臺灣博碩士論文加值系統

Z-Scheme 是一種利用兩種光觸媒進行水分解產氫的系統，而光觸媒可分為產氫觸媒與產氧觸媒兩種，分別進行產氫與產氧的反應。過去使用Z-Scheme 來進行光催化水分解反應時，都是將兩種光觸媒混合後再進行照光反應，所以產生的氣體是氫氣和氧氣的混合氣體，不但會發生逆反應，降低水分解效率，更有爆炸安全上的顧慮，而且氫氣尚須經過分離的步驟才可使用。故本實驗是以Pt/SrTiO3:Rh作為產氫觸媒，以WO3作為產氧觸媒，分開至兩個連結式的反應器中，以Fe3+/Fe2+為電子傳遞媒介在水溶液中，利用Nafion 離子交換膜隔開兩觸媒，照射可見光進行光催化水分解反應，以達到氫氣與氧氣及時分離的效果。實驗是以500W鹵素燈作為可見光源，使用經過Fe3+前處理的Nafion 膜進行反應，由結果發現確實可以做到氫氣與氧氣分開生成的效果，且與單一反應器系統相比，由於阻止逆反應的發生，使其具有更高的產氫和產氧產量，而在最佳的條件下，產氫速率可以達到2.22 μmol/g-hr且符合H2:O2=2:1的水分解化學當量比。

The Z-scheme is a two-photocatalyst system for photocatalytic water splitting to produce hydrogen. The two-photocatalyst system is comprised of H2-catalyst and O2-catalyst to produce hydrogen and oxygen, respectively. Conventionally in Z-scheme, two catalysts are mixed in one reactor to perform photocatalytic water splitting, thus hydrogen and oxygen are produced as a mixture. Thus, the reverse reaction occurs to reduce the efficiency of water splitting. The cost of H2 separation is another drawback. Furthermore, a safety issue of H2-O2 explosion must be considered in the commercial process. This research used Pt/SrTiO3:Rh (H2-catalyst) and WO3 (O2-catalyst) discretely in two compartments of a connected twin reactor filled with aqueous solution. Two compartments of the twin reactor was separated by Nafion ion-exchanged membrane. Fe3+ and Fe2+ were added and served as electron-transfer mediates for redox reaction. The Nafion membrane was pretreated under Fe ion solution. The light source was 500W Halogen lamp. Under the visible-light irradiation, hydrogen and oxygen can be separately produced in two compartments simultaneously by photocatalytic water splitting. Under the optimal condition, the H2 yield reached 2.22 mole/g-h, and the molar ratio of H2/O2 was matched the stoichiometry of water splitting.

摘要 1
Abstract II
目錄 III
圖目錄 VII
表目錄 X
第一章 緒論 1
第二章 文獻回顧 3
2.1 原理 3
2.1.1 水分解 3
2.1.2 光觸媒反應之基本理論 4
2.1.3 光觸媒反應過程 6
2.1.4 反應器的種類 7
2.2 影響水分解反應活性的因素 9
2.2.1 摻雜元素的效應 9
2.2.2 添加共觸媒的效應 13
2.2.3 添加犧牲試劑的效應 18
2.3光催化水分解系統 22
2.3.1 單觸媒反應系統 (one step system) 22
2.3.2 雙觸媒反應系統 (two step system , Z-Scheme system) 22
第三章 實驗方法 29
3.1 實驗藥品與儀器設備 29
3.1.1 藥品 29
3.1.2 器材 31
3.2 觸媒之製備 32
3.2.1固態高溫熔融法( Solid-State Fusion Method ) 32
3.2.2光催化沈積法( Photocatalytic Deposition Method ) 32
3.3 離子交換膜的前處理 35
3.4 觸媒特性分析原理與方法 37
3.4.1 儀器型號與規格 37
3.4.2 X光繞射儀(X-Ray Diffractometer，XRD) 38
3.4.3 紫外光-可見光光譜儀( UV-Visible Spectrometer，UV-VIS ) 41
3.4.4 場發射掃描式電子顯微鏡
( Field Emission Scanning Electron Microscope，FE-SEM ) 43
3.4.5 能量分散光譜儀( Energy Dispersive Spectrometer，EDS ) 44
3.4.6 氣相管柱層析儀–熱導偵測器( GC–TCD ) 44
3.5 光催化活性檢測 46
3.5.1 檢量線製作 46
3.5.1.1 氧氣與氮氣檢量線 46
3.5.1.2 氫氣檢量線 50
3.5.2 光催化水分解活性實驗-單一反應器系統( Single Reactor System ) 53
3.5.3 光催化水分解活性實驗-分離式雙反應器系統 ( Twin Reactor System ) 60
3.5.4 訊華軟體-SISC色層分析數據處理系統 68
第四章 觸媒特性分析與討論 69
4.1 Pt/SrTiO3:Rh光觸媒 69
4.2 觸媒檢測 71
4.2.1 XRD 71
4.2.2 UV-VIS 73
4.2.3 SEM 76
4.2.4 EDS 78
4.3 Nafion離子交換膜定性分析 79
第五章 光催化水分解活性實驗結果與討論 82
