此研究中，我們利用兩種不同型態的中孔洞二氧化鈦材料做為擔體吸附金奈 米粒子前驅液，再分別利用光、熱、氣相以及液相四種不同的還原方法，對金進 行還原反應，進而比較此二種不同型態、四種不同還原方法下，所合成出的金奈 米粒子與中孔洞二氧化鈦複合材料的差異性。
在使用中孔洞二氧化鈦奈米粒子(MTN)做為擔體的部份，我們發現，只有利用 熱還原做為金奈米粒子的還原方法可以成功合成出金奈米粒子與中孔洞二氧化鈦 複合材料(Au@MTNs)，而其金奈米粒子的粒徑分布較廣，粒徑大小約為 6.7 nm 左 右。
在使用中孔洞二氧化鈦薄膜(MTTF)做為擔體的部份，我們分別在 MTTF 表面 以及內部孔洞結構裡合成出均勻的金奈米粒子。我們發現，不論是合成哪種形式 的金奈米粒子於中孔洞二氧化鈦薄膜之複合材料(Au@MTTF)，利用光還原法進行 合成Au@MTTF 會得到最佳的結果。我們皆能得到薄膜結構完整且粒徑大小分布 均勻、分散性好的金奈米粒子。其中在MTTF 表面長金奈米粒子的部份，我們合 成出的金奈米粒子粒徑大小約為18 nm 左右；而在 MTTF 內部孔洞結構裡則合成 出粒徑大小約4.1 nm 的金奈米粒子。
78
合成Au@MTNs ：
Au / MTNs Size distribution Shape Average size
Photo-reduction --- --- ---
Thermal-reduction Broad sphere 6.7 nm
Solution-reduction --- --- ---
Vapor-reduction --- --- ---
在MTTF 表面合成 Au@MTTF：
Au / MTTF Size distribution Shape Average size
Photo-reduction Narrow sphere 17.8 nm
Thermal-reduction Broad sphere 44.6 nm
Solution-reduction --- bulk ---
Vapor-reduction --- bulk ---
distribution Shape
Average size
Photo-reduction ⊚ Narrow sphere 4.10 nm
Thermal-reduction 〇 Broad sphere 7.43 nm Solution-reduction X Narrow sphere 3.60 nm
Vapor-reduction ⊚ Broad sphere 5.79 nm
79
參考文獻
1 Vartuli, J. C. et al. SYNTHESIS OF MESOPOROUS MATERIALS - LIQUID-CRYSTAL TEMPLATING VERSUS INTERCALATION OF LAYERED SILICATES. Chem. Mat. 6, 2070-2077 (1994).
2 Beck, J. S. et al. A NEW FAMILY OF MESOPOROUS MOLECULAR-SIEVES
PREPARED WITH LIQUID-CRYSTAL TEMPLATES. Journal of the American Chemical
Society 114, 10834-10843 (1992).
3 Kresge, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C. & Beck, J. S. ORDERED MESOPOROUS MOLECULAR-SIEVES SYNTHESIZED BY A LIQUID-CRYSTAL TEMPLATE MECHANISM. Nature 359, 710-712 (1992).
4 Ying, J. Y., Mehnert, C. P., Wong, M. S. Synthesis and applications of supramolecular-templated mesoporous materials. Angewandte
Chemie-International Edition 38, 56-77 (1999).
5 Firouzi, A. et al. COOPERATIVE ORGANIZATION OF INORGANIC-SURFACTANT AND BIOMIMETIC ASSEMBLIES. Science 267, 1138-1143 (1995).
6 Zhao, D. Y. et al. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279, 548-552 (1998).
7 Zhao, D. Y., Huo, Q. S., Feng, J. L., Chmelka, B. F. & Stucky, G. D. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly
ordered, hydrothermally stable, mesoporous silica structures. Journal of the
American Chemical Society 120, 6024-6036 (1998).
8 Imperor-Clerc, M., Davidson, P. & Davidson, A. Existence of a microporous corona around the mesopores of silica-based SBA-15 materials templated by triblock copolymers. Journal of the American Chemical Society 122,
11925-11933 (2000).
