化学液相法合成纳米硒
摘要
硒是重要的半导体材料，同时也是生命的必需元素，而纳米尺寸的硒所具有的在材料上的独特性能和在生命中的特殊生物活性更是引起了人们对硒化学的研究热潮。化学液相纳米合成技术具有方法简单、产品的化学组成易控制等优点，在纳米材料的制备方面显示了广阔的应用前景。本论文用几种低温液相合成技术制备纳米硒，旨在寻找有效控制合成各种结构纳米硒的方法。
1．反相微乳液法：以十二烷基硫酸钠为表面活性剂，正丁醇为助表面活性剂，环己烷为溶剂，以硒代硫酸钠的歧化反应为基础制备纳米硒，得到了粒径较均匀的球形颗粒和长径比较大的纳米线。讨论了影响产物形貌的因素和产物形成的机理。
2．有机介质超声法：以无水乙醇作为反应介质，在超声波作用下合成纳米硒，得到了由球形α-晶形硒定向聚集成的纳米线。在聚乙二醇辛基苯基醚(OP)介质中，超声法合成了微米级的OP-Se复合球结构。
3．水溶液体系表面活性剂模板法：以聚乙烯吡咯烷酮(PVP)为模板，用浓HCI自然扩散法和沉淀法，合成了球形、棒状和线状的的纳米硒。分别以十二烷基硫酸钠(SDS)、聚乙二醇辛基苯基醚(OP)、氯代十六烷基吡啶、聚丙烯酰胺、L—苯丙氨酸为模板，用沉淀法合成了线状和球形纳米硒。对模板的保护诱导作用作了阐述，对纳米线的形成路线作了总结。
4．Ag核诱导法：在PVP的保护下以生成的Ag核为晶种合成纳米硒，得到了Se的棒状结构，并有Se纳米管的存在。对Ag核的诱导作用进行了分析与讨论。
Selenium (Se) is not only an important semiconductor material but also an essential element in life. The Se nanoparticles have aroused great interest due to its special properties on material and biological activity in life. In synthesizing Se nanoparticles, chemical technology with low temperature liquid phase, which possesses some virtues such as low reaction temperature, low cost as well as high control ability for the morphology of products, has received much attention. In this thesis, some chemical approaches with low temperature liquid phase have been employed to prepare Se nanoparticles and varied Se nanoparticles were obtained.
1. Reverse microemulsion method Se nanoparticles were prepared by using sodium dodecane (SDS) as surfactant, n-butanol as aid-surfactant and cyclohesane as solvent. The reaction was based the reduction of Na2SeSO3 to elemental Se in acid environment. The uniform spherical Se nanoparticles and Se nanowires were obtained. The factors affecting the morphologies of the products and the formation mechanism of Se nanoparticles were discussed.
2. Organic-medium ultrasonic method Se nanoparticles were prepared under ultrasound irradiation condition in organic solvent. One-dimension selenium nonostructures were obtained under ultrasound irradiation condition in ethanol medium. Spherical OP-Se micronscale compound was prepared under ultrasound irradiation condition in OP medium.
3. Aqueous method using surfactants as soft templates Using polyvinylpyrrolidone (PVP) as a template, Se nanoparticles with various morphologies, such as nanospheres, nanorods and nanowires, were prepared in HCl-diffusing method and precipitation method. Se nanospheres and nanowires were also obtained using other surfactants as templates, such as sodium
dodecylsulfate, polyethylene glycol tert-octylpheneylether, hexadecyl pyridinium chloride, polyacrylamide and L-phenyl alanine. The function of templates to the formation of nanoparticles and the synthesis mechanism were discussed.
4. Ag crystal nucleus method Se nanoparticles were prepared by using Ag crystal nucleus as inducing reagent in the presence of PVP. Se nanorods containing nanotubes were obtained. The function of Ag crystal nucleus was studied.
