本研究利用水熱法合成空間群為R3c之一維錫酸鋅奈米線 (ZnSnO3 NWs) 陣列，為具有非對稱中心之鈮酸鋰 (LiNbO3) 結構，有著高比表面積與載子傳遞路徑短的特性，可以有效地分離電子電洞對，提升光催化水分解的性能，因此可以推論ZnSnO3 NWs陣列為一個具有潛力的半導體材料。除此之外，透過一個簡單的氫氣處理步驟能有效地增加氧空缺濃度，改善其載子濃度大小，提升產氫的轉換效率，並在能隙中形成氧空缺的能階，增加可見光的利用。
在產氫的應用中，利用電化學方法分析ZnSnO3 NWs的轉換效率，本研究使用三極式電化學系統，利用線性掃描伏安法可以得知ZnSnO3 NWs試片的光電流密度大小為3.2 mA/cm2，為氧化鋅的5.3倍，經過氫氣後處理試片的光電流大小為9.6 mA/cm2，為未處理的試片的3倍。經由安培式電流時間曲線圖顯示ZnSnO3 NWs對開燈與關燈的反應性與穩定性；進一步透過電化學交流阻抗分析，了解光催化水分解內部細微的電化學反應，將ZnSnO3 NWs的電化學反應槽用Simplified Randles等效電路擬合，其中電荷轉移電阻 (Rct) 越小，代表電子在界面的轉移越容易，進而改善產氫效率，因此可以推論進行表面改質的試片由於載子濃度上升，電荷轉移能力改善，包括載子遷移率以及降低傳遞過程的阻抗等，有效改善光催化水分解的效率。綜合以上結果可以說明ZnSnO3 NWs結構可望成為永續生產氫能的方案之一。

One dimension zinc tin oxide (ZnSnO3) with noncentrosymmetric (NCS) centers synthesized by one-step hydrothermal method on F-doped tin oxide glass substrate has been successfully applied for water splitting and ZnSnO3 NWs is provided with more stable and higher performance than ZnO NRs because of some excellence characteristic. Additionally, annealing under hydrogen atmosphere is a simple, fast and eco-friendly approach to enhance the solar-to-hydrogen efficiency up to 5 times. The relationship of oxygen vacancy and carriers can be deduced two conclusions against physical and electrochemical characterization techniques；the carrier concentration is proportional to oxygen vacancy and the defect energy level will create within bandgap. In summary, the work provides a facile, low cost, fast strategy to construct ZnSnO3 NWs and H2-ZnSnO3 NWs photoelectrodes and the material is potential to employ in water splitting for solving energy shortage.

目錄
第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
第二章 文獻回顧 3
2.1 光催化水分解 3
2.1.1 光催化水分解歷史 3
2.1.2 光催化水分解機制 4
2.1.3 光催化水分解之電化學反應探討 5
2.1.4 光催化水分解材料特性 7
2.1.5 光能轉換氫能的效率 11
2.1.6 參考電極 12
2.1.7 光催化水分解常見材料 13
2.1.7.1 在氧化鋅表面修飾貴重金屬奈米粒子 14
2.1.7.2 二氧化鈦奈米線透過氫氣後處理方式 16
2.2 電化學阻抗頻譜 18
2.2.1 簡介 18
2.2.2 電化學阻抗理論 19
2.2.3 Simplified Randles circuit 20
2.3 錫酸鋅材料簡介 23
2.4 錫酸鋅製備方法 24
2.4.1 水熱法 24
2.4.2 化學溶液法 29
2.4.3 固態反應法 32
2.4.4 溶膠-凝膠法 34
2.4.5 化學氣相沉積法 36
第三章 實驗方法與步驟 38
3.1 實驗合成步驟 39
3.2 實驗儀器 41
3.2.1 電化學分析儀 41
3.2.2 氙燈光源 41
3.3 材料特性分析方法 43
3.3.1 冷場發射掃描式電子顯微鏡 43
3.3.2 WAG 廣角X 光繞射分析 44
3.3.3 場發射掃描穿透式球差修正電子顯微鏡 45
3.3.4 拉曼光譜儀以及光致發光光譜儀 46
3.3.5 壓電響應力顯微鏡 47
3.3.6 穿隧式原子力顯微鏡 48
3.3.7 高解析X光光電子能譜儀 49
3.3.8 紫外-可見光光譜分析儀 50
第四章 結果與討論 51
4.1 錫酸鋅奈米線特性分析 51
4.1.1 晶格結構分析 51
4.1.2 掃描式電子顯微鏡表面形貌分析 54
4.1.3 X光繞射之結構與成分分析 56
4.1.4 拉曼光譜分析 58
4.1.5 穿透式電子顯微鏡之晶體結構分析 59
4.1.6 壓電性質分析 61
4.1.7 X光光電子能譜分析 63
4.1.8 紫外-可見光光譜之晶體能隙分析 65
4.2 光催化水分解實驗與分析 67
4.2.1 實驗方式與架構 67
4.2.2 線性掃描伏安法 68
4.2.3 光能轉換氫能效率圖 70
4.2.4 安培式電流時間曲線圖 72
4.2.5 電化學阻抗頻譜圖 74
4.2.6 莫特肖特基分析 77
4.2.7 光催化水分解機制 79
4.2.8 氫氣後處理反應機制 81
4.2.9 電化學量測結果分析 82
第五章 結論 83
第六章 未來展望 84
第七章 參考文獻 85

1. Inaguma, Y., M. Yoshida, and T. Katsumata, A polar oxide ZnSnO3 with a LiNbO3-type structure. Journal of the American Chemical Society, 2008. 130(21): p. 6704-6705.
