掺杂纳米二氧化钛光催化抑杀蓝藻生长的研究
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摘要
水体富营养化，导致滇池蓝藻生长泛滥，恶化了滇池水域，严重影响了滇池的旅游景观。迄今为止，为治理滇池蓝藻，国家已投入大量资金，使用过物理、化学、生物等方法进行治理或抑制滇池蓝藻生长；从应用的效果看，这些方法都有一定的作用，但尚不能彻底解决滇池的蓝藻问题。
近年来，大量文献对以纳米二氧化钛作为光催化剂矿化有机污染物为CO_2和H_2O、杀灭细菌和病毒等进行了报道。纳米二氧化钛作为光催化剂，除了有较高的光催化活性、微粒简便易得、成本低廉、原料丰富外，其化学稳定性好、无毒、使用后不会产生有害的化学物质。目前，纳米二氧化钛应用于治理或抑制滇池蓝藻(又名蓝细菌)生长的实验尚未见报道。
本文尝试用改性纳米二氧化钛进行抑杀滇池蓝藻的生长。首先采用溶胶-凝胶法，通过水解钛酸正丁酯制备纳米二氧化钛；用合成的纳米二氧化钛分别在高压汞灯、紫外灯和太阳光照射下，对取自滇池的蓝藻进行了各种条件下的抑杀试验研究，为合成改性纳米二氧化钛及其应用奠定了基础。此外，在水解钛酸正丁酯过程中，根据实验的要求，分别加入不同比例的掺杂组分的前驱体：Fe(NO_3)_3·6H_2O、Zn(NO)_3·9H_2O、(NH_4)_2WO_4、Mn(NO_3)·2H_2O、Ce(NO_3)_3·6H_2O、活性炭、AgNO_3和RuCl_3溶液，并进一步处理制得不同比例复合氧化物Fe_2O_3，ZnO和WO_3，稀土3.3％MnO_2／6.7％CeO_2，活性炭和贵金属Ag或Ru各自掺杂的纳米二氧化钛。用NaBH_4还原含有PdCl_2(或H_2PtCl_6)的纳米TiO_2的乙醇的悬浊液，制备Pd(或Pt)掺杂的纳米TiO_2。利用IR、UV-Vis、XRD、TEM、XPS、ICP等现代仪器对合成的改性材料的结构进行了分析和表征。
论文用稀土Mn、Ce改性的纳米TiO_2、纳米TiO_2凹扣于活性炭表面的粉体材料、不同比例Fe_2O_3，ZnO和WO_3各自掺杂的纳米二氧化钛复合半导体催化剂在太阳光照射下，对取自滇池的蓝藻进行了各种条件下的抑杀试验研究；用不同比例贵金属掺杂的改性纳米二氧化钛分别在太阳光和暗室条件下对取自滇池的蓝藻进行了各种条件下的抑杀试验研究；通过暗室条件下的实验结果，排除了贵金属离子的杀藻作用对光催化剂的干扰；论文还分析并比较了各类催化剂的相对活性，讨论了催化剂用量对抑杀蓝藻的活性的大小；选用1％Pt／TiO_2光催化剂进行模拟滇池的小试实验；提出了改性纳米TiO_2抑制蓝藻的机理。
经过研究，得到以下结论：
1、纳米二氧化钛在太阳光照射下，对蓝藻生长的抑制效果较小，在紫外光和高压汞灯照射下具有较好的抑杀效果。经过改性的纳米二氧化钛中，贵金属掺杂、5％ZnO复合半导体掺杂、40％活性炭掺杂、稀土改性的纳米二氧化钛光催化剂在太阳光照射下都能有效地抑杀蓝藻的生长。
2、通过选择各种类型掺杂的、活性相对较高的改性纳米TiO_2，在同一条件下进行抑杀蓝藻的实验得出，光催化剂的相对活性为：1％Ag／TiO_2＞1％Pt／TiO_2＞40％活性炭／TiO_2＞3.3％MnO_2／6.7％CeO_2／TiO_2＞5％ZnO／TiO_2；
3、通过不同用量的光催化剂抑杀蓝藻的实验得出，催化剂的用量应控制在一定的范围，量太少，吸附蓝藻不充分，光催化剂抑制蓝藻的效果会受到影响，而用量太多，成本增大。在抑制蓝藻的实验中，叶绿素含量在4.2mg·L~(-1)以内的蓝藻(250mL)，催化剂用量选择0.1g就能取得满意的效果。
4、提出了改性纳米二氧化钛抑杀蓝藻的机理。
本论文的创新之处在于，首次分别用Fe_2O_3，ZnO和WO_3各自掺杂的纳米TiO_2复合半导体材料抑制、杀灭取自滇池蓝藻的研究；首次将稀土Mn、Ce改性的纳米TiO_2用于抑制、杀灭取自滇池蓝藻的研究；首次分别将贵金属铂、钯、钌、银改性的纳米TiO_2用于抑制、杀灭取自滇池蓝藻的研究；首次将纳米TiO_2凹扣于活性炭表面的粉体材料用于抑制、杀灭取自滇池蓝藻的研究。其次，为了检测掺杂贵金属在纳米二氧化钛中的量和存在形式，最新合成了4-(2-羟基萘酚-1-亚甲烯)-若丹宁(HNMTD)试剂，通过IR、~1HNMR、MS、碳、氢分析等确定了化合物的结构，并用它为柱前衍生试剂，用ZORBAX Stable Bound(4.6×50mm，1.8μm)快速分离柱为固定相，结合微波消化样品和二极管矩阵检测器检测建立了一种高效液相色谱测定铂、钯、钌含量的方法，该法用于纳米二氧化钛材料中铂、钯、钌的测定和检测催化剂抑杀蓝藻后水样中的贵金属离子的含量，取得了较好的效果。