1．反相微乳液法：以十二烷基硫酸钠为表面活性剂，正丁醇为助表面活性剂，环己烷为溶剂，以硒代硫酸钠的歧化反应为基础制备纳米硒，得到了粒径较均匀的球形颗粒和长径比较大的纳米线。讨论了影响产物形貌的因素和产物形成的机理。
2．有机介质超声法：以无水乙醇作为反应介质，在超声波作用下合成纳米硒，得到了由球形α-晶形硒定向聚集成的纳米线。在聚乙二醇辛基苯基醚(OP)介质中，超声法合成了微米级的OP-Se复合球结构。
3．水溶液体系表面活性剂模板法：以聚乙烯吡咯烷酮(PVP)为模板，用浓HCI自然扩散法和沉淀法，合成了球形、棒状和线状的的纳米硒。分别以十二烷基硫酸钠(SDS)、聚乙二醇辛基苯基醚(OP)、氯代十六烷基吡啶、聚丙烯酰胺、L—苯丙氨酸为模板，用沉淀法合成了线状和球形纳米硒。对模板的保护诱导作用作了阐述，对纳米线的形成路线作了总结。
4．Ag核诱导法：在PVP的保护下以生成的Ag核为晶种合成纳米硒，得到了Se的棒状结构，并有Se纳米管的存在。对Ag核的诱导作用进行了分析与讨论。
Selenium (Se) is not only an important semiconductor material but also an essential element in life. The Se nanoparticles have aroused great interest due to its special properties on material and biological activity in life. In synthesizing Se nanoparticles, chemical technology with low temperature liquid phase, which possesses some virtues such as low reaction temperature, low cost as well as high control ability for the morphology of products, has received much attention. In this thesis, some chemical approaches with low temperature liquid phase have been employed to prepare Se nanoparticles and varied Se nanoparticles were obtained.
1. Reverse microemulsion method Se nanoparticles were prepared by using sodium dodecane (SDS) as surfactant, n-butanol as aid-surfactant and cyclohesane as solvent. The reaction was based the reduction of Na2SeSO3 to elemental Se in acid environment. The uniform spherical Se nanoparticles and Se nanowires were obtained. The factors affecting the morphologies of the products and the formation mechanism of Se nanoparticles were discussed.
2. Organic-medium ultrasonic method Se nanoparticles were prepared under ultrasound irradiation condition in organic solvent. One-dimension selenium nonostructures were obtained under ultrasound irradiation condition in ethanol medium. Spherical OP-Se micronscale compound was prepared under ultrasound irradiation condition in OP medium.
3. Aqueous method using surfactants as soft templates Using polyvinylpyrrolidone (PVP) as a template, Se nanoparticles with various morphologies, such as nanospheres, nanorods and nanowires, were prepared in HCl-diffusing method and precipitation method. Se nanospheres and nanowires were also obtained using other surfactants as templates, such as sodium
dodecylsulfate, polyethylene glycol tert-octylpheneylether, hexadecyl pyridinium chloride, polyacrylamide and L-phenyl alanine. The function of templates to the formation of nanoparticles and the synthesis mechanism were discussed.
4. Ag crystal nucleus method Se nanoparticles were prepared by using Ag crystal nucleus as inducing reagent in the presence of PVP. Se nanorods containing nanotubes were obtained. The function of Ag crystal nucleus was studied.
引文
1. Ball P, Garwin L, Nature. 1992, 355:761
2. Kamat P V, Dimitry N D, Solar Energy. 1990, 44:83
3. Cavicchi P E, Silsbee R H, Phys. Rew. Lett. 1984, 52:1453
4．张立德，牟季美，物理．1992，21(3)：167