2. Qiu, J., et al., The growth mechanism and optical properties of ultralong ZnO nanorod arrays with a high aspect ratio by a preheating hydrothermal method. Nanotechnology, 2009. 20(15): p. 155603.
3. Polsongkram, D., et al., Effect of synthesis conditions on the growth of ZnO nanorods via hydrothermal method. Physica B: Condensed Matter, 2008. 403(19-20): p. 3713-3717.
4. Zhang, Z., et al., Rational tailoring of ZnSnO 3/TiO 2 heterojunctions with bioinspired surface wettability for high-performance humidity nanosensors. Nanoscale, 2015. 7(9): p. 4149-4155.
5. Xu, J., et al., One-step hydrothermal synthesis and gas sensing property of ZnSnO3 microparticles. Solid-State Electronics, 2006. 50(3): p. 504-507.
6. Han, F., et al., Selective Formation of Carbon‐Coated, Metastable Amorphous ZnSnO3 Nanocubes Containing Mesopores for Use as High‐Capacity Lithium‐Ion Battery. Small, 2014. 10(13): p. 2637-2644.
7. Chen, Y., et al., Synthesis of ZnSnO 3 mesocrystals from regular cube-like to sheet-like structures and their comparative electrochemical properties in Li-ion batteries. Journal of Materials Chemistry, 2012. 22(48): p. 25373-25379.
8. Yuan, Z., et al., An amorphous nanosized tin-zinc composite oxide as a high capacity anode material for lithium ion batteries. Chemistry letters, 2002. 31(3): p. 408-409.
9. Choi, Y.-Y., et al., Nano-sized Ag-inserted amorphous ZnSnO 3 multilayer electrodes for cost-efficient inverted organic solar cells. Solar Energy Materials and Solar Cells, 2011. 95(7): p. 1615-1623.
10. Wu, J.M., et al., Ultrahigh sensitive piezotronic strain sensors based on a ZnSnO3 nanowire/microwire. ACS nano, 2012. 6(5): p. 4369-4374.
11. Guo, R., et al., Synthesis of Orthorhombic Perovskite-Type ZnSnO3 Single-Crystal Nanoplates and Their Application in Energy Harvesting. ACS Applied Materials & Interfaces, 2017. 9(9): p. 8271-8279.
12. Wu, J.M. and Y.N. Chen, The surface plasmon resonance effect on the enhancement of photodegradation activity by Au/ZnSn (OH) 6 nanocubes. Dalton Transactions, 2015. 44(37): p. 16294-16303.
13. Dong, S., et al., ZnSnO 3 hollow nanospheres/reduced graphene oxide nanocomposites as high-performance photocatalysts for degradation of metronidazole. Applied Catalysis B: Environmental, 2014. 144: p. 386-393.
14. Kim, J.H., et al., Defective ZnFe(2)O(4) nanorods with oxygen vacancy for photoelectrochemical water splitting. Nanoscale, 2015. 7(45): p. 19144-51.
15. Gan, J., et al., Oxygen vacancies promoting photoelectrochemical performance of In(2)O(3) nanocubes. Sci Rep, 2013. 3: p. 1021.
16. Ahmad, H., et al., Hydrogen from photo-catalytic water splitting process: A review. Renewable and Sustainable Energy Reviews, 2015. 43: p. 599-610.
