메뉴 건너뛰기




Volumn 276, Issue 5314, 1997, Pages 923-926

Functionalized monolayers on ordered mesoporous supports

Author keywords

[No Author keywords available]

Indexed keywords

MONOLAYERS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POROUS MATERIALS; SURFACE PROPERTIES; SURFACE TREATMENT; SURFACES; SYNTHESIS (CHEMICAL);

EID: 0031560772     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.276.5314.923     Document Type: Article
Times cited : (1566)

References (38)
  • 1
    • 0012247651 scopus 로고
    • J. S. Beck et al., J. Am. Chem, Soc. 114, 10834 (1992); C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, J. S. Beck, Nature 359, 710 (1992).
    • (1992) J. Am. Chem, Soc. , vol.114 , pp. 10834
    • Beck, J.S.1
  • 3
    • 0029676390 scopus 로고    scopus 로고
    • Many papers on mesoporous materials have been published recently [for reviews, see J. S. Beck and J. C. Vartuli, Curr. Opin. Solid State Mater. Sci. 1, 76 (1996); J, Liu et al., Adv. Colloid Interface Sci. 69, 131 (1996)].
    • (1996) Curr. Opin. Solid State Mater. Sci. , vol.1 , pp. 76
    • Beck, J.S.1    Vartuli, J.C.2
  • 4
    • 0030381170 scopus 로고    scopus 로고
    • Many papers on mesoporous materials have been published recently [for reviews, see J. S. Beck and J. C. Vartuli, Curr. Opin. Solid State Mater. Sci. 1, 76 (1996); J, Liu et al., Adv. Colloid Interface Sci. 69, 131 (1996)].
    • (1996) Adv. Colloid Interface Sci. , vol.69 , pp. 131
    • Liu, J.1
  • 5
    • 0001736091 scopus 로고    scopus 로고
    • A. Sayari, Chem. Mater. 8, 1840 (1996); R. G. Anthony, C. V. Philips, R. G. Dosch, Waste Manage. 13, 503 (1993); K. D. Schierbaum, Science 265, 1413 (1994).
    • (1996) Chem. Mater. , vol.8 , pp. 1840
    • Sayari, A.1
  • 7
    • 0027968597 scopus 로고
    • A. Sayari, Chem. Mater. 8, 1840 (1996); R. G. Anthony, C. V. Philips, R. G. Dosch, Waste Manage. 13, 503 (1993); K. D. Schierbaum, Science 265, 1413 (1994).
    • (1994) Science , vol.265 , pp. 1413
    • Schierbaum, K.D.1
  • 8
    • 15144347458 scopus 로고    scopus 로고
    • note
    • 2, TMA/Si molar ratio 0.5, SACHEM Inc.), and 28 g of mesitylene (Eastman Kodak) were added to each 100 g of CTAC/OH solution. The mixture was sealed in a Teflon-lined vessel and heated at 105°C for 1 week. The product was recovered by suction filtration, dried at ambient temperature, and calcined at 540°C for 12 hours under flowing air.
  • 9
    • 15144346327 scopus 로고    scopus 로고
    • note
    • For synthesis of 10% FMMS samples, 2.0 ml of TMMPS was mixed with 1.288 g of mesoporous silica in 100 ml of chloroform. This mixture was stirred at room temperature for 5 days and then filtered. The collected solid was washed copiously with chloroform to rinse away any surplus mercaptan and then dried under vacuum. For synthesis of 25% FMMS samples, 4.32 g of mesoporous silica was suspended in 125 ml of reverse osmosis (RO) water and taken to reflux for 4 hours. After cooling to room temperature, the sample was centrifuged down, the water was decanted off, and the silica was air-dried for 5 days. This hydrated mesoporous silica was then suspended in 250 ml of toluene, treated with 30 ml of TMMPS, and taken to reflux for 4 hours. After cooling to room temperature, the reaction mixture was filtered. The solid was washed copiously with chloroform and dried under vacuum. For synthesis of 75% FMMS samples, 3.5 g of mesoporous