碳纳米管吸附香烟烟气中有害物质与对TiO_2的改性研究
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摘要
碳纳米管(CNTs)，自从发现以来就成为富勒烯领域的研究热点。本文对碳纳米管的应用作了简要的介绍，并着重对与碳纳米管孔结构以及气体吸附，液体浸润、填充作用，催化剂载体等应用研究进行了报道。
本文研究了碳纳米管吸附性能应用：作吸附材料，吸附香烟烟气有害成分；作TiO_2光催化剂载体，制成复合光催化剂CNTs-TiO_2改进TiO_2光催化性能。
碳纳米管降低香烟毒性的研究中，在滤嘴中添加碳纳米管、活性炭、无机盐，提高滤嘴的滤毒能力。利用称重法评价所添加试剂对总粒相物的吸附量，其中CNTs的去除效果最好，而且浅处理的CNTs吸附效果优于深处理的CNTs，对不同加入量的CNTs的去除效率作了研究，综合两种因素，既去除烟气有害成分，同时节约成本，每支香烟中添加30mg的深处理的CNTs比较合适。
TiO_2光催化剂改性研究中，采用活性炭和CNTs两种材料作催化剂载体，制备了复合催化剂TiO_2／A.C和CNTs-TiO_2，并利用甲胺磷农药光降解对其光催化性能进行评价。采用溶胶—凝胶法制备复合光催化剂TiO_2／A.C和CNTs-TiO_2。在溶胶形成之前加入活性炭与CNTs，超声分散后，在磁力搅拌、机械搅拌下形成混合溶胶，陈化为凝胶、水洗、干燥、活化处理制得新光催化剂。制得的复合光催化剂的TEM谱图表明，纳米TiO_2颗粒附着在活性炭表面与CNTs管壁上。同时研究了复合光催化剂的光催化活性，对40.71mg／L甲胺磷农药光催化降解数据表明，350℃活化处理的TiO_ 2／A.C、CNTs-TiO_2光催化效果高于同等条件下机械混合的TiO_2和A.C、TiO_2和CNTs，前者的表观速率常数是后者的2.78和5.73倍。对于TiO_2／A.C，活性炭重量为30%，在500℃活化温度处理的光催化剂的光催化效果最好。CNTs-TiO_2复合光催化剂在CNTs重量含量为0％～1％光催化活性升高，450℃为适宜的活化温度。
Carbon nanotubes (CNTs), have bee a hot spot in studies on fullerene since it was discovered. In this thesis, the study on the application of CNTs was reported briefly. Pore structure and specific surface area of CNTs, the application of absorption properties, such as gas storage, liquid infiltrate or staffer, and catalytic carrier,, have been stressed.
In this thesis, the application of adsorption properties of CNTs were investigated. As adsorption materials, CNTs adsorbed the harmful substance of cigarettes; As the carrier of TiO2 photocatalyst, CNTs were added into TiO2 and made into CNTs-TiO2 compound photocatalyst to improve the photocatalytic ability of TiO2.
In study on reducing the toxicity of cigarettes, the reagents, such as CNTs.activated carbon,NaCI,MgSO4,Al(OH)3,were put into normal filtertips to remove nicotine and tar from the fume of cigarettes, adsorption capacity of the reagents was evaluated by the method of weighing by difference. Removing effect of CNTs was most effective among the above reagents and removing effect of list processing CNTs was better than that of deep processing CNTs. Considering the removing rate and removing efficiency at different additional amounts of CNTsJOmg CNTs per cigarette was suggested because this amount could remove the harmful substance effectively and save cost at the same time.
In study on TiO2 compound photocatalysts, activated carbon and CNTs were used as catalytic carriers in TiO2/A.C and CNTs-TiO2.The photocatalytic effects of these two compound photocatalysts were evaluated by photodegrading methamidophos.
TiO2/A.C and CNTs-TiO2 were made by the method of sol-gel. A.C and CNTs
were added and dispersed into the solution by ultrasound before gelate, then formed compound sol with magnetic stirring and mechanic stirring, mellowed into gel, rinsed and desiccated, activatively processed and we could get compound photocatalysts. From their TEM, nanoparticles of TiO2 were adhere to the surface of A. C and external wall of CNTs. The photocatalytic properties of compound photocatalysts were investigated. The data of degrading methamidophos of the concentration of 40.71 mg/L in the same condition showed that the photocatalytic effects of compound photocatalyst activated at 350?C were better than mechanical mixed TiO2 and A.C or TiO2 and CNTs. The apparent photodegradation rate constants of the former were 2.78 and 5.73 fold. The photocatalytic effect of a.c-containing(30wt%) TiO2/A.C activated at 500℃ was best. Photoactivity of CNTs-TiO2 was improved when the content of CNTs varied from 0% to 1%, and the appropricate activation temperature of CNTs-TiO2 was about 450℃.