17. Maeda, K. and K. Domen, New non-oxide photocatalysts designed for overall water splitting under visible light. The Journal of Physical Chemistry C, 2007. 111(22): p. 7851-7861.
18. Revie, R.W., Corrosion and corrosion control. 2008: John Wiley & Sons.
19. Bazant, Z.P., Physical model for steel corrosion in concrete sea structures--theory. Journal of the Structural Division, 1979. 105(ASCE 14651 Proceeding).
20. Abe, R., Recent progress on photocatalytic and photoelectrochemical water splitting under visible light irradiation. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2010. 11(4): p. 179-209.
21. van de Krol, R., Y. Liang, and J. Schoonman, Solar hydrogen production with nanostructured metal oxides. Journal of Materials Chemistry, 2008. 18(20): p. 2311.
22. Galińska, A. and J. Walendziewski, Photocatalytic water splitting over Pt− TiO2 in the presence of sacrificial reagents. Energy & Fuels, 2005. 19(3): p. 1143-1147.
23. Kudo, A. and I. Mikami, New In2O3 (ZnO) m photocatalysts with laminal structure for visible light-induced H2 or O2 evolution from aqueous solutions containing sacrificial reagents. Chemistry letters, 1998. 27(10): p. 1027-1028.
24. Schneider, J. and D.W. Bahnemann, Undesired role of sacrificial reagents in photocatalysis. 2013, ACS Publications.
25. Ding, C., et al., Solar-to-hydrogen efficiency exceeding 2.5% achieved for overall water splitting with an all earth-abundant dual-photoelectrode. Physical Chemistry Chemical Physics, 2014. 16(29): p. 15608-15614.
26. Chen, J., et al., Recent progress in enhancing solar-to-hydrogen efficiency. Journal of Power Sources, 2015. 280: p. 649-666.
27. Bard, A.J., et al., Electrochemical methods: fundamentals and applications. Vol. 2. 1980: Wiley New York.
28. Meites, L., Handbook of Analytical Chemistry. Soil Science, 1963. 96(5): p. 358.
29. Plieth, W., Electrochemistry for materials science. 2008: Elsevier.
30. Khan, S.U., M. Al-Shahry, and W.B. Ingler, Efficient photochemical water splitting by a chemically modified n-TiO2. science, 2002. 297(5590): p. 2243-2245.
31. Tang, J., J.R. Durrant, and D.R. Klug, Mechanism of photocatalytic water splitting in TiO2. Reaction of water with photoholes, importance of charge carrier dynamics, and evidence for four-hole chemistry. Journal of the American Chemical Society, 2008. 130(42): p. 13885-13891.
32. Yu, J., L. Qi, and M. Jaroniec, Hydrogen production by photocatalytic water splitting over Pt/TiO2 nanosheets with exposed (001) facets. The Journal of Physical Chemistry C, 2010. 114(30): p. 13118-13125.
33. Ni, M., et al., A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production. Renewable and Sustainable Energy Reviews, 2007. 11(3): p. 401-425.
34. Yang, X., et al., Nitrogen-doped ZnO nanowire arrays for photoelectrochemical water splitting. Nano Letters, 2009. 9(6): p. 2331-2336.
35. Steinfeld, A., Solar hydrogen production via a two-step water-splitting thermochemical cycle based on Zn/ZnO redox reactions. International Journal of Hydrogen Energy, 2002. 27(6): p. 611-619.
36. Wolcott, A., et al., Photoelectrochemical study of nanostructured ZnO thin films for hydrogen generation from water splitting. Advanced Functional Materials, 2009. 19(12): p. 1849-1856.
37. Zhang, X., Y. Liu, and Z. Kang, 3D branched ZnO nanowire arrays decorated with plasmonic au nanoparticles for high-performance photoelectrochemical water splitting. ACS Appl Mater Interfaces, 2014. 6(6): p. 4480-9.
38. Zhang, C., et al., Au nanoparticles sensitized ZnO nanorod@nanoplatelet core–shell arrays for enhanced photoelectrochemical water splitting. Nano Energy, 2015. 12: p. 231-239.
39. Linic, S., P. Christopher, and D.B. Ingram, Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy. Nature materials, 2011. 10(12): p. 911-921.
40. Reyes-Gil, K.R., E.A. Reyes-García, and D. Raftery, Nitrogen-doped In2O3 thin film electrodes for photocatalytic water splitting. The Journal of Physical Chemistry C, 2007. 111(39): p. 14579-14588.