The eutrophication of natural waters in Dianchi Lake has led to an increase in the incidence of cyanobacteria or blue-green algae, which subsequently causes the deterioration of water resources and seriously affects the scenery of Lake Dianchi. So far, Physical, chemical and biological approaches to curb cyanobacteria in Dianchi Lake there have been used, and some of them have made positive effects, however, these methods were also limited in practical use. Over the recent years, there has been an extensive literature on the application of TiO_2 as photocatalyst in destroying bacteria, degrading or mineralizing organic compounds, such as aromatic and haloaromatic, to CO_2 and H_2O. Nano-TiO_2 has been widely employed as photocatalyst due to its high activity of photocatalysis, its availability at a reasonable cost, in addition to its nontoxic nature, its chemical stability, and its capability of being used repeatedly without substantial loss of catalytic activity. Furthermore, TiO_2 photo-catalyst does not produce hazardous waste byproducts in the process of photocatalysis. Up to now, the application of nano-TiO_2 photocatalysts to curb cyanobacteria or blue bacteria from Dianchi Lake has not been reported.
This thesis was aimed to study the possibility for the application of modified nano-TiO_2 photocatalysts inhibiting the growth of cyanobacteria from Lake Dianchi under the irradiation of sunlight. Firstly, nano-TiO_2 was prepared by Sol-Gel method with hydrolysis of Ti(OC_4H_9) _4．Secondly, Pd (or Pt) doped nano-TiO_2 was prepared by means of using NaBH_4 to reduce the mixture of PdCl_2 (or H_2PtCl_6) and nano-TiO_2 in the ethanol. Moreover, according to the requirements of experiment, different proportion of Fe_2O_3, ZnO, WO_3, rare-earth element, active carbon, noble metal Ag and Ru doped respectively on nano-TiO_2 were made, during the process of hydrolysis of Ti(OC_4H_9) _4, by treating Ti(OC_4H_9) _4 which served as precursor to prepare homogeneous and transparent solution, and the different content of compounds which were introduced from Fe(NO_3) _3·6H_2O, Zn(NO)_3·9H_2O, (NH_4) _2WO_4, Mn(NO_3) _2·2H_2O, Ce(NO_3) _3·6H_2O, actived carbon, AgNO_3 and RuCl_3 solution. The structure of modifi-ed nano-TiO_2 were measured and determined by means of IR, UV-Vis , XRD, TEM, XPS, ICP and HPLC.
