臺灣博碩士論文加值系統

由於近年環保概念興起，不論是產業或者是理論研究多以降低環境汙染、減緩溫室效應為主旨，綠色化學就是在此前提下受到注目，而與生活和產業二者相關的無非是廢水和廢氣的控制，如何能達到對環境無害的排放標準便是很重要的議題；對於廢水、廢氣的研究多以金屬或其氧化物擔載於氧化矽材料後，以吸附的方式達到降低污染的效果，本研究則以氧化銅做為氧化矽材料擔載的金屬氧化物成分，並以之做為工業染料廢水、半導體產業之毒性PH3氣體的高效能吸附材。
本研究則以矽/銅莫耳比 = 2 : 1製備出高表面積(約500 m2/g)以及高氧化銅分散性之孔洞複合材料，合成方式如下所示：
1. 異相成核製備Cu-silicate
本實驗以工業級之界面活性劑Polyethylene Glycol(簡稱PEG)製備出中孔洞氧化矽材料，並可利用不同水熱pH值環境而得以調整氧化矽的孔洞性質；而氧化矽表面具有矽醇基，利用矽醇基螯合金屬氫氧化物之能力，而達到將氫氧化銅均勻分散於溶液之效果，並加入微量NaF，使其在水熱過程產生微量HF的方式加速氧化矽的溶解，矽酸鹽則得以穩定地和氫氧化銅進行重組，進一步降低了氫氧化銅聚集的現象，也因此水熱時間縮短至一天便可完成，大幅增進實驗效率；本研究更利用碳酸鈉和尿素調控水熱pH值，避免氫氧化銅於溶液中的局部聚集，降低實驗誤差，並且結合工業銅離子廢液，亦能成功製備出具有良好的孔洞性質(表面積 〉 450 m2/g)、氧化銅分散性的Cu-silicate孔洞複合材料，其對於PH3毒性氣體的最大攔截效率可達到99%以上，以及吸附工業染料廢水後，能降低汙水濃度至遠低於排放標準之濃度(吸附前340 ppm，吸附後為45 ppm)。


2. 綠色化學製備Cu-silicate
以往研究利用模板法製備孔洞材料，不論是軟式或者硬式模板，其原理皆是利用模板與欲擔載物間的作用力，將無機物生成至模板上而具有與模板相似之構型，並利用酸洗或者是高溫鍛燒的方式移除模板，因此實驗過程相當繁雜。本研究直接以層狀氫氧化銅做為模板，將氧化矽材料在pH=11的水熱環境下，溶解出矽酸鹽並與氫氧化銅螯合，降低氫氧化銅層間的作用力達到intercalation的效果，並以高溫水熱環境之能量，使得氧化矽得以對氫氧化銅進行剝蝕，且由於兩者之晶格大小不同，造成重組後之結構具有應力差，因而捲曲形成管狀結構。

除了以一般氧化矽材料製備Cu-silicate，本研究更直接利用稻殼和稻桿製備孔洞複合材料；由於大部分的禾本科植物都含有氧化矽成分用以增強結構強度，因此可利用在高溫、高鹼的環境下，使得稻殼、稻桿內的氧化矽組成溶出而和氫氧化銅模板進行重組，並利用尿素的緩衝溶液效果，將水熱pH值保持在pH=9以上，稻殼、稻桿中之氧化矽成分便可穩定溶解，而增進和氫氧化銅的重組效果，降低了氫氧化銅結晶化的趨勢，利用此法製備出的孔洞材料，表面積可達到450 m2/g，並且亦能結合半導體工業銅離子廢液成功製備出同樣的孔洞材料，而同時達到回收工業廢液中之銅離子，降低回收成本，以及增進農業廢棄物的應用價值等成效。