silica was suspended in 100 ml of RO water and heated to reflux to 3 hours. The mixture was cooled and filtered. The wet product was placed in a round-bottom flask along with 250 ml of benzene. The flask was fitted with a Dean-Stark trap and the mixture was heated to reflux. The wet product was heavily aggregated for about the first half of the azeotropic distillation, and then it dispersed nicely. The Dean-Stark distillation was continued until 4.5 ml of water had been removed. This left ∼2.0 ml of water dispersed across the silica surface, which is approximately equal to four monolayers of water. This suspension was then treated with 20 ml of TMMPS, stirred overnight at room temperature, and heated to reflux for 4 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with 2-propanol and dried under vacuum to yield 6.2 g of derivatized material.
  • 11
    • 15144355668 scopus 로고    scopus 로고
    • note
    • 4Si] as an internal standard. Integration of the peaks from functionalized monolayers and from the internal standard allowed the determination of the number of alkylsiloxanes on the substrate.
  • 15
    • 1942481178 scopus 로고
    • M. D. Porter, T. B. Bright, D. L. Allara, A. E. D. Chidsey, J. Am. Chem. Soc. 109, 3559 (1987); C. D. Troughton et al., ibid. 111, 321 (1989); L. Netzer, R. Iscovici, J. Sagiv, Thin Solid Films 100, 67 (1983).
    • (1989) J. Am. Chem. Soc. , vol.111 , pp. 321
    • Troughton, C.D.1
  • 16
    • 0021094396 scopus 로고
    • M. D. Porter, T. B. Bright, D. L. Allara, A. E. D. Chidsey, J. Am. Chem. Soc. 109, 3559 (1987); C. D. Troughton et al., ibid. 111, 321 (1989); L. Netzer, R. Iscovici, J. Sagiv, Thin Solid Films 100, 67 (1983).
    • (1983) Thin Solid Films , vol.100 , pp. 67
    • Netzer, L.1    Iscovici, R.2    Sagiv, J.3
  • 18
    • 0001549364 scopus 로고    scopus 로고
    • L.-Q. Wang, J. Liu, G. J. Exarhos, B. C. Bunker, Langmuir 12, 2663 (1996); A. Badia et al., ibid., p. 1262.
    • Langmuir , pp. 1262
    • Badia, A.1
  • 19
    • 15144352463 scopus 로고    scopus 로고
    • note
    • 29Si NMR chemical shifts were referenced to TMS at 0 ppm.
  • 21
    • 36749107588 scopus 로고
    • III absorption edge on beamline X18B at the National Synchrotron Light Source. Measurements of tape mounts of mercury sulfide and mercury oxide standards were made in the transmission mode. Measurements on the FMMS samples were performed in the fluorescence mode, using the Stern-Heald configuration while simultaneously monitoring the absorption signal of the mercury sulfide reference on the downside of the experiment to allow investigation of the valence state of mercury in the sample. Data reduction and analysis were performed according to recommended procedures [E. A. Stem and S. M. Heald, Rev. Sci. Instrum. 50, 1579 (1979);
    • (1979) Rev. Sci. Instrum. , vol.50 , pp. 1579
    • Stem, E.A.1    Heald, S.M.2
  • 22
    • 0001188159 scopus 로고
    • D. C. Koningsberger and R. Prins, Eds. Wiley, New York, chap. 6
    • D. E. Sayers and B. A. Bunker, in X-ray Absorption, Principles, Applications, Techniques of EXAFS, SEXAFS, and XANES, D. C. Koningsberger and R. Prins, Eds. (Wiley, New York, 1988), pp. 211-256 and chap. 6]. The National Synchrotron Light Source at Brookhaven National Laboratory is supported by the U.S. Department of Energy, Office of Energy Research, Division of Materials Sciences and Division of Chemical Sciences.