本文研究了碳纳米管吸附性能应用：作吸附材料，吸附香烟烟气有害成分；作TiO_2光催化剂载体，制成复合光催化剂CNTs-TiO_2改进TiO_2光催化性能。
碳纳米管降低香烟毒性的研究中，在滤嘴中添加碳纳米管、活性炭、无机盐，提高滤嘴的滤毒能力。利用称重法评价所添加试剂对总粒相物的吸附量，其中CNTs的去除效果最好，而且浅处理的CNTs吸附效果优于深处理的CNTs，对不同加入量的CNTs的去除效率作了研究，综合两种因素，既去除烟气有害成分，同时节约成本，每支香烟中添加30mg的深处理的CNTs比较合适。
TiO_2光催化剂改性研究中，采用活性炭和CNTs两种材料作催化剂载体，制备了复合催化剂TiO_2／A.C和CNTs-TiO_2，并利用甲胺磷农药光降解对其光催化性能进行评价。采用溶胶—凝胶法制备复合光催化剂TiO_2／A.C和CNTs-TiO_2。在溶胶形成之前加入活性炭与CNTs，超声分散后，在磁力搅拌、机械搅拌下形成混合溶胶，陈化为凝胶、水洗、干燥、活化处理制得新光催化剂。制得的复合光催化剂的TEM谱图表明，纳米TiO_2颗粒附着在活性炭表面与CNTs管壁上。同时研究了复合光催化剂的光催化活性，对40.71mg／L甲胺磷农药光催化降解数据表明，350℃活化处理的TiO_ 2／A.C、CNTs-TiO_2光催化效果高于同等条件下机械混合的TiO_2和A.C、TiO_2和CNTs，前者的表观速率常数是后者的2.78和5.73倍。对于TiO_2／A.C，活性炭重量为30%，在500℃活化温度处理的光催化剂的光催化效果最好。CNTs-TiO_2复合光催化剂在CNTs重量含量为0％～1％光催化活性升高，450℃为适宜的活化温度。
Carbon nanotubes (CNTs), have bee a hot spot in studies on fullerene since it was discovered. In this thesis, the study on the application of CNTs was reported briefly. Pore structure and specific surface area of CNTs, the application of absorption properties, such as gas storage, liquid infiltrate or staffer, and catalytic carrier,, have been stressed.
In this thesis, the application of adsorption properties of CNTs were investigated. As adsorption materials, CNTs adsorbed the harmful substance of cigarettes; As the carrier of TiO2 photocatalyst, CNTs were added into TiO2 and made into CNTs-TiO2 compound photocatalyst to improve the photocatalytic ability of TiO2.
In study on reducing the toxicity of cigarettes, the reagents, such as CNTs.activated carbon,NaCI,MgSO4,Al(OH)3,were put into normal filtertips to remove nicotine and tar from the fume of cigarettes, adsorption capacity of the reagents was evaluated by the method of weighing by difference. Removing effect of CNTs was most effective among the above reagents and removing effect of list processing CNTs was better than that of deep processing CNTs. Considering the removing rate and removing efficiency at different additional amounts of CNTsJOmg CNTs per cigarette was suggested because this amount could remove the harmful substance effectively and save cost at the same time.
In study on TiO2 compound photocatalysts, activated carbon and CNTs were used as catalytic carriers in TiO2/A.C and CNTs-TiO2.The photocatalytic effects of these two compound photocatalysts were evaluated by photodegrading methamidophos.
TiO2/A.C and CNTs-TiO2 were made by the method of sol-gel. A.C and CNTs
were added and dispersed into the solution by ultrasound before gelate, then formed compound sol with magnetic stirring and mechanic stirring, mellowed into gel, rinsed and desiccated, activatively processed and we could get compound photocatalysts. From their TEM, nanoparticles of TiO2 were adhere to the surface of A. C and external wall of CNTs. The photocatalytic properties of compound photocatalysts were investigated. The data of degrading methamidophos of the concentration of 40.71 mg/L in the same condition showed that the photocatalytic effects of compound photocatalyst activated at 350?C were better than mechanical mixed TiO2 and A.C or TiO2 and CNTs. The apparent photodegradation rate constants of the former were 2.78 and 5.73 fold. The photocatalytic effect of a.c-containing(30wt%) TiO2/A.C activated at 500℃ was best. Photoactivity of CNTs-TiO2 was improved when the content of CNTs varied from 0% to 1%, and the appropricate activation temperature of CNTs-TiO2 was about 450℃.