For the concept of green chemistry, the scientists put much effort to reduce environmental pollution and slow down the greenhouse effect. It would be an important issue to control the effluent amount of waste water and toxic gas for the purpose of environmental protection. Mesostructural materials of high-surface area, tunable pore size and large pore volume have obvious potentials for the applications in adsorption, catalysis, enzyme-stabilization, and optical devices.
In this research, we prepared the mesoporous copper-silicate of high surface area (〉 450 m2g-1), well-dispersed of CuO, tunable mesopores (pore size  3.4 ~ 4.0 nm) and high thermal stability was obtained from heterogeneous nucleation and hydrothermal treatment for 1 day on a mixture of copper hydroxide and porous silica without adding any organic template. Adding proper amount of sodium fluoride can accelerate the silica dissolving rate and reduce the reaction time. The base sources in the alkaline solution can affect the aggregation extent of Cu(OH)2. Using different silica sources such as mesoporous silica, rice husk porous silica and fumed silica can also get the mesoporous copper-silicate. In brief, we provided a new synthesis method to prepare the mesoporous copper-silicate by hydrothermal treatment on the simple mixtures of Cu(OH)2 precipitation, NaF and silica source. This synthetic method can be successfully extended to use the industry slurry (Cu-CMP) and agricultural waste stuff (rice husk and straw) to prepare mesoporous copper-silicates with excellent porous properties.
In application, the mesoporous copper silicate act as a high-performance absorbent to remove the toxic gas of PH3 as dopant in IC industry (the maximum removal percentage = 99%), and reduce the COD values and heavy metal ions in the industrial waste water to below the legal limited in effluent (about 45 ppm).

第一章 序論 1
1.1 中孔洞材料介紹 1
1.1.1 中孔洞材料主要的研究範疇 2
1.2 界面活性劑簡介 3
1.2.1 界面活性劑分類 4
1.3 微胞的簡介 5
1.3.1 微胞的生成 6
1.3.2 界面活性劑的聚集體結構 7
1.4 矽酸鹽的化學概念 8
1.5 結合金屬氧化物之中孔洞氧化矽材料合成 10
1.5.1 觸媒的合成方法 10
1.6 禾本科植物簡介及工業廢液利用 12
1.6.1 稻桿、稻殼再利用 13
1.6.2 Cu-CMP廢液再利用 14
1.7 PH3氣體及其吸附特性 14
1.7.1 PH3氣體的基本特性 15
1.7.2 局部廢氣處理設備去除廢棄之方法 15
1.7.3 乾式吸附法處理氫化物系氣體之吸附劑 16
1.8 化學需氧量(COD) 18
第二章 實驗部分 19
2.1 化學藥品 19
2.2 實驗流程 20
2.2.1 異相成核法製備Cu-silicate 20
2.2.2 綠色化學製備 Cu-silicate 21
2.3 儀器鑑定分析 22
2.3.1 熱重分析儀(Thermogravimetry Analysis; TGA) 22
2.3.2 穿透式電子顯微鏡(Transmission Electron Microscopy; TEM) 22
2.3.3 氮氣等溫吸附/脫附測量 (N2 adsorption / desorption isotherm) 23
2.3.4 X-射線粉末繞射光譜 (Powder X-Ray Diffraction；PXRD) 26
2.3.5 能量分散光譜儀 (Energy Dispersive Spectrometer；EDX) 27
第三章 異相成核法製備copper-silicate 28
3.1 研究目的與動機 28
3.2 調動含浸氧化銅比例於異相成核法之結果 29
3.3 改良高含浸氧化銅比例的copper-silicate 33
3.4 加入氟化鈉後的CuO/SiO2反應機構探討 35
3.5 Copper-silicate 最佳化參數討論 52
3.6 更換鹼性溶液調整水熱pH值之影響 65
3.7 以工業銅廢液做為氫氧化銅來源 72
第四章 綠色化學製備copper-silicate 81
4.1 研究動機與目的 81
4.2 最佳反應參數 83
4.3 利用稻殼、稻桿做為氧化矽原料 90
4.4 利用稻殼製備copper-silicate之結果。 92
4.4.1 加入碳酸鈉或尿素做為水熱pH值的緩衝溶液 97
4.5 利用稻桿製備copper-silicate之結果 106
4.6 以工業銅廢液做為氫氧化銅模板來源 115
第五章 應用範疇 117
5.1 研究目的與動機 117
5.2 PH3氣體之吸附成果 118
5.3 工業染料廢水之吸附成果 123
第六章 總結 128
參考文獻 130