    • (1988) X-ray Absorption, Principles, Applications, Techniques of EXAFS, SEXAFS, and XANES , pp. 211-256
    • Sayers, D.E.1    Bunker, B.A.2
  • 23
    • 15144357162 scopus 로고    scopus 로고
    • U.S. Department of Energy, Mixed Waste Focus Area, Technical Baseline Results (World Wide Web: http://wastenot.inel.gov/mwfa/results.html); U.S. Department of Energy, FY91 Waste and Hazard Minimization Accomplishments (DOE Report MHSMP-91-37, Pantex Plant, Amarillo, TX, 1991); J. E. Klein, Westinghouse Savannah River Company Inter-Office Memorandum SRT-HTS-94-0235 (11 July 1994).
    • Technical Baseline Results
  • 24
    • 0344434595 scopus 로고
    • DOE Report MHSMP-91-37, Pantex Plant, Amarillo, TX
    • U.S. Department of Energy, Mixed Waste Focus Area, Technical Baseline Results (World Wide Web: http://wastenot.inel.gov/mwfa/results.html); U.S. Department of Energy, FY91 Waste and Hazard Minimization Accomplishments (DOE Report MHSMP-91-37, Pantex Plant, Amarillo, TX, 1991); J. E. Klein, Westinghouse Savannah River Company Inter-Office Memorandum SRT-HTS-94-0235 (11 July 1994).
    • (1991) FY91 Waste and Hazard Minimization Accomplishments
  • 25
    • 15144350751 scopus 로고
    • 11 July
    • U.S. Department of Energy, Mixed Waste Focus Area, Technical Baseline Results (World Wide Web: http://wastenot.inel.gov/mwfa/results.html); U.S. Department of Energy, FY91 Waste and Hazard Minimization Accomplishments (DOE Report MHSMP-91-37, Pantex Plant, Amarillo, TX, 1991); J. E. Klein, Westinghouse Savannah River Company Inter-Office Memorandum SRT-HTS-94-0235 (11 July 1994).
    • (1994) Westinghouse Savannah River Company Inter-Office Memorandum SRT-HTS-94-0235
    • Klein, J.E.1
  • 27
    • 15144350364 scopus 로고    scopus 로고
    • note
    • The tests with simulated waste were performed in batch mode. The waste solutions were mixed with FMMS powders at volume ratios of 20 to 100 at room temperature with agitation for 2 hours. The remaining metal concentrations in solutions were analyzed by cold vapor atomic absorption for mercury and by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) for other metals. For hydrolytic stability, mercury-loaded FMMS was added to deionized water in a Teflon vessel and heated at 70°C for 24 hours. The original mercury concentration in the FMMS was 505 mg per gram of FMMS. After the heating, only 0.4% mercury was released from the materials. This is within the uncertainty involved in experimental procedures in which the mercury-loaded FMMS was washed to remove physically attached mercury before the release test. The regeneration test was performed as follows: Mercury-loaded FMMS was mixed with a concentrated HCl (12.1 M) solution for 4 hours. The solid materials were then separated by filtration. Analysis of the Hg concentration in the filtrate indicated that the mercury was 100% removed. The regenerated FMMS was used to treat a mercury nitrate solution. A mercury loading of 210 mg per gram of FMMS was obtained, corresponding to ∼50% of the original loading capacity. The same results were obtained for a third regeneration and reuse cycle. Although the total loading capacity was reduced in regeneration, it still outperforms alternative materials. Some loading capacity was lost as a result of the oxidation of the thiol group and can be recovered by treating the regenerated materials with a reducing agent. Some loading capacity loss may also be attributable to the interactions of FMMS with strong acid, but the densely populated organic monolayers improved the stability of the silica-based materials, so that the FMMS was not dissolved even in concentrated acid and remained effective after the acid treatment.