引文
1. DresselhausM.S. Nanotechnology: new tricks with nanotubes. Nature [J], 1998, 391: 19.
2. CollinsPG, ZettlA, BandsH. Nanotube nanodevice. Science[J], 1997, 278: 100 102.
3. ChiohioL, CrespiVH. Pure carbon nanoscale devices: nanotube hetero junctions. Phys. Rev lett[J], 1996, 76: 971.
4．陈久岭．博士论文，天津大学，1999
5．解思深，潘正伟．物理[J]，1999，(28)1：1
6．朱绍文，贾志杰．碳纳米管及其应用的研究现状．功能材料[J]，2000，31(2)：119-120．
7. GaoHJ,XueZQ, WuQD, etal. Solid State Communication, 1996, 7(97): 579～582
8．王文英．新型化工材料[J]，，2000，(1)：12
9. SaitoR, FujitaM, DresselhausG, etal. Appl Phys Lett [J], 1992, (60): 2204
10. CollinsPG, ZettlA, BandoH, etal. Science [J], 1997,(278):100
11. SaitoR, DresselhausG, DresselhausMS. Phys Rev[J], 1996,(53):11108
12. BezryadinA,VerschuerenARM, TansSJ. Phys Rev Lett[J] ,1998,(80):4036
13. LangerL, StookmanL, HeremansJP, etal. J. mater Res[J], 1994,(9):927
14. DeHeerWA, ChatelainA, VgarteK. Science[J], 1995,(270):1179
15. Niuc, SichelEK, HochR,etal. High Power Electrochemical Capacitors Based on Carbon Nanotubes. Appl. Phys. Lett[J]. 1997,70(11):1480
16. YuRQ, ChenLW, etal. Chem. Mater[J], 1998, 10: 718
17. DaiHJ, HafmerJH, RinzlerAG. Nanotubes as Nanoprobes in Scanning Probe Microscopy. Nature[J], 1996, 384: 147
18．董树荣，张效彬，徐江平．材料科学与技术[J]，1998，16(2)：19
19．张宇，吴汜昕，张鸿斌．物理化学学报[J]，1997，13(12)：1057
20．王文英．新型化工材料[J]，2000，(1)：12
21. DillonAC, JonesKM, BekedahlTA, KlangCH. Nature[J], 1997,(386):377
22. ChenP, WuX, LinJ, etal. High H_2 up take by alkali doped carbon nanotubes under ambient pressure and moderate temperature. Science[J], 1999, 285:91 93.
23. Q. H. Yang, P. X. Hou, S. Bai, etal. phys. lett[J]. accepted for publication.
24. 金子克美．固体物理[J] 1992，27(6)，403
25. S. Inoue, N. Ichikuni, T. Suzuki, etal. J. Phys. Chem. B[J], 1998, 102(24), 4689
26. M. Eswaramoorthy, R. Sen, C. N. R. Rao. Chem. Phys. Lett. [J], 1999, 304,207
27. Q. H. Yang, Y. Y. Fan, F. Li, etal. Extended Abstracts Eurocarbon, 2000, (Berlin, German Carbon Group, 2000) p1023
28. M. Jagtoyen, F. Derbyshire, J. Pardue, etal. Extended Abstracts Carbon'99. (USA. AmericanCarbon Society. 1999) p.86
29. E. Alain. B. McEnaney. T. Mays. Extended Abstracts. Carbon'99. (USA. American Carbon Society. 1999) p.88
30. 杨全红，李峰，侯鹏翔，刘畅，刘敏，成会明．科学通报[J]，2001，46(7)，600
31. G. Gadd, M. Blackford, S. Morica, etal. Science[J], 1997, 277, 933
32. P. G. Collins, K. Bradley, M. Ishigami, etal. Science [J], 2000, 87, 1801
33. G. Stan, M. Cole. Surface Science [J], 1998, 395, 280
34. D. Ugarte,T. Stockli, J. Bonard, etal. The Science and Technology of Carbon nanotubes. Edited by K. Tanaka, T. Yamabe, K. Fukui (Netherlands, Elsevier Science Ltd., 1999)p. 136
35. E.Dujardin, T. W. Ebbesen, H. Hiura, etal. Science [J], 1994, 265, 1850
36. Planeix J M, Coustel N, Coq B, etal. Application of carbon nanotubes as supports in heterogeneous catalysis[J]. J. Am. Chem. Soc. [J], 1994, 116: 7935～7936.
