mg/L的MO進(jìn)行光催化效果明顯,在2h汞燈照射下施加+0.8 V偏壓,同樣實(shí)驗(yàn)條件重復(fù)6次對(duì)MO的去除率仍大于98%。③光電催化降解率受有機(jī)污染物濃度、催化劑濃度、反應(yīng)溫度、光強(qiáng)、電解質(zhì)濃度的影響。在電解質(zhì)濃度一致下,低濃度污染物光電去除率符合一級(jí)動(dòng)力學(xué),-ln(C_t/C_0)=kt,且反應(yīng)速率常數(shù)k與污染物初始濃度呈指數(shù)關(guān)系k=aC_0~(n1),與反應(yīng)溫度符合阿倫尼烏斯公式k=Aexp(-Ea/RT),與光強(qiáng)符合指數(shù)關(guān)系k=aIn3,與電極材料面積符合k=b(A_sD)~n,總結(jié)反應(yīng)速率常數(shù)與各個(gè)參數(shù)的關(guān)系為k = A·e~(Ea/RT)·C_0~(n1)·I~(n2)·(A_sD)~(n3),確定污染物濃度與時(shí)間的關(guān)系為C_t/C_0=e~(-kt)=e~(-A·e~(-Ea/RT)·C_0~(n1)·I~(n2)·(A_sD)~(n3)·t)。
[Abstract]:Organic matter pollution is one of the biggest environmental protection problems in China. As a polymer, dye wastewater is a polymer with high concentration, high chromaticity, poor biodegradability and lack of effective treatment. It has become a difficult problem in the field of water treatment and has caused great harm to human and environment. Photocatalytic technology is a kind of advanced oxidation technology. Nanoscale titanium dioxide is often used as a catalyst. This is because its chemical properties are stable, nontoxic, and the cost of materials is low. However, the recovery of nanomaterials is difficult and the reutilization rate is low. Therefore, the new TiO_2 carbon electrode and 3D-TiO_2 nanotube are studied in this paper. The preparation and modification of the electrode, the formation mechanism of the material, the physical and chemical properties and the photoelectric catalytic properties are analyzed, and the various influence factors of the photocatalytic degradation of methyl orange are analyzed, and the theoretical basis for the application of the photoelectrocatalysis to remove the organic pollutants is provided. The main research results are as follows: (1) the synthesis of TiO_2 electricity based on the carbon cloth by hydrothermal method is as follows. The optimum experimental conditions of synthetic electrode are: 0.6mL isopropyl titanate, 10mL hydrochloric acid solution, 0.2 g sixteen alkyl ammonium bromide, 0.34mL ethylene glycol, 150 C hydrothermal temperature and 5 reaction time, respectively. H. (2) is a rutile type TiO_2 nanocluster electrode. Its physical and chemical properties are stable, electrical conductivity is superior, +0.7 V bias is applied under UV light, 2 h photodegradation 5 mg/L methyl orange removal rate is 98%, and the 2 h degradation rate is still greater than 85%. (2) by electrochemical anodic oxidation, with titanium screen as the base. 3D-TiO_2 nanotube array (3D-TNAs) electrode was synthesized by the substrate. (1) the optimum anodic oxidation experiment conditions were as follows: the solvent was V ethylene glycol: V water =1:1,0.5wt%NH4F, anodic oxidation voltage 20V, TiO_2 nanotube produced by ultrasonic oscillation mass transfer oxidation 90min., compared with the titanium plate as the base anode oxidation electrode under the same experimental condition, the electrochemical active area and light. The rate constants of the current and photoelectric catalytic degradation were increased by 2 times, 1 times and 2 times respectively. By continuous ion layer adsorption, the synthesized 3D-TNAs electrodes were impregnated with ethanol: H_2O=1:1 as solvent, zinc acetate, cadmium acetate and Na2S solution. The optimum experimental condition was that the concentration was 0.01 mol/L, respectively. The time of loading is 12 times. The conditions of calcining are that the nitrogen atmosphere is heated at 2 /min to 500 C to maintain 2h. at the load of sulfide, and the anode oxidation electrode impregnated with 1 mg/L graphene oxide (GO), then the sulphide is loaded, and the presence of graphene oxide makes the system form a Z shape model and obviously improves the photocatalytic performance. 3. Sulfide modified electrode is reduced to the actual wastewater. The results of the solution are not ideal, and the stability needs to be improved. (3) using the solution evaporation self assembly (EISA) method to prepare the rutile anatase titanium dioxide 3D-TNAs electrode material. (1) the optimum experimental conditions are P123 as a template, aging 2D, and drying in gelatin gel directly after anodizing, and rising to 500 at the temperature of /min at 5. The 3D-TNAs/TiO_2 (EISA) electrode was synthesized by calcined 2h, the photoelectric current was 2.5 times higher than that of the 3D-TNAs electrode, and the photoelectric coupling performance was the best in +0.8 V. 2. The photocatalytic effect on MO of 5 mg/L was obvious, the +0.8 V bias was applied under the 2H mercury lamp, and the removal rate of the MO was still greater than the photoelectric catalytic degradation rate 6 times more than the photoelectric catalytic degradation rate. The effect of dye concentration, catalyst concentration, reaction temperature, light intensity and electrolyte concentration. Under the consistency of electrolyte concentration, the photoelectric removal rate of low concentration pollutants accords with the first order kinetics, -ln (C_t/C_0) =kt, and the reaction rate constant k is exponentially related to the initial concentration of pollutants k= aC_0~ (N1), and the reaction temperature conforms to the Arrhenius formula k=Aexp (-Ea/). RT), in accordance with the exponential relationship with the light intensity, k=aIn3, and the area of the electrode material in line with the k=b (A_sD) ~n. The relation between the reaction rate constant and the parameters is k = A / e~ (Ea/RT) C_0~ (N1) and I~.
【學(xué)位授予單位】：中央民族大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X703

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