1.C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and J. S. Beck, Nature, 1992, 359, 710-712.
2.J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kresge, K. D. Schmitt, C. T. W. Chu, D. H. Olson, E. W. Sheppard, S. B. Mccullen, J. B. Higgins and J. L. Schlenker, J Am Chem Soc, 1992, 114, 10834-10843.
3.R. L. Burwell, Pure Appl Chem, 1976, 46, 71-＆.
4.J. Fan, C. Z. Yu, T. Gao, J. Lei, B. Z. Tian, L. M. Wang, Q. Luo, B. Tu, W. Z. Zhou and D. Y. Zhao, Angew Chem Int Edit, 2003, 42, 3146-3150.
5.A. Vinu, V. Murugesan and M. Hartmann, Chem Mater, 2003, 15, 1385-1393.
6.H. P. Lin, C. L. Kuo, B. Z. Wan and C. Y. Mou, Journal of the Chinese Chemical Society, 2002, 49, 899-906.
7.V. Alfredsson and M. W. Anderson, Chem Mater, 1996, 8, 1141-1146.
8.H. P. Lin and C. Y. Mou, Accounts of Chemical Research, 2002, 35, 927-935.
9.J. M. Kim, Y. Sakamoto, Y. K. Hwang, Y. U. Kwon, O. Terasaki, S. E. Park and G. D. Stucky, J Phys Chem B, 2002, 106, 2552-2558.
10.A. Bhaumik and S. Inagaki, J Am Chem Soc, 2001, 123, 691-696.
11.Z. T. Zhang, Y. Han, L. Zhu, R. W. Wang, Y. Yu, S. L. Qiu, D. Y. Zhao and F. S. Xiao, Angew Chem Int Edit, 2001, 40, 1258-+.
12.A. Walcarius, M. Etienne and B. Lebeau, Chem Mater, 2003, 15, 2161-2173.
13.T. Yokoi, H. Yoshitake and T. Tatsumi, J Mater Chem, 2004, 14, 951-957.
14.J. N. Cha, G. D. Stucky, D. E. Morse and T. J. Deming, Nature, 2000, 403, 289-292.
15.E. Bauerlein, Angew Chem Int Edit, 2003, 42, 614-641.
16.Z. R. R. Tian, J. Liu, J. A. Voigt, B. McKenzie and H. F. Xu, Angew Chem Int Edit, 2003, 42, 414-+.
17.F. Noll, M. Sumper and N. Hampp, Nano Letters, 2002, 2, 91-95.
18.Z. Y. Zhong, Y. D. Yin, B. Gates and Y. N. Xia, Adv Mater, 2000, 12, 206-+.
19.P. Jiang, J. F. Bertone and V. L. Colvin, Science, 2001, 291, 453-457.
20.C. E. Fowler, D. Khushalani and S. Mann, Chem Commun, 2001, 2028-2029.
21.Q. S. Huo, J. L. Feng, F. Schuth and G. D. Stucky, Chem Mater, 1997, 9, 14-＆.
22.Y. F. Lu, H. Y. Fan, A. Stump, T. L. Ward, T. Rieker and C. J. Brinker, Nature, 1999, 398, 223-226.