5. Laford A, Meerschaut A, Gressier P, Rouxel J, J Solid State Chem. 1993, 103: 458
6．李新勇，李树本，化学进展．1996，8：231
7．宫晓梅，半导体纳米微晶的控制合成及非线性光学性能研究．安徽大学．2003
8. Moffitt M, Vali H, Elisenberg A, Chem. Mater. 1998, 10:1021
9. Meldrum F C, Wade V J, Nimmo D L, Mann S, Nature. 1991, 349:684
10. Chen M, Xie Y, Chen H, J. Colloid Interf. Soc. 2000, 229:217
11. Touroude R, Girarard P, Maire G, Colloids Surfaces. 1992, 67:19
12. Ding J H, Douglas G, Chem. Mater. 2000, 12: 22
13．杨中民，信文瑜，王月平，云南化工．2002，27(1)：22
14．张立德，现化科学仪器．1998，1-2：27
15．凌永乐，化学元素的发现．科学出版社．1981
16. Bloomfield M M, Chemistry and the Living Organism. 1977
17. Johnson J A, Saboungi M L, Thiyagarajan P, Csencsits R, Meisel D J, Phys. Chem B. 1999, 103:59
18. Bailar J C, Comprehensive Inorganic Chemistry. Pergamon Press. 1973, 2
19. Cotton F A, Wilkinson G, Advanced Inorganic Chemistry. 4th, ed. John Wiley &Sons, 1980
20．冯光熙，黄祥玉，申泮文，等．无机化学丛书(第一卷)．科学出版社．1984
21. Emeleus H J, Sharpe A G, Advances Inorganic Chemistry and Radiochemistry. Academic Press. 1981, 24
22．杨俊诚，朱永懿，陈景坚，农业环境与发展．1994，42：37
23. Banuelos, et al. Commun. in Soil Plant Anal. 1990, 21:13
24. Rosenfeld I, Academic Press. New York. 1964
25. Underwood, E J. Academic Press. New York. 1977
26．杜式华等，环境科学．1988，8(6)
27．姚凤仪，郭德威，桂明德，无机化学丛书(第五卷)．北京科学出版社，1998
28. Paulmier C, Selenium reagents and intermediates in org. Synthesis. Pergamon Press. 1986
29．刘进国，于建宁，广东饮料．2003．12(4)：20
30．高学云，张劲松，等．中国公共卫生．2000，16(5)：421
31．张劲松，高学云，张立德，等．营养学报．2001，23(1)：32
32．郑青山，张劲松，桂常青，等．中国药理学通报．2002，18(1)：99
33．张劲松，高学云，张立德，等．营养学报，2000，22(3)：219
34. Gates B, Mayers B, Cattle B, Xia Y N, Adv. Funct. Mater. 2002, 12:3
35. Chizhikov D M, Shchastlivyi V P, Selenium and Selenides. Collets Publishing. London. 1968
36. Best E, Hinz I, Wendt H, Gmelin Handbuch der Anorganischen Chemie. Spinger. Berlin. 1979, 10
37. Patil K R, Paranjape D V, Sathaye S D, Mitra A, Padalkar S R, Mandale A B, Materials Letters. 2000, 46:81
38. Umehara A, Nitta S, Furukawa H, Nonomura S, Applied Surface Science. 1997, 119:176
39．张皓月，卢柯，胡壮麟，物理学报．1995，44(1)：109
40. Abdelouas A, Gong W L, Lutze W, et al. Chem. Mater. 2000, 12:1510
41．张旭，谢毅，徐芬，刘晓惠，无机化学学报．2003，19(1)：77
42. Johnson J A, Saboungi M L, Thiyagarajan P, et al. J. Phys. Chem. B. 1999, 103: 59
43. Smith T W, Cheatham R A, Macromolecules. 1980, 13: 1203
44. Rajalakshmi M, Arora A K, Solid State Communications. 1999, 110: 75
45. Gao X Y, Zhang J S, Zhang L D, Adv. Mater. 2002, 14: 4;
46. Mees D R, Pysto W, Tarcha P J, Journal of Colloid and Interface Science. 1995, 170: 254
47. Watilion A, Dauchot J, Journal of Colloid and Interface Science. 1968, 27(3): 507
48. Gates B, Mayers B, Grossman A, Xia Y N, Adv. Mater. 2002, 14(23): 1749
49. Zhu Y J, Qian Y T, Huang H, Zhang M W, Materials Letters. 1996, 28: 119
50．黄峙，郑文杰，李乐农，郭宝江，中国生物工程杂志．2003，7：76
51．黄峙，食品科学．2001，22(5)：90
2. Kamat P V, Dimitry N D, Solar Energy. 1990, 44:83