41. Mihajlović, E., et al., PVC material fire retardants. Facta universitatis-series: Working and Living Enviromental Protection, 2010. 7(1): p. 1-11.
42. Liu, Z., et al., Plasmon resonant enhancement of photocatalytic water splitting under visible illumination. Nano letters, 2011. 11(3): p. 1111-1116.
43. Wu, F., et al., Photocatalytic activity of Ag/TiO2 nanotube arrays enhanced by surface plasmon resonance and application in hydrogen evolution by water splitting. Plasmonics, 2013. 8(2): p. 501-508.
44. Wang, G., et al., Hydrogen-treated TiO2 nanowire arrays for photoelectrochemical water splitting. Nano Lett, 2011. 11(7): p. 3026-33.
45. Bard, A.J. and L.R. Faulkner, Fundamentals and applications. Electrochemical Methods, 2001. 2.
46. Fontana, M.G., Corrosion engineering. 2005: Tata McGraw-Hill Education.
47. Jüttner, K., Electrochemical impedance spectroscopy (EIS) of corrosion processes on inhomogeneous surfaces. Electrochimica Acta, 1990. 35(10): p. 1501-1508.
48. Instruments, G., Basics of electrochemical impedance spectroscopy. G. Instruments, Complex impedance in Corrosion, 2007: p. 1-30.
49. Gao, Z., et al., Electrochemical and spectroscopic studies of cobalt-hexacyanoferrate film modified electrodes. Electrochimica acta, 1991. 36(1): p. 147-152.
50. Hunter, R.J., Zeta potential in colloid science: principles and applications. Vol. 2. 2013: Academic press.
51. Sekar, N. and R.P. Ramasamy, Electrochemical impedance spectroscopy for microbial fuel cell characterization. J Microb Biochem Technol S, 2013. 6(2).
52. Gou, H., F. Gao, and J. Zhang, Structural identification, electronic and optical properties of ZnSnO 3: First principle calculations. Computational Materials Science, 2010. 49(3): p. 552-555.
53. Kovacheva, D. and K. Petrov, Preparation of crystalline ZnSnO 3 from Li 2 SnO 3 by low-temperature ion exchange. Solid State Ionics, 1998. 109(3): p. 327-332.
54. Wu, J.M., et al., Lead-free nanogenerator made from single ZnSnO3 microbelt. ACS nano, 2012. 6(5): p. 4335-4340.
55. Zhang, J., et al., First-principles study of the ferroelectric and nonlinear optical properties of the LiNbO3-type ZnSnO3. Phys Chem Chem Phys, 2010. 12(32): p. 9197-204.
56. Nakayama, M., et al., First-principles studies on novel polar oxide ZnSnO3; pressure-induced phase transition and electric properties. Adv Mater, 2010. 22(23): p. 2579-82.
57. Lo, M.-K., S.-Y. Lee, and K.-S. Chang, Study of ZnSnO3-Nanowire Piezophotocatalyst Using Two-Step Hydrothermal Synthesis. The Journal of Physical Chemistry C, 2015. 119(9): p. 5218-5224.
58. Mukherjee, D., et al., Intrinsic anomalous ferroelectricity in vertically aligned LiNbO3-type ZnSnO3 hybrid nanoparticle-nanowire arrays. Applied Physics Letters, 2014. 105(21): p. 212903.
59. Para, T.A., H.A. Reshi, and V. Shelke, Synthesis of ZnSnO3 nanostructure by sol gel method. 2016. 1731: p. 050002.
60. Datta, A., et al., Evidence of superior ferroelectricity in structurally welded ZnSnO3 nanowire arrays. Small, 2014. 10(20): p. 4093-9.
61. Lee, J.-H., et al., Rhombohedral–orthorhombic morphotropic phase boundary in BiFeO3-based multiferroics: first-principles prediction. J. Mater. Chem., 2012. 22(4): p. 1667-1672.
62. Park, S.-M., T. Ikegami, and K. Ebihara, Effects of substrate temperature on the properties of Ga-doped ZnO by pulsed laser deposition. Thin Solid Films, 2006. 513(1): p. 90-94.
63. Mani, A., et al., Mott− Schottky Analysis and Impedance Spectroscopy of TiO2/6T and ZnO/6T devices. The Journal of Physical Chemistry B, 2008. 112(33): p. 10086-10091.
64. Bott, A.W., Electrochemistry of semiconductors. Current Separations, 1998. 17: p. 87-92.