23.C. E. Fowler, D. Khushalani, B. Lebeau and S. Mann, Adv Mater, 2001, 13, 649-652.
24.S. Mann, Angew Chem Int Edit, 2000, 39, 3393-3406.
25.N. Kroger, R. Deutzmann and M. Sumper, Science, 1999, 286, 1129-1132.
26.E. G. Vrieling, T. P. M. Beelen, R. A. van Santen and W. W. C. Gieskes, Angew Chem Int Edit, 2002, 41, 1543-1546.
27.C. Fox, Cosmet Toiletries, 1984, 99, 28-31.
28.C. T. Kresge, M. E. Leonowicz , J. Roth, J. C. Vartuli and J. S. Beck, Nature, 1992, 359, 710-712.
29.B. W. N. D. J. Mithchell, J. Chem. Soc., 1981, 77, 1264.
30.R. K. Iler, The Chemistry of Silica John Wiley, New York, 1979.
31.C. J. Brinker and G. W. Scherer, J Non-Cryst Solids, 1985, 70, 301-322.
32.R. A. Sheldon, M. Wallau, I. W. C. E. Arends and U. Schuchardt, Accounts Chem Res, 1998, 31, 485-493.
33.A. Voigt, R. Murugavel, M. L. Montero, H. Wessel, F. Q. Liu, H. W. Roesky, I. Uson, T. Albers and E. Parisini, Angewandte Chemie-International Edition in English, 1997, 36, 1001-1003.
34.R. Murugavel and H. W. Roesky, Angewandte Chemie-International Edition in English, 1997, 36, 477-479.
35.M. G. Clerici, G. Bellussi and U. Romano, J Catal, 1991, 129, 159-167.
36.C. B. Dartt, C. B. Khouw, H. X. Li and M. E. Davis, Abstr Pap Am Chem S, 1993, 206, 57-Petr.
37.J. C. van der Waal, P. J. Kooyman, J. C. Jansen and H. van Bekkum, Micropor Mesopor Mat, 1998, 25, 43-57.
38.C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and J. S. Beck, Nature, 1992, 359, 710-712.
39.A. Corma, V. Fornes, M. T. Navarro and J. Perezpariente, J Catal, 1994, 148, 569-574.
40.M. D. Alba, Z. H. Luan and J. Klinowski, J Phys Chem-Us, 1996, 100, 2178-2182.
41.R. Mokaya, W. Jones, Z. H. Luan, M. D. Alba and J. Klinowski, Catal Lett, 1996, 37, 113-120.
42.B. L. Newalkar, J. Olanrewaju and S. Komarneni, Chem Mater, 2001, 13, 552-557.
43.D. R. Rolison, Science, 2003, 299, 1698-1701.
44.F. A. C. Garcia, J. C. M. Silva, J. L. de Macedo, J. A. Dias, S. C. L. Dias and G. N. R. Filho, Micropor Mesopor Mat, 2008, 113, 562-574.
45.M. Plabst, L. B. McCusker and T. Bein, J Am Chem Soc, 2009, 131, 18112-18118.
46.M. Haruta, N. Yamada, T. Kobayashi and S. Iijima, J Catal, 1989, 115, 301-309.
47.R. Nares, J. Ramirez, A. Gutierrez-Alejandre, C. Louis and T. Klimova, J Phys Chem B, 2002, 106, 13287-13293.
48.Y. Chi, T. Y. Chou, Y. J. Wang, S. F. Huang, A. J. Carty, L. Scoles, K. A. Udachin, S. M. Peng and G. H. Lee, Organometallics, 2004, 23, 95-103.
49.L. M. Xiong, E. H. Sekiya, S. Wada and K. Saito, Acs Appl Mater Inter, 2009, 1, 2509-2518.
50.S. M. Chang, Y. Y. Hsu and T. S. Chan, J Phys Chem C, 2011, 115, 2005-2013.
51.Robert Quinn,Thomas A. Dahl, Barry W. Diamond, and Bernard A. Toseland, Ind. Eng. Chem. Res. 2006, 45, 6272-6278.
52.Yi Honghong, Yang Lina, Tang Xiaolong, Yu Lili, Wang Hongyan, MASS. 2010,1-4.
53.Ning Ping, Bart Hans-Jorg, Ma Liping, Chen Liang, Engineering Sciences, 2005, 7(6), 27-35.
54.Zumin Qiu, Yunbing He, Xiaocheng Liu, Shuxian Yu, Chemical Engineering and Processing ,2005, 44, 1013–1017.
55.Shilpi Verma, Basheshwar Prasad, and Indra Mani Mishra, Ind. Eng. Chem. Res. 2011, 50, 5352–5359.
56.Minghuang Huang, Carl Boone, Michelle Roberts, Don E. Savage, Max G. Lagally, Nakul Shaji, Adv. Mater. 2005, 17, 2860–2864.
57.Oliver G. Schmidt, Nicole Schmarje, Christoph Deneke, Claudia Muller, and Neng-Yun Jin-Phillipp, Adv. Mater. 2001, 13, 756–759
58.Fabrice Leroux, and Jean-Pierre Besse, Chem. Mater. 2001, 13, 3507–3515
59.J. J. Lin, C. C. Chu, C. C. Chou, Adv. Mater. 2005, 13, 17, 301.
60.J. J. Lin, C. C. Chu, M. L. Chiang, W. C. Tsai, Journal of Physicl Cemestry B. 2006, 110, 18115-18120.
61.L. Pauling, Pord. Nat. Acad. Sci. U.S.A, 1930, 16, 578.
62.Ji Zang, Minghuang Huang, Feng Liu, Physical Review Letters, 2007, 98, 146102(4).
63.Y. M. Senousy, E. V. Moiseeva, and C. K. Harnett, Poster Presentation of Harnnet Lab, University of Louisville, 2008
64.環保署, 水中化學需氧量檢測方法－密閉迴流滴定法, 環署檢字第0960058228B號公告, NIEA W517.51B,(1997)
65.郭茂松,中華民國環境保護學會會誌,第九卷,第二期,(1987)