Then, the experiments on nano-TiO_2 inhibitory effect on the growth of cyanobacteria taken from Dianchi Lake were conducted under the irradiation of the high pressure mercury lamp、ultraviolet light lamp and the sunlight, respectively, which lay foundation for the preparation and application of modified nano-TiO_2．In the experiments, different proportion of Fe_2O_3, ZnO, WO_3, rare-earth element, and active carbon doped, respectively, on nano-TiO_2 were used to curb the growth of cyanobacteria taken from Dianchi Lake under the irradiation of sunlight. And different proportion of Ru、Ag、Pd and Pt doped nano-TiO_2 were used to study their inhibitory effects on growth of cyanobacteria from Dianchi Lake under the irradiation of sunlight and in dark room. The case in dark room eliminated the capability of noble metal ions to destroy cyanobacteria. Finally, the relatively high active of modified nano-TiO_2 photocatalysts selected from different types of photocatalysts were used in the study on the inhibitory effect on the growth of cyanobacteria from Dianchi Lake under the irradiation of sunlight. 1%Pt doped on nano-TiO_2 was used in small-scaled experiment in imitation of Dianchi Lake.
From above experiments, we could come to the following conclusions:
1．Using nano-TiO_2 under the irradiation of sunlight exerted little effect on curbing the growth of cyanobacteria from Dianchi Lake. However, it has exhibited better inhibitory effects under irradiation of the high pressure mercury lamp and ultraviolet light lamp. In the experiments of differently modified nano-TiO_2 photocatalysts, the noble metal doped nano-TiO_2, 5%ZnO doped nano-TiO_2, 40% actived carbon doped nano-TiO_2 and rare-earth element 3．3%MnO_2/6．7%CeO_2 doped nano-TiO_2 could effectively curb the growth of cyanobacteria from the Dianchi Lake exposed to the sunlight.
2．After the experiments of the modified nano-TiO_2 photocatalysts on the studies of inhibitory effects on the growth of cyanobacteria under the same condition, we got the activity sequence of the modified nano-TiO_2, which was 1%Ag/TiO_2 > 1% Pt/ TiO_2 > 40%active carbon/TiO_2 > 3．3%MnO_2/6．7% CeO_2 / TiO_2 >5%ZnO/ TiO_2．
3．It was found that the amount of photocatalyst had effect on the growth of Cyanobacteria .If the amount was too small, the adsorption of Cyanobacteria would be incompleted, where as too high amount would result in high cost.The suitable amount was found to be 0．1g photocalyst when the chlorophyll is 4．2g·L~(-1) in 25mL liqual.
4．The mechanism how modified nano-TiO_2 photocatalysts exert inhibitory effect on the growth of Cyanobacteria was studied.
To summary in this thesis, it is for the first time to apply different proportion of Fe_2O_3, ZnO, WO_3 doped respectively on nano-TiO_2 complex semiconductor to the studies on inhibitory effects on growth of cyanobacteria taken from Dianchi Lake, to use modified nano-TiO_2 by rare-earth element to the studies on inhibitory effects on growth of cyanobacteria taken from Dianchi Lake, to employ the noble metal Ru, Ag, Pd and Pt doped respectively on nano-TiO_2 to the studies on inhibitory effects on growth of cyanobacteria from Dianchi Lake, and to use TiO_2-mounted activated carbon to the studies on inhibitory effects on the growth of cyanobacteria. Finally, a new reagent, 4-(2-hydroxy-naphthalene-1-ylmefhylene)-thiazolidine-2, 5-dithione (HNMTD) was synthesized during the process of determination of the content and form of noble metal existing in the photocatalyst. A new method for the simultaneous determination of palladium, platinum and rutium ions as metal-HNMTD chelates was developed using high performance liquid chromatography equipped with an on-line enrichment technique, and the method was applied with good results to the determination of the content and form of Ru, Ag, Pd and Pt in the photocatalyst.