5.1 單一反應器系統( Single Reactor System ) 82
5.1.1 空白實驗 82
5.1.2 光催化水分解活性實驗 84
5.1.2.1 三價鐵離子溶液的反應 84
5.1.2.2 二價鐵離子溶液的反應 86
5.1.2.3 不同價數鐵離子溶液之活性比較 88
5.2 分離式雙反應器系統( Twin Reactors System ) 90
5.2.1光催化水分解活性實驗-有利條件 90
5.2.2光催化水分解活性實驗-不利條件 92
5.2.3觸媒失活反應的測試 93
5.2.4不同反應器系統的活性比較 95
第六章 結論 97
參考文獻 98
個人小傳 101

1.Fujishima, A. and K. Honda, Electrochemical Photolysis of Water at a Semiconductor Electrode, Nature, 238 (1972) 37-38.
2.Konta, R., T. Ishii, H. Kato, and A. Kudo, Photocatalytic activities of noble metal ion doped SrTiO3 under visible light irradiation, Journal of Physical Chemistry B, 108 (2004) 8992-8995.
3.Kudo, A., H. Kato, and I. Tsuji, Strategies for the Development of Visible-light-driven Photocatalysts for Water Splitting, Chemistry Letters, 33 (2004) 1534-1539.
4.Fujishima, A., T.N. Rao, and D.A. Tryk, Titanium dioxide photocatalysis, Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 1 (2000) 1-21.
5.Kudo, A., Photocatalyst material for water splitting, Catalysis Surveys from Asia, 7 (2003) 31-38.
6.Sayama, K., R. Yoshida, H. Kusama, K. Okabe, Y. Abe, and H. Arakawa, Photocatalytic decomposition of water into H2 and O2 by a two-step photoexcitation reaction using a WO3 suspension catalyst and an Fe3+/Fe2+ redox system, Chemical Physics Letters, 277 (1997) 387-391.
7.Kato, H. and A. Kudo, Water Splitting into H2 and O2 on Alkali Tantalate Photocatalysts ATaO3 (A = Li, Na, and K), Journal of Physical Chemistry B, 105 (2001) 4285-4292.
8.Matsuoka, M., M. Kitano, M. Takeuchi, K. Tsujimaru, M. Anpo, and J.M. Thomas, Photocatalysis for new energy production: Recent advances in photocatalytic water splitting reactions for hydrogen production, Catalysis Today, 122 (2007) 51-61.
9.Kitano, M., K. Tsujimaru, and M. Anpo, Decomposition of water in the separate evolution of hydrogen and oxygen using visible light-responsive TiO2 thin film photocatalysts: Effect of the work function of the substrates on the yield of the reaction, Applied Catalysis A: General, 314 (2006) 179-183.
10.Kato, H. and A. Kudo, Visible-Light-Response and Photocatalytic Activities of TiO2 and SrTiO3 Photocatalysts Codoped with Antimony and Chromium, The Journal of Physical Chemistry B, 106 (2002) 5029-5034
11.Sayama, K., K. Mukasa, R. Abe, Y. Abe, and H. Arakawa, A new photocatalytic water splitting system under visible light irradiation mimicking a Z-scheme mechanism in photosynthesis, Journal of Photochemistry and Photobiology A: Chemistry, 148 (2002) 71-77.
12.Domen, K., A. Kudo, T. Onishi, N. Kosugi, and H. Kuroda, Photocatalytic decomposition of water into hydrogen and oxygen over nickel(II) oxide-strontium titanate (SrTiO3) powder. 1. Structure of the catalysts, The Journal of Physical Chemistry, 90 (1986) 292-295.
13.Sayama, K. and H. Arakawa, Remarkable Effect of Na2CO3 Addition on Photodecomposition of Liquid Water into H2 and O2 from Suspension of Semiconductor Powder Loaded with Various Metals Chemistry Letters, 21 (1992) 233.