9 Wang, W. H., Xie, S. H., Zhou, W. Z. & Sayari, A. Synthesis of periodic
mesoporous ethylenesilica under acidic conditions. Chem. Mat. 16, 1756-1762 (2004).
10 Brinker, C. J., Lu, Y. F., Sellinger, A. & Fan, H. Y. Evaporation-induced self-assembly: Nanostructures made easy. Adv. Mater. 11, 579-+ (1999).
11 Ogawa, M. FORMATION OF NOVEL ORIENTED TRANSPARENT FILMS OF LAYERED SILICA-SURFACTANT NANOCOMPOSITES. Journal of the American Chemical
Society 116, 7941-7942 (1994).
12 Bruinsma, P. J., Kim, A. Y., Liu, J. & Baskaran, S. Mesoporous silica synthesized by solvent evaporation: Spun fibers and spray-dried hollow spheres. Chem. Mat. 9, 2507-2512 (1997).
80
13 Lu, Y. F. et al. Continuous formation of supported cubic and hexagonal mesoporous films by sol gel dip-coating. Nature 389, 364-368 (1997).
14 Yang, H., Coombs, N., Sokolov, I. & Ozin, G. A. Free-standing and oriented mesoporous silica films grown at the air-water interface. Nature 381, 589-592 (1996).
15 Yang, P. D., Zhao, D. Y., Margolese, D. I., Chmelka, B. F. & Stucky, G. D. Block copolymer templating syntheses of mesoporous metal oxides with large ordering lengths and semicrystalline framework. Chem. Mat. 11, 2813-2826 (1999).
16 Bell, A. T. The impact of nanoscience on heterogeneous catalysis. Science 299, 1688-1691 (2003).
17 Schlogl, R. & Abd Hamid, S. B. Nanocatalysis: Mature science revisited or something really new? Angewandte Chemie-International Edition 43, 1628-1637 (2004).
18 Rao, C. N. R., Kulkarni, G. U., Thomas, P. J. & Edwards, P. P. Size-dependent chemistry: Properties of nanocrystals. Chemistry-a European Journal 8, 29-35 (2002).
19 Kizuka, T., Ichinose, H. & Ishida, Y. Structure and hardness of nanocrystalline silver. J. Mater. Sci. 32, 1501-1507 (1997).
20 Gates, B. C. SUPPORTED METAL-CLUSTERS - SYNTHESIS, STRUCTURE, AND CATALYSIS. Chem. Rev. 95, 511-522 (1995).
21 Moulijn, J. A., van Diepen, A. E. & Kapteijn, F. Catalyst deactivation: is it predictable? What to do? Appl. Catal. A-Gen. 212, 3-16 (2001).
22 Qi, W. H. Size effect on melting temperature of nanosolids. Physica B 368, 46-50, (2005).
23 Buffat, P. & Borel, J. P. SIZE EFFECT ON MELTING TEMPERATURE OF GOLD PARTICLES. Phys. Rev. A 13, 2287-2298 (1976).
24 Shi, J. L., Hua, Z. L. & Zhang, L. X. Nanocomposites from ordered mesoporous materials. J. Mater. Chem. 14, 795-806 (2004).
25 Lu, A. H. & Schuth, F. Nanocasting: A versatile strategy for creating nanostructured porous materials. Adv. Mater. 18, 1793-1805 (2006).
26 Joo, S. H. et al. Ordered nanoporous arrays of carbon supporting high dispersions of platinum nanoparticles. Nature 412, 169-172 (2001).
27 Wang, X. D. & Caruso, R. A. Enhancing photocatalytic activity of titania materials by using porous structures and the addition of gold nanoparticles. J. Mater.
Chem. 21, 20-28 (2011).
28 Hoffmann, F., Cornelius, M., Morell, J. & Froba, M. Silica-based mesoporous organic-inorganic hybrid materials. Angewandte Chemie-International Edition
81
45, 3216-3251 (2006).
29 Korzhak, A. V. et al. Photocatalytic hydrogen evolution over mesoporous TiO2/metal nanocomposites. J. Photochem. Photobiol. A-Chem. 198, 126-134 (2008).
30 Kafizas, A., Kellici, S., Darr, J. A. & Parkin, I. P. Titanium dioxide and composite metal/metal oxide titania thin films on glass: A comparative study of
photocatalytic activity. J. Photochem. Photobiol. A-Chem. 204, 183-190 (2009).
