掺杂TiO_2光催化剂的制备、表征及降解含聚污水研究
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摘要
为了研究TiO_2光催化降解聚丙烯酰胺(HPAM)的可行性,采用溶胶-凝胶法制备了锐钛矿型纳米TiO_2,研究了合成催化剂反应条件对光催化降解含油废水中HPAM的影响。结果表明,最佳反应条件分别为:煅烧温度在500℃时,光催化活性达到最高;最佳老化时间为1天左右;当钛酸丁酯与醇的比例为1:8时,钛酸丁酯与水的比例为10:4,制备出的TiO_2催化活性最大。
掺杂有利于TiO_2光催化活性的提高。首先,以P123为模板剂,采用溶胶-凝胶的溶剂热合成方法制备了H_3PW_(12)O_(40)掺杂的介孔结构TiO_2。利用紫外漫反射光谱、红外光谱、X射线粉末衍射、拉曼光谱和电感耦合等离子原子发射光谱等手段对上述新材料进行结构表征。结果表明,被制备的复合物具有锐钛矿与板钛矿复合的晶型结构、大的BET比表面积和统一孔尺寸分布的介孔结构。H_3PW_(12)O_(40)以完整的Keggin结构固定在TiO_2的晶格间隙,并且和TiO_2表面发生化学的相互作用。复合物对降解MO,RB,MB和CV显示出较高的紫外光催化活性,对CV显示出可见光催化活性。通过ES-MS检测CV降解的中间产物及最终产物,从而推出CV紫外光催化降解的机理。然后,利用一步溶胶-凝胶的溶剂热合成方法制备稀土掺杂的TiO_2纳米粒子(RE~(3+)/TiO_2,RE~(3+) = Eu~(3+),Pr~(3+),Nd~(3+),Gd~(3+)和Y~(3+))。结果表明,所制备的样品均为锐钛矿型纳米晶,粒子尺寸在9 nm左右,稀土以氧化物的形式存在于TiO_2的晶格间隙。在紫外光条件下降解HPAM,比较不同稀土掺杂对催化活性的影响,Eu~(3+) (Gd~(3+),Pr~(3+))/TiO_2展示了良好的催化活性,最佳掺杂量为2.4%(w),矿化率最大可达67%。通过液质联机测定HAPM降解的中间产物,推断出HAPM的紫外光催化降解机理。
研究了在紫外光作用下催化条件对光催化降解HPAM的影响,如:光催化时间、催化剂的浓度、HAPM的初始浓度、反应的pH值及Na_2CO_3,NaHCO_3和NaCl浓度对催化的影响。实验结果表明,除NaCl的存在对催化活性影响较小外,其它条件对HPAM的催化降解均有显著的影响。增加催化时间、最佳的催化剂浓度、pH≈6和较低的初始浓度有利于催化反应的进行。
In order to research feasibility of TiO_2 photocatalytic degradation partially hydrolysis polyacrylamide (HPAM), anatase nanocrystallin TiO_2 was prepared by sol-gel method. The conditions of synthesis catalyst were studied according to effect of photocatalytic degradation HPAM solution of containing oil waste. The results show that the best reaction conditions were gained: when calcination temperature is 500℃, catalytic activity achieved high; The optimal aging time is about 1 day; When ratio of Ti(OBu)4 and alcohol is 1:8, ratio of Ti(OBu)4 and water is 10:4 photocatalytic activity of as prepared TiO_2 is highest.
Doping is in favor of enhancing photocatalytic activity of TiO_2. Firstly, the mesoporous TiO_2 was prepared from a poly(ethylene glycol)-poly(propylene glycol)-based triblock copolymer (P123), titanium isopropoxide and H_3PW_(12)O_(40) by using sol–gel and solvothermal method. The structure of as-synthesized composites were Characterizaed by UV/DRS, FT-IR,XRD, solid Raman and ICP-AES. The results show the as-prepared compositions exhibited anatase and brookite phase structure, larger BET areas, and mesoporosity with uniform pore size distribution. It also indicated that the primary Keggin structure remained intact after immobilization of the unit into TiO_2 network, and chemical interactions between the unit and the TiO_2 network existed in the composites. The composites exhibited UV-light photocatalytic activity to degradation of MO, RB, MB and CV and visible-light activity to degradation CV. The intermediates and the final products of CV degradation were detected by ES-MS. According to the experimental results, we proposed a possible mechanism of the photodegradation of CV under UV-light irradiation in the aqueous system. Afterwards, rare-earth oxide doped titania nanocomposites (RE~(3+)/TiO_2, where RE~(3+) = Eu~(3+), Pr~(3+), Nd~(3+), Gd~(3+), and Y~(3+)) were prepared by a single step sol-gel-solvothermal method. The products exhibited anatase phase structure, nanosized with average size of 9 nm, and rare erath entered into the crystal cell of TiO_2 (interstitial mode) in the form of oxide. Furthermore, the photocatalytic activity of prepared RE~(3+) doped TiO_2 was studied by degrading HPAM under UV light irradiation. The results showed that the enhanced photocatalytic activity was obtained on Eu~(3+) (Gd~(3+), Pr~(3+))/TiO_2. HPAM was completely degraded and maximal mineralization ratio reached 67% when Eu~(3+), Gd~(3+) and Pr~(3+) loading were 2.4% (w). In addition, intermediate products were detected via liquid chromatography/mass spectrometry/ mass spectrometry, and degradation mechanism was analyzed.