37. Hoogenraad M S, Onwezen M F, van Dillen A J, etal. Supported catalysts based on carbon fibers [A]. Hightower JW, Delgass W N, Iglesia E, etal. (eds.). Stud. Surf. Sci. Catal. [M]. Amsterdam: Elsevier, 1996, 101: 1331～1339
38. Rodriguez Nelly M, Kim myungsoo, Terry R, etal, Carbon nanofibers: a unique catalyst support medium, J. Phys. Chem. [J], 1994, 98: 13108～13111.
39．陈萍，张鸿斌，林国栋，等．高等学校化学学报[J]，1998，19(5)：765～769．
40. Chenhongbo, Linjing dong, Caiyun, etal. Novelmultiwalled nanotubes supported and alkali promoted Rucdatalysts for ammonia synthesis under atmosphenic pressure [J]. Appl Surf Sci, 2001, 180: 328～335.
41．姜明．除去烟焦油的香烟滤嘴的制备方法[P]．CN11 94，123．1998-09-30
42. Covarrubias, Jesus. Cigaret filter for the administration of taurine by inhalation[P]. EP 591, 048. 1994-04--06
43. Yokota, Hiroshi; Kojima, Akio. Tobaccofilter containing aminobenzoic acid[P]. JP 04 16, 178. 1992-01-21
44. Stavidis, Loanais; Deliconstantinos, Geroge. PCT INT. W. O. WO 96 0,019.1996-01-04
45. Nishii, Junji; Da Silva: Adilsonoliveira et al. Film of TiO2 containing SiO2 and a method of forming the same[P]. Eur. pat. Appl. EP 96 7,008.1999-11-29
46. Ogawa, Mayumi. Filter for cigarette[P]. JP 2000 210, 069. 2000-08-02
47. Umemeto, Masao. Nicotine-removing cigarette filter[P]. JP 2000 300, 239. 2000-10-31
48. Hoffmann MR, Martin ST, Choi W et al. Chem. Rev.[J], 1995, 95(1), 69～96
49. Torimoto T, Ito S, Kuwabata S etal., Environ. Sci .Technol. [J], 1996, 30, 1275
50. Xu Y M, Langford C H. J. Phys. Chem.[J], 1995, 99, 11501～11507
2. CollinsPG, ZettlA, BandsH. Nanotube nanodevice. Science[J], 1997, 278: 100 102.
3. ChiohioL, CrespiVH. Pure carbon nanoscale devices: nanotube hetero junctions. Phys. Rev lett[J], 1996, 76: 971.
4．陈久岭．博士论文，天津大学，1999
5．解思深，潘正伟．物理[J]，1999，(28)1：1
6．朱绍文，贾志杰．碳纳米管及其应用的研究现状．功能材料[J]，2000，31(2)：119-120．
7. GaoHJ,XueZQ, WuQD, etal. Solid State Communication, 1996, 7(97): 579～582
8．王文英．新型化工材料[J]，，2000，(1)：12
9. SaitoR, FujitaM, DresselhausG, etal. Appl Phys Lett [J], 1992, (60): 2204
10. CollinsPG, ZettlA, BandoH, etal. Science [J], 1997,(278):100
11. SaitoR, DresselhausG, DresselhausMS. Phys Rev[J], 1996,(53):11108
12. BezryadinA,VerschuerenARM, TansSJ. Phys Rev Lett[J] ,1998,(80):4036
13. LangerL, StookmanL, HeremansJP, etal. J. mater Res[J], 1994,(9):927
14. DeHeerWA, ChatelainA, VgarteK. Science[J], 1995,(270):1179
15. Niuc, SichelEK, HochR,etal. High Power Electrochemical Capacitors Based on Carbon Nanotubes. Appl. Phys. Lett[J]. 1997,70(11):1480
16. YuRQ, ChenLW, etal. Chem. Mater[J], 1998, 10: 718
17. DaiHJ, HafmerJH, RinzlerAG. Nanotubes as Nanoprobes in Scanning Probe Microscopy. Nature[J], 1996, 384: 147
18．董树荣，张效彬，徐江平．材料科学与技术[J]，1998，16(2)：19
19．张宇，吴汜昕，张鸿斌．物理化学学报[J]，1997，13(12)：1057
20．王文英．新型化工材料[J]，2000，(1)：12
21. DillonAC, JonesKM, BekedahlTA, KlangCH. Nature[J], 1997,(386):377
22. ChenP, WuX, LinJ, etal. High H_2 up take by alkali doped carbon nanotubes under ambient pressure and moderate temperature. Science[J], 1999, 285:91 93.