近年来，大量文献对以纳米二氧化钛作为光催化剂矿化有机污染物为CO_2和H_2O、杀灭细菌和病毒等进行了报道。纳米二氧化钛作为光催化剂，除了有较高的光催化活性、微粒简便易得、成本低廉、原料丰富外，其化学稳定性好、无毒、使用后不会产生有害的化学物质。目前，纳米二氧化钛应用于治理或抑制滇池蓝藻(又名蓝细菌)生长的实验尚未见报道。
本文尝试用改性纳米二氧化钛进行抑杀滇池蓝藻的生长。首先采用溶胶-凝胶法，通过水解钛酸正丁酯制备纳米二氧化钛；用合成的纳米二氧化钛分别在高压汞灯、紫外灯和太阳光照射下，对取自滇池的蓝藻进行了各种条件下的抑杀试验研究，为合成改性纳米二氧化钛及其应用奠定了基础。此外，在水解钛酸正丁酯过程中，根据实验的要求，分别加入不同比例的掺杂组分的前驱体：Fe(NO_3)_3·6H_2O、Zn(NO)_3·9H_2O、(NH_4)_2WO_4、Mn(NO_3)·2H_2O、Ce(NO_3)_3·6H_2O、活性炭、AgNO_3和RuCl_3溶液，并进一步处理制得不同比例复合氧化物Fe_2O_3，ZnO和WO_3，稀土3.3％MnO_2／6.7％CeO_2，活性炭和贵金属Ag或Ru各自掺杂的纳米二氧化钛。用NaBH_4还原含有PdCl_2(或H_2PtCl_6)的纳米TiO_2的乙醇的悬浊液，制备Pd(或Pt)掺杂的纳米TiO_2。利用IR、UV-Vis、XRD、TEM、XPS、ICP等现代仪器对合成的改性材料的结构进行了分析和表征。
论文用稀土Mn、Ce改性的纳米TiO_2、纳米TiO_2凹扣于活性炭表面的粉体材料、不同比例Fe_2O_3，ZnO和WO_3各自掺杂的纳米二氧化钛复合半导体催化剂在太阳光照射下，对取自滇池的蓝藻进行了各种条件下的抑杀试验研究；用不同比例贵金属掺杂的改性纳米二氧化钛分别在太阳光和暗室条件下对取自滇池的蓝藻进行了各种条件下的抑杀试验研究；通过暗室条件下的实验结果，排除了贵金属离子的杀藻作用对光催化剂的干扰；论文还分析并比较了各类催化剂的相对活性，讨论了催化剂用量对抑杀蓝藻的活性的大小；选用1％Pt／TiO_2光催化剂进行模拟滇池的小试实验；提出了改性纳米TiO_2抑制蓝藻的机理。
经过研究，得到以下结论：
1、纳米二氧化钛在太阳光照射下，对蓝藻生长的抑制效果较小，在紫外光和高压汞灯照射下具有较好的抑杀效果。经过改性的纳米二氧化钛中，贵金属掺杂、5％ZnO复合半导体掺杂、40％活性炭掺杂、稀土改性的纳米二氧化钛光催化剂在太阳光照射下都能有效地抑杀蓝藻的生长。
2、通过选择各种类型掺杂的、活性相对较高的改性纳米TiO_2，在同一条件下进行抑杀蓝藻的实验得出，光催化剂的相对活性为：1％Ag／TiO_2＞1％Pt／TiO_2＞40％活性炭／TiO_2＞3.3％MnO_2／6.7％CeO_2／TiO_2＞5％ZnO／TiO_2；
3、通过不同用量的光催化剂抑杀蓝藻的实验得出，催化剂的用量应控制在一定的范围，量太少，吸附蓝藻不充分，光催化剂抑制蓝藻的效果会受到影响，而用量太多，成本增大。在抑制蓝藻的实验中，叶绿素含量在4.2mg·L~(-1)以内的蓝藻(250mL)，催化剂用量选择0.1g就能取得满意的效果。
4、提出了改性纳米二氧化钛抑杀蓝藻的机理。
本论文的创新之处在于，首次分别用Fe_2O_3，ZnO和WO_3各自掺杂的纳米TiO_2复合半导体材料抑制、杀灭取自滇池蓝藻的研究；首次将稀土Mn、Ce改性的纳米TiO_2用于抑制、杀灭取自滇池蓝藻的研究；首次分别将贵金属铂、钯、钌、银改性的纳米TiO_2用于抑制、杀灭取自滇池蓝藻的研究；首次将纳米TiO_2凹扣于活性炭表面的粉体材料用于抑制、杀灭取自滇池蓝藻的研究。其次，为了检测掺杂贵金属在纳米二氧化钛中的量和存在形式，最新合成了4-(2-羟基萘酚-1-亚甲烯)-若丹宁(HNMTD)试剂，通过IR、~1HNMR、MS、碳、氢分析等确定了化合物的结构，并用它为柱前衍生试剂，用ZORBAX Stable Bound(4.6×50mm，1.8μm)快速分离柱为固定相，结合微波消化样品和二极管矩阵检测器检测建立了一种高效液相色谱测定铂、钯、钌含量的方法，该法用于纳米二氧化钛材料中铂、钯、钌的测定和检测催化剂抑杀蓝藻后水样中的贵金属离子的含量，取得了较好的效果。