31 Burdett, J. K., Hughbanks, T., Miller, G. J., Richardson, J. W. & Smith, J. V.
STRUCTURAL ELECTRONIC RELATIONSHIPS IN INORGANIC SOLIDS - POWDER NEUTRON-DIFFRACTION STUDIES OF THE RUTILE AND ANATASE POLYMORPHS OF TITANIUM-DIOXIDE AT 15 AND 295-K. Journal of the American Chemical
Society 109, 3639-3646 (1987).
32 Antonelli, D. M. & Ying, J. Y. SYNTHESIS OF HEXAGONALLY PACKED
MESOPOROUS TIO2 BY A MODIFIED SOL-GEL METHOD. Angew. Chem.-Int. Edit.
Engl. 34, 2014-2017 (1995).
33 Yang, P. D., Zhao, D. Y., Margolese, D. I., Chmelka, B. F. & Stucky, G. D.
Generalized syntheses of large-pore mesoporous metal oxides with semicrystalline frameworks. Nature 396, 152-155 (1998).
34 Alberius, P. C. A. et al. General predictive syntheses of cubic, hexagonal, and lamellar silica and titania mesostructured thin films. Chem. Mat. 14, 3284-3294 (2002).
35 Smarsly, B. et al. Highly crystalline cubic mesoporous TiO2 with 10-nm pore diameter made with a new block copolymer template. Chem. Mat. 16, 2948-2952 (2004).
36 Boettcher, S. W., Bartl, M. H., Hu, J. G. & Stucky, G. D. Structural analysis of hybrid titania-based mesostructured composites. Journal of the American
Chemical Society 127, 9721-9730 (2005).
37 Harizanov, O. & Harizanova, A. Development and investigation of sol-gel solutions for the formation of TiO2 coatings. Sol. Energy Mater. Sol. Cells 63, 185-195 (2000).
38 Yoldas, B. E. HYDROLYSIS OF TITANIUM ALKOXIDE AND EFFECTS OF HYDROLYTIC POLYCONDENSATION PARAMETERS. J. Mater. Sci. 21, 1087-1092 (1986).
39 Houas, A. et al. Photocatalytic degradation pathway of methylene blue in water.
Appl. Catal. B-Environ. 31, 145-157 (2001).
40 Haruta, M., Yamada, N., Kobayashi, T. & Iijima, S. GOLD CATALYSTS PREPARED BY COPRECIPITATION FOR LOW-TEMPERATURE OXIDATION OF HYDROGEN AND OF CARBON-MONOXIDE. J. Catal. 115, 301-309 (1989).
41 Haruta, M. et al. LOW-TEMPERATURE OXIDATION OF CO OVER GOLD
82
SUPPORTED ON TIO2, ALPHA-FE2O3, AND CO3O4. J. Catal. 144, 175-192 (1993).
42 Haruta, M. Size- and support-dependency in the catalysis of gold. Catal. Today
36, 153-166 (1997).
43 Haruta, M. & Date, M. Advances in the catalysis of Au nanoparticles. Appl. Catal.
A-Gen. 222, 427-437 (2001).
44 Bartlett, N. Relativistic effects and the chemistry of gold. Gold Bull. 31, 22-25 (1998).
45 Chen, X. & Mao, S. S. Titanium dioxide nanomaterials: Synthesis, properties, modifications, and applications. Chem. Rev. 107, 2891-2959 (2007).
46 Carneiro, J. T., Savenije, T. J. & Mul, G. Experimental evidence for electron localization on Au upon photo-activation of Au/anatase catalysts. Phys. Chem.
Chem. Phys. 11, 2708-2714 (2009).
47 Mizukoshi, Y. et al. Immobilization of noble metal nanoparticles on the surface of TiO2 by the sonochemical method: Photocatalytic production of hydrogen from an aqueous solution of ethanol. Ultrason. Sonochem. 14, 387-392 (2007).
48 Iliev, V., Tomova, D., Bilyarska, L. & Tyuliev, G. Influence of the size of gold nanoparticles deposited on TiO2 upon the photocatalytic destruction of oxalic acid. J. Mol. Catal. A-Chem. 263, 32-38 (2007).