3. Cavicchi P E, Silsbee R H, Phys. Rew. Lett. 1984, 52:1453
4．张立德，牟季美，物理．1992，21(3)：167
5. Laford A, Meerschaut A, Gressier P, Rouxel J, J Solid State Chem. 1993, 103: 458
6．李新勇，李树本，化学进展．1996，8：231
7．宫晓梅，半导体纳米微晶的控制合成及非线性光学性能研究．安徽大学．2003
8. Moffitt M, Vali H, Elisenberg A, Chem. Mater. 1998, 10:1021
9. Meldrum F C, Wade V J, Nimmo D L, Mann S, Nature. 1991, 349:684
10. Chen M, Xie Y, Chen H, J. Colloid Interf. Soc. 2000, 229:217
11. Touroude R, Girarard P, Maire G, Colloids Surfaces. 1992, 67:19
12. Ding J H, Douglas G, Chem. Mater. 2000, 12: 22
13．杨中民，信文瑜，王月平，云南化工．2002，27(1)：22
14．张立德，现化科学仪器．1998，1-2：27
15．凌永乐，化学元素的发现．科学出版社．1981
16. Bloomfield M M, Chemistry and the Living Organism. 1977
17. Johnson J A, Saboungi M L, Thiyagarajan P, Csencsits R, Meisel D J, Phys. Chem B. 1999, 103:59
18. Bailar J C, Comprehensive Inorganic Chemistry. Pergamon Press. 1973, 2
19. Cotton F A, Wilkinson G, Advanced Inorganic Chemistry. 4th, ed. John Wiley &Sons, 1980
20．冯光熙，黄祥玉，申泮文，等．无机化学丛书(第一卷)．科学出版社．1984
21. Emeleus H J, Sharpe A G, Advances Inorganic Chemistry and Radiochemistry. Academic Press. 1981, 24
22．杨俊诚，朱永懿，陈景坚，农业环境与发展．1994，42：37
23. Banuelos, et al. Commun. in Soil Plant Anal. 1990, 21:13
24. Rosenfeld I, Academic Press. New York. 1964
25. Underwood, E J. Academic Press. New York. 1977
26．杜式华等，环境科学．1988，8(6)
27．姚凤仪，郭德威，桂明德，无机化学丛书(第五卷)．北京科学出版社，1998
28. Paulmier C, Selenium reagents and intermediates in org. Synthesis. Pergamon Press. 1986
29．刘进国，于建宁，广东饮料．2003．12(4)：20
30．高学云，张劲松，等．中国公共卫生．2000，16(5)：421
31．张劲松，高学云，张立德，等．营养学报．2001，23(1)：32
32．郑青山，张劲松，桂常青，等．中国药理学通报．2002，18(1)：99
33．张劲松，高学云，张立德，等．营养学报，2000，22(3)：219
34. Gates B, Mayers B, Cattle B, Xia Y N, Adv. Funct. Mater. 2002, 12:3
35. Chizhikov D M, Shchastlivyi V P, Selenium and Selenides. Collets Publishing. London. 1968
36. Best E, Hinz I, Wendt H, Gmelin Handbuch der Anorganischen Chemie. Spinger. Berlin. 1979, 10
37. Patil K R, Paranjape D V, Sathaye S D, Mitra A, Padalkar S R, Mandale A B, Materials Letters. 2000, 46:81
38. Umehara A, Nitta S, Furukawa H, Nonomura S, Applied Surface Science. 1997, 119:176
39．张皓月，卢柯，胡壮麟，物理学报．1995，44(1)：109
40. Abdelouas A, Gong W L, Lutze W, et al. Chem. Mater. 2000, 12:1510
41．张旭，谢毅，徐芬，刘晓惠，无机化学学报．2003，19(1)：77
42. Johnson J A, Saboungi M L, Thiyagarajan P, et al. J. Phys. Chem. B. 1999, 103: 59
43. Smith T W, Cheatham R A, Macromolecules. 1980, 13: 1203
44. Rajalakshmi M, Arora A K, Solid State Communications. 1999, 110: 75
45. Gao X Y, Zhang J S, Zhang L D, Adv. Mater. 2002, 14: 4;
46. Mees D R, Pysto W, Tarcha P J, Journal of Colloid and Interface Science. 1995, 170: 254
47. Watilion A, Dauchot J, Journal of Colloid and Interface Science. 1968, 27(3): 507
48. Gates B, Mayers B, Grossman A, Xia Y N, Adv. Mater. 2002, 14(23): 1749
49. Zhu Y J, Qian Y T, Huang H, Zhang M W, Materials Letters. 1996, 28: 119
50．黄峙，郑文杰，李乐农，郭宝江，中国生物工程杂志．2003，7：76
51．黄峙，食品科学．2001，22(5)：90