The eutrophication of natural waters in Dianchi Lake has led to an increase in the incidence of cyanobacteria or blue-green algae, which subsequently causes the deterioration of water resources and seriously affects the scenery of Lake Dianchi. So far, Physical, chemical and biological approaches to curb cyanobacteria in Dianchi Lake there have been used, and some of them have made positive effects, however, these methods were also limited in practical use. Over the recent years, there has been an extensive literature on the application of TiO_2 as photocatalyst in destroying bacteria, degrading or mineralizing organic compounds, such as aromatic and haloaromatic, to CO_2 and H_2O. Nano-TiO_2 has been widely employed as photocatalyst due to its high activity of photocatalysis, its availability at a reasonable cost, in addition to its nontoxic nature, its chemical stability, and its capability of being used repeatedly without substantial loss of catalytic activity. Furthermore, TiO_2 photo-catalyst does not produce hazardous waste byproducts in the process of photocatalysis. Up to now, the application of nano-TiO_2 photocatalysts to curb cyanobacteria or blue bacteria from Dianchi Lake has not been reported.
This thesis was aimed to study the possibility for the application of modified nano-TiO_2 photocatalysts inhibiting the growth of cyanobacteria from Lake Dianchi under the irradiation of sunlight. Firstly, nano-TiO_2 was prepared by Sol-Gel method with hydrolysis of Ti(OC_4H_9) _4．Secondly, Pd (or Pt) doped nano-TiO_2 was prepared by means of using NaBH_4 to reduce the mixture of PdCl_2 (or H_2PtCl_6) and nano-TiO_2 in the ethanol. Moreover, according to the requirements of experiment, different proportion of Fe_2O_3, ZnO, WO_3, rare-earth element, active carbon, noble metal Ag and Ru doped respectively on nano-TiO_2 were made, during the process of hydrolysis of Ti(OC_4H_9) _4, by treating Ti(OC_4H_9) _4 which served as precursor to prepare homogeneous and transparent solution, and the different content of compounds which were introduced from Fe(NO_3) _3·6H_2O, Zn(NO)_3·9H_2O, (NH_4) _2WO_4, Mn(NO_3) _2·2H_2O, Ce(NO_3) _3·6H_2O, actived carbon, AgNO_3 and RuCl_3 solution. The structure of modifi-ed nano-TiO_2 were measured and determined by means of IR, UV-Vis , XRD, TEM, XPS, ICP and HPLC.