49 Xu, J. et al. Photocatalytic inactivation effect of gold-doped TiO2 (Au/TiO2) nanocomposites on human colon carcinoma LoVo cells. Int. J. Photoenergy, 7 (2007).
50 Daniel, M. C. & Astruc, D. Gold nanoparticles: Assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. Chem. Rev. 104, 293-346 (2004).
51 Dozzi, M. V., Prati, L., Canton, P. & Selli, E. Effects of gold nanoparticles
deposition on the photocatalytic activity of titanium dioxide under visible light.
Phys. Chem. Chem. Phys. 11, 7171-7180 (2009).
52 Wang, X. D., Mitchell, D. R. G., Prince, K., Atanacio, A. J. & Caruso, R. A. Gold nanoparticle incorporation into porous titania networks using an agarose gel templating technique for photocatalytic applications. Chem. Mat. 20 (2008).
53 Kiyonaga, T., Fujii, M., Akita, T., Kobayashi, H. & Tada, H. Size-dependence of Fermi energy of gold nanoparticles loaded on titanium(IV) dioxide at
photostationary state. Phys. Chem. Chem. Phys. 10, 6553-656 (2008).
54 Elmoula, M. A. et al. Controlled attachment of gold nanoparticles on ordered titania nanotube arrays. J. Mater. Chem. 19, 4483-4487 (2009).
55 Rupa, A. V., Divakar, D. & Sivakumar, T. Titania and Noble Metals Deposited Titania Catalysts in the Photodegradation of Tartazine. Catal. Lett. 132, 259-267 (2009).
83
56 Soejima, T., Tada, H., Kawahara, T. & Ito, S. Formation of Au nanoclusters on TiO2 surfaces by a two-step method consisting of Au(III)-complex
chemisorption and its photoreduction. Langmuir 18, 4191-4194 (2002).
57 Chan, S. C. & Barteau, M. A. Preparation of highly uniform Ag/TiO2 and Au/TiO2 supported nanoparticle catalysts by photodeposition. Langmuir 21, 5588-5595 (2005).
58 Uddin, M. J. et al. Cotton textile fibres coated by Au/TiO2 films: Synthesis, characterization and self cleaning properties. J. Photochem. Photobiol. A-Chem.
199, 64-72 (2008).
59 Lee, S. L., Scott, J., Chiang, K. & Amal, R. Nanosized metal deposits on titanium dioxide for augmenting gas-phase toluene photooxidation. J. Nanopart. Res. 11, 209-219 (2009).
60 Hidalgo, M. C., Maicu, M., Navio, J. A. & Colon, G. Effect of Sulfate Pretreatment on Gold-Modified TiO2 for Photocatalytic Applications. J. Phys. Chem. C 113, 12840-12847 (2009).
61 Mendez, V., Caps, V. & Daniele, S. Design of hybrid titania nanocrystallites as supports for gold catalysts. Chem. Commun., 3116-3118 (2009).
62 Pradhan, S., Ghosh, D. & Chen, S. W. Janus Nanostructures Based on Au-TiO2 Heterodimers and Their Photocatalytic Activity in the Oxidation of Methanol.
ACS Appl. Mater. Interfaces 1, 2060-2065 (2009).
63 Xie, Y. et al. In Situ Controllable Loading of Ultrafine Noble Metal Particles on Titania. Journal of the American Chemical Society 131, 6648-+ (2009).
64 Zanella, R., Giorgio, S., Henry, C. R. & Louis, C. Alternative methods for the preparation of gold nanoparticles supported on TiO2. Journal of Physical
Chemistry B 106, 7634-7642 (2002).
65 Zanella, R., Giorgio, S., Shin, C. H., Henry, C. R. & Louis, C. Characterization and reactivity in CO oxidation of gold nanoparticles supported on TiO2 prepared by deposition-precipitation with NaOH and urea. J. Catal. 222, 357-367 (2004).
66 Cui, F. M. et al. Highly dispersed Au nanoparticles incorporated mesoporous TiO2 thin films with ultrahigh Au content. J. Mater. Chem. 19, 7632-7637 (2009).