  • 28
    • 15144354583 scopus 로고
    • Y. Otanl, H. Eml, C. Kanaoka, H. Nishino, Environ. Sci. Technol. 22 (no. 6), 70 (1988); K. A. Larson and J. M. Wiencek, Environ. Prog. 13 (no. 4), 253 (1994); S. E. Ghazy, Sep. Sci. Technol. 30, 933 (1995); J. A. Ritter and J. P. Bibler, Water Sci. Technol. 25 (no. 3), 165 (1992).
    • (1988) Environ. Sci. Technol. , vol.22 , Issue.6 , pp. 70
    • Otanl, Y.1    Eml, H.2    Kanaoka, C.3    Nishino, H.4
  • 29
    • 0028534710 scopus 로고
    • Y. Otanl, H. Eml, C. Kanaoka, H. Nishino, Environ. Sci. Technol. 22 (no. 6), 70 (1988); K. A. Larson and J. M. Wiencek, Environ. Prog. 13 (no. 4), 253 (1994); S. E. Ghazy, Sep. Sci. Technol. 30, 933 (1995); J. A. Ritter and J. P. Bibler, Water Sci. Technol. 25 (no. 3), 165 (1992).
    • (1994) Environ. Prog. , vol.13 , Issue.4 , pp. 253
    • Larson, K.A.1    Wiencek, J.M.2
  • 30
    • 84892902381 scopus 로고
    • Y. Otanl, H. Eml, C. Kanaoka, H. Nishino, Environ. Sci. Technol. 22 (no. 6), 70 (1988); K. A. Larson and J. M. Wiencek, Environ. Prog. 13 (no. 4), 253 (1994); S. E. Ghazy, Sep. Sci. Technol. 30, 933 (1995); J. A. Ritter and J. P. Bibler, Water Sci. Technol. 25 (no. 3), 165 (1992).
    • (1995) Sep. Sci. Technol. , vol.30 , pp. 933
    • Ghazy, S.E.1
  • 31
    • 0026617325 scopus 로고
    • Y. Otanl, H. Eml, C. Kanaoka, H. Nishino, Environ. Sci. Technol. 22 (no. 6), 70 (1988); K. A. Larson and J. M. Wiencek, Environ. Prog. 13 (no. 4), 253 (1994); S. E. Ghazy, Sep. Sci. Technol. 30, 933 (1995); J. A. Ritter and J. P. Bibler, Water Sci. Technol. 25 (no. 3), 165 (1992).
    • (1992) Water Sci. Technol. , vol.25 , Issue.3 , pp. 165
    • Ritter, J.A.1    Bibler, J.P.2
  • 33
    • 0029373885 scopus 로고
    • September
    • G. M. Whitesides, Sci. Am. 273, 146 (September 1995); G. E. Fryxell et al., Langmuir 12, 5064 (1996).
    • (1995) Sci. Am. , vol.273 , pp. 146
    • Whitesides, G.M.1
  • 34
    • 0000148653 scopus 로고    scopus 로고
    • G. M. Whitesides, Sci. Am. 273, 146 (September 1995); G. E. Fryxell et al., Langmuir 12, 5064 (1996).
    • (1996) Langmuir , vol.12 , pp. 5064
    • Fryxell, G.E.1
  • 35
    • 0028299525 scopus 로고
    • B. C. Bunker et al., Science 264, 48 (1994); P. Calvert, Nature 334, 651 (1988); _and P. Rieke, Chem. Mater. 8, 1715 (1996).
    • (1994) Science , vol.264 , pp. 48
    • Bunker, B.C.1
  • 36
    • 0005768241 scopus 로고
    • B. C. Bunker et al., Science 264, 48 (1994); P. Calvert, Nature 334, 651 (1988); _and P. Rieke, Chem. Mater. 8, 1715 (1996).
    • (1988) Nature , vol.334 , pp. 651
    • Calvert, P.1
  • 37
    • 0001713166 scopus 로고    scopus 로고
    • B. C. Bunker et al., Science 264, 48 (1994); P. Calvert, Nature 334, 651 (1988); _and P. Rieke, Chem. Mater. 8, 1715 (1996).
    • (1996) Chem. Mater. , vol.8 , pp. 1715
    • Rieke, P.1
  • 38
    • 15144346551 scopus 로고    scopus 로고
    • note
    • Pacific Northwest National Laboratory is operated for the U.S. Department of Energy by Battelle under contract DE-AC06-76RLO 1830. We thank S. McGuire and W. Cosby for editorial assistance.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.