14.Ogura, S., M. Kohno, K. Sato, and Y. Inoue, Effects of RuO2 on activity for water decomposition of a RuO2/Na2Ti3O7 photocatalyst with a zigzag layer structure Journal of Materials Chemistry 8(1998) 2335-2337
15.Sato, J., N. Saito, H. Nishiyama, and Y. Inoue, Photocatalytic activity for water decomposition of indates with octahedrally coordinated d10 configuration. I. Influences of preparation conditions on activity, Journal of Physical Chemistry B, 107 (2003) 7965-7969
16.Dickinson, A., D. James, N. Perkins, T. Cassidy, and M. Bowker, The photocatalytic reforming of methanol, Journal of Molecular Catalysis A-Chemical, 146 (1999) 211-221
17.Kato, H., K. Asakura, and A. Kudo, Highly Efficient Water Splitting into H2 and O2 over Lanthanum-Doped NaTaO3 Photocatalysts with High Crystallinity and Surface Nanostructure, Journal of The American Chemical Society, 125 (2003) 3082-3089.
18.Ishii, T., H. Kato, and A. Kudo, H2 evolution from an aqueous methanol solution on SrTiO3 photocatalysts codoped with chromium and tantalum ions under visible light irradiation Journal of Photochemistry and Photobiology A: Chemistry, 163 (2004) 181-186.
19.Hara, M., J. Nunoshige, T. Takata, J.N. Kondo, and K. Domen, Unusual enhancement of H2 evolution by Ru on TaON photocatalyst under visible light irradiation, Chemical Communications, (2003) 3000-3001
20.Yamasita, D., T. Takata, M. Hara, J.N. Kondo, and K. Domen, Recent progress of visible-light-driven heterogeneous photocatalysts for overall water splitting, Solid State Ionics, 172 (2004) 591-595
21.Fujihara, K., T. Ohno, and M. Matsumura, Splitting of water by electrochemical combination of two photocatalytic reactions on particles TiO2, J. Chem. Soc., Faraday Trans, 94 (1998) 3705-3709.
22.Abe, R., T. Takata, H. Sugihara, and K. Domen, Photocatalytic overall water splitting under visible light by TaON and WO3 with an IO3-/I- shuttle redox midiater, Chem. Commun., (2005) 3829 - 3831.
23.Kato, H., M. Hori, R. Konta, Y. Shimodaira, and A. Kudo, Construction of Z-scheme Type Heterogeneous Photocatalysis Systems for Water Splitting into H2 and O2 under Visible Light Irradiation Chemistry Letters, 33 (2004) 1348-1349.
24.Goswami, A., A. Acharya, and A.K. Pandey, Study of self-diffusion of monovalent and divalent cations in Nafion-117 ion-exchange membrane, Journal of Physical Chemistry B, 105 (2001) 9196-9201.
25.William D. Callister, J., Materials science and engineering:an introduction. 7. Wiley, New York; 1985, 68.
26.Swarthmore, Powder Diffraction File Card No.79-0174, in JCPDS--International Centre for Diffraction Data. 1997.
27.Swarthmore, Powder Diffraction File Card No.74-1624, in JCPDS--International Centre for Diffraction Data. 1997.
28.Swarthmore, Powder Diffraction File Card No.89-0555, in JCPDS--International Centre for Diffraction Data. 1997.
29.Swarthmore, Powder Diffraction File Card No.89-4479, in JCPDS--International Centre for Diffraction Data. 1997.
30.Bao, D., X. Yao, N. Wakiya, K. Shinozaki, and N. Mizutani, Band-gap energies of sol-gel-derived SrTiO3 thin films, Applied Physics Letters, 79 (2001) 3767-3769.
31.Hoffmann, M.R., S.T. Martin, W. Choi, and D.W. Bahnemann, Environmental applications of semiconductor photocatalysis, Chemical Reviews, 95 (1995) 69-96.
32.Haapala, H., The use of SEM/EDX for studying the distribution of air pollutants in the surroundings of the emission source, Environmental Pollution, 99 (1998) 361-363.
33.SISC層析儀積分數據處理系統操作手冊(上). 2.1. 訊華股份有限公司, 台北縣新店市; 2005, chapter 1, 31-32.
34.SISC層析儀積分數據處理系統操作手冊(上). 2.1. 訊華股份有限公司, 台北縣新店市; 2005, chapter 2, 2-38.
35.Swarthmore, Powder Diffraction File Card No.89-1383, in JCPDS--International Centre for Diffraction Data. 1997.
36.Kebes. Nafion structure. 2005. http://en.wikipedia.org/wiki/File:Nafion_structure.png.