23. Q. H. Yang, P. X. Hou, S. Bai, etal. phys. lett[J]. accepted for publication.
24. 金子克美．固体物理[J] 1992，27(6)，403
25. S. Inoue, N. Ichikuni, T. Suzuki, etal. J. Phys. Chem. B[J], 1998, 102(24), 4689
26. M. Eswaramoorthy, R. Sen, C. N. R. Rao. Chem. Phys. Lett. [J], 1999, 304,207
27. Q. H. Yang, Y. Y. Fan, F. Li, etal. Extended Abstracts Eurocarbon, 2000, (Berlin, German Carbon Group, 2000) p1023
28. M. Jagtoyen, F. Derbyshire, J. Pardue, etal. Extended Abstracts Carbon'99. (USA. AmericanCarbon Society. 1999) p.86
29. E. Alain. B. McEnaney. T. Mays. Extended Abstracts. Carbon'99. (USA. American Carbon Society. 1999) p.88
30. 杨全红，李峰，侯鹏翔，刘畅，刘敏，成会明．科学通报[J]，2001，46(7)，600
31. G. Gadd, M. Blackford, S. Morica, etal. Science[J], 1997, 277, 933
32. P. G. Collins, K. Bradley, M. Ishigami, etal. Science [J], 2000, 87, 1801
33. G. Stan, M. Cole. Surface Science [J], 1998, 395, 280
34. D. Ugarte,T. Stockli, J. Bonard, etal. The Science and Technology of Carbon nanotubes. Edited by K. Tanaka, T. Yamabe, K. Fukui (Netherlands, Elsevier Science Ltd., 1999)p. 136
35. E.Dujardin, T. W. Ebbesen, H. Hiura, etal. Science [J], 1994, 265, 1850
36. Planeix J M, Coustel N, Coq B, etal. Application of carbon nanotubes as supports in heterogeneous catalysis[J]. J. Am. Chem. Soc. [J], 1994, 116: 7935～7936.
37. Hoogenraad M S, Onwezen M F, van Dillen A J, etal. Supported catalysts based on carbon fibers [A]. Hightower JW, Delgass W N, Iglesia E, etal. (eds.). Stud. Surf. Sci. Catal. [M]. Amsterdam: Elsevier, 1996, 101: 1331～1339
38. Rodriguez Nelly M, Kim myungsoo, Terry R, etal, Carbon nanofibers: a unique catalyst support medium, J. Phys. Chem. [J], 1994, 98: 13108～13111.
39．陈萍，张鸿斌，林国栋，等．高等学校化学学报[J]，1998，19(5)：765～769．
40. Chenhongbo, Linjing dong, Caiyun, etal. Novelmultiwalled nanotubes supported and alkali promoted Rucdatalysts for ammonia synthesis under atmosphenic pressure [J]. Appl Surf Sci, 2001, 180: 328～335.
41．姜明．除去烟焦油的香烟滤嘴的制备方法[P]．CN11 94，123．1998-09-30
42. Covarrubias, Jesus. Cigaret filter for the administration of taurine by inhalation[P]. EP 591, 048. 1994-04--06
43. Yokota, Hiroshi; Kojima, Akio. Tobaccofilter containing aminobenzoic acid[P]. JP 04 16, 178. 1992-01-21
44. Stavidis, Loanais; Deliconstantinos, Geroge. PCT INT. W. O. WO 96 0,019.1996-01-04
45. Nishii, Junji; Da Silva: Adilsonoliveira et al. Film of TiO2 containing SiO2 and a method of forming the same[P]. Eur. pat. Appl. EP 96 7,008.1999-11-29
46. Ogawa, Mayumi. Filter for cigarette[P]. JP 2000 210, 069. 2000-08-02
47. Umemeto, Masao. Nicotine-removing cigarette filter[P]. JP 2000 300, 239. 2000-10-31
48. Hoffmann MR, Martin ST, Choi W et al. Chem. Rev.[J], 1995, 95(1), 69～96
49. Torimoto T, Ito S, Kuwabata S etal., Environ. Sci .Technol. [J], 1996, 30, 1275
50. Xu Y M, Langford C H. J. Phys. Chem.[J], 1995, 99, 11501～11507