The photocatalytic degradation of HPAM has been studied in the presence of UV light under different conditions such as pH, catalyst concentration, substrate concentration, Na_2CO_3, NaHCO_3 and NaCl concentration. The degradation of HPAM was found to be strongly influenced by all the above parameters except for NaCl concentration. Increasing reaction time, optimal concentration of catalyst, pH≈6 and lower substrate concentration are in favor of photocatalytic reaction.
掺杂有利于TiO_2光催化活性的提高。首先,以P123为模板剂,采用溶胶-凝胶的溶剂热合成方法制备了H_3PW_(12)O_(40)掺杂的介孔结构TiO_2。利用紫外漫反射光谱、红外光谱、X射线粉末衍射、拉曼光谱和电感耦合等离子原子发射光谱等手段对上述新材料进行结构表征。结果表明,被制备的复合物具有锐钛矿与板钛矿复合的晶型结构、大的BET比表面积和统一孔尺寸分布的介孔结构。H_3PW_(12)O_(40)以完整的Keggin结构固定在TiO_2的晶格间隙,并且和TiO_2表面发生化学的相互作用。复合物对降解MO,RB,MB和CV显示出较高的紫外光催化活性,对CV显示出可见光催化活性。通过ES-MS检测CV降解的中间产物及最终产物,从而推出CV紫外光催化降解的机理。然后,利用一步溶胶-凝胶的溶剂热合成方法制备稀土掺杂的TiO_2纳米粒子(RE~(3+)/TiO_2,RE~(3+) = Eu~(3+),Pr~(3+),Nd~(3+),Gd~(3+)和Y~(3+))。结果表明,所制备的样品均为锐钛矿型纳米晶,粒子尺寸在9 nm左右,稀土以氧化物的形式存在于TiO_2的晶格间隙。在紫外光条件下降解HPAM,比较不同稀土掺杂对催化活性的影响,Eu~(3+) (Gd~(3+),Pr~(3+))/TiO_2展示了良好的催化活性,最佳掺杂量为2.4%(w),矿化率最大可达67%。通过液质联机测定HAPM降解的中间产物,推断出HAPM的紫外光催化降解机理。
研究了在紫外光作用下催化条件对光催化降解HPAM的影响,如:光催化时间、催化剂的浓度、HAPM的初始浓度、反应的pH值及Na_2CO_3,NaHCO_3和NaCl浓度对催化的影响。实验结果表明,除NaCl的存在对催化活性影响较小外,其它条件对HPAM的催化降解均有显著的影响。增加催化时间、最佳的催化剂浓度、pH≈6和较低的初始浓度有利于催化反应的进行。
In order to research feasibility of TiO_2 photocatalytic degradation partially hydrolysis polyacrylamide (HPAM), anatase nanocrystallin TiO_2 was prepared by sol-gel method. The conditions of synthesis catalyst were studied according to effect of photocatalytic degradation HPAM solution of containing oil waste. The results show that the best reaction conditions were gained: when calcination temperature is 500℃, catalytic activity achieved high; The optimal aging time is about 1 day; When ratio of Ti(OBu)4 and alcohol is 1:8, ratio of Ti(OBu)4 and water is 10:4 photocatalytic activity of as prepared TiO_2 is highest.
Doping is in favor of enhancing photocatalytic activity of TiO_2. Firstly, the mesoporous TiO_2 was prepared from a poly(ethylene glycol)-poly(propylene glycol)-based triblock copolymer (P123), titanium isopropoxide and H_3PW_(12)O_(40) by using sol–gel and solvothermal method. The structure of as-synthesized composites were Characterizaed by UV/DRS, FT-IR,XRD, solid Raman and ICP-AES. The results show the as-prepared compositions exhibited anatase and brookite phase structure, larger BET areas, and mesoporosity with uniform pore size distribution. It also indicated that the primary Keggin structure remained intact after immobilization of the unit into TiO_2 network, and chemical interactions between the unit and the TiO_2 network existed in the composites. The composites exhibited UV-light photocatalytic activity to degradation of MO, RB, MB and CV and visible-light activity to degradation CV. The intermediates and the final products of CV degradation were detected by ES-MS. According to the experimental results, we proposed a possible mechanism of the photodegradation of CV under UV-light irradiation in the aqueous system. Afterwards, rare-earth oxide doped titania nanocomposites (RE~(3+)/TiO_2, where RE~(3+) = Eu~(3+), Pr~(3+), Nd~(3+), Gd~(3+), and Y~(3+)) were prepared by a single step sol-gel-solvothermal method. The products exhibited anatase phase structure, nanosized with average size of 9 nm, and rare erath entered into the crystal cell of TiO_2 (interstitial mode) in the form of oxide. Furthermore, the photocatalytic activity of prepared RE~(3+) doped TiO_2 was studied by degrading HPAM under UV light irradiation. The results showed that the enhanced photocatalytic activity was obtained on Eu~(3+) (Gd~(3+), Pr~(3+))/TiO_2. HPAM was completely degraded and maximal mineralization ratio reached 67% when Eu~(3+), Gd~(3+) and Pr~(3+) loading were 2.4% (w). In addition, intermediate products were detected via liquid chromatography/mass spectrometry/ mass spectrometry, and degradation mechanism was analyzed.
The photocatalytic degradation of HPAM has been studied in the presence of UV light under different conditions such as pH, catalyst concentration, substrate concentration, Na_2CO_3, NaHCO_3 and NaCl concentration. The degradation of HPAM was found to be strongly influenced by all the above parameters except for NaCl concentration. Increasing reaction time, optimal concentration of catalyst, pH≈6 and lower substrate concentration are in favor of photocatalytic reaction.
引文
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