Then, the experiments on nano-TiO_2 inhibitory effect on the growth of cyanobacteria taken from Dianchi Lake were conducted under the irradiation of the high pressure mercury lamp、ultraviolet light lamp and the sunlight, respectively, which lay foundation for the preparation and application of modified nano-TiO_2．In the experiments, different proportion of Fe_2O_3, ZnO, WO_3, rare-earth element, and active carbon doped, respectively, on nano-TiO_2 were used to curb the growth of cyanobacteria taken from Dianchi Lake under the irradiation of sunlight. And different proportion of Ru、Ag、Pd and Pt doped nano-TiO_2 were used to study their inhibitory effects on growth of cyanobacteria from Dianchi Lake under the irradiation of sunlight and in dark room. The case in dark room eliminated the capability of noble metal ions to destroy cyanobacteria. Finally, the relatively high active of modified nano-TiO_2 photocatalysts selected from different types of photocatalysts were used in the study on the inhibitory effect on the growth of cyanobacteria from Dianchi Lake under the irradiation of sunlight. 1%Pt doped on nano-TiO_2 was used in small-scaled experiment in imitation of Dianchi Lake.
From above experiments, we could come to the following conclusions:
1．Using nano-TiO_2 under the irradiation of sunlight exerted little effect on curbing the growth of cyanobacteria from Dianchi Lake. However, it has exhibited better inhibitory effects under irradiation of the high pressure mercury lamp and ultraviolet light lamp. In the experiments of differently modified nano-TiO_2 photocatalysts, the noble metal doped nano-TiO_2, 5%ZnO doped nano-TiO_2, 40% actived carbon doped nano-TiO_2 and rare-earth element 3．3%MnO_2/6．7%CeO_2 doped nano-TiO_2 could effectively curb the growth of cyanobacteria from the Dianchi Lake exposed to the sunlight.
2．After the experiments of the modified nano-TiO_2 photocatalysts on the studies of inhibitory effects on the growth of cyanobacteria under the same condition, we got the activity sequence of the modified nano-TiO_2, which was 1%Ag/TiO_2 > 1% Pt/ TiO_2 > 40%active carbon/TiO_2 > 3．3%MnO_2/6．7% CeO_2 / TiO_2 >5%ZnO/ TiO_2．
3．It was found that the amount of photocatalyst had effect on the growth of Cyanobacteria .If the amount was too small, the adsorption of Cyanobacteria would be incompleted, where as too high amount would result in high cost.The suitable amount was found to be 0．1g photocalyst when the chlorophyll is 4．2g·L~(-1) in 25mL liqual.
4．The mechanism how modified nano-TiO_2 photocatalysts exert inhibitory effect on the growth of Cyanobacteria was studied.
To summary in this thesis, it is for the first time to apply different proportion of Fe_2O_3, ZnO, WO_3 doped respectively on nano-TiO_2 complex semiconductor to the studies on inhibitory effects on growth of cyanobacteria taken from Dianchi Lake, to use modified nano-TiO_2 by rare-earth element to the studies on inhibitory effects on growth of cyanobacteria taken from Dianchi Lake, to employ the noble metal Ru, Ag, Pd and Pt doped respectively on nano-TiO_2 to the studies on inhibitory effects on growth of cyanobacteria from Dianchi Lake, and to use TiO_2-mounted activated carbon to the studies on inhibitory effects on the growth of cyanobacteria. Finally, a new reagent, 4-(2-hydroxy-naphthalene-1-ylmefhylene)-thiazolidine-2, 5-dithione (HNMTD) was synthesized during the process of determination of the content and form of noble metal existing in the photocatalyst. A new method for the simultaneous determination of palladium, platinum and rutium ions as metal-HNMTD chelates was developed using high performance liquid chromatography equipped with an on-line enrichment technique, and the method was applied with good results to the determination of the content and form of Ru, Ag, Pd and Pt in the photocatalyst.
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