太陽能是已知最乾淨且取之不盡用之不竭的能源。目前最理想的利用太陽的方法是將太陽的光能以氫氣的方式儲存起來，具體來說是透過光電化學反應(photoelectrochemical, PEC)去分解水得到氫氣。氧化亞銅是相當具有潛力的光電極材料候選者，因其製程簡單成本低且耗能少。然而，氧化亞銅在作為光陰極材料時具有嚴重的光腐蝕問題，這會降低氧化亞銅的光電化學反應性能。為了解決這些問題，我們利用無電電鍍的方式將奈米顆粒的鈀沉積在電鍍的氧化亞銅薄膜上，這將有利於從氧化亞銅提取光電子。此外，我們用厚度小於100 nm的檸檬酸鈉(trisodium citrate, TSC)作為鈍化層以披覆含有奈米顆粒鈀的氧化亞銅薄膜，以增強電子傳輸並防止氧化亞銅薄膜受到光腐蝕。本研究將探討Cu2O/Pd/TSC複合結構材料的光電化學性質。

The global energy shortage has become an imminent issue due to overpopulation and inefficient energy usage of human society. The most environment-friendly, green and abundant energy source is solar energy. Currently, the most ideal way to store and utilize solar energy is to produce hydrogen based on photoelectrochemical (PEC) water splitting reaction. Cuprous oxide (Cu2O) is a potential candidate of photoelectrode material because of its low synthesis cost and low energy-consumption fabrication processes. Nevertheless, Cu2O has a severe photocorrosion problem which would degrade the PEC performance and decrease the photoactivity of Cu2O. To resolve the problems, we have introduced palladium (Pd) nanoparticles on the electroplated Cu2O film by electroless deposition, facilitating the extraction of photoelectrons from the Cu2O. Moreover, we passivate the Pd-decorated Cu2O film with a thin trisodium nitrate (TSC) layer to enhance electron transport and prevent the Cu2O film from photocorrosion. The photoelectrochemical property of the Cu2O/Pd/TSC composite structure is investigated in this study.

1 第一章 緒論 3
1.1 前言 3
1.1.1 氫能 5
1.1.2 太陽能產氫 8
1.2 研究動機 11
2 第二章 文獻回顧 13
2.1 光電化學分解水產氫 13
2.1.1 光電產氫材料介紹 13
2.1.2 影響光電化學電極材料效能的因素 20
2.1.3 氧化亞銅作為光電產氫材料的挑戰 20
2.2 提升氧化亞銅光電性質的方法 21
2.2.1 能帶結構排列 21
2.2.2 共催化劑 22
2.2.3 鈍化層(Passivation) 25
3 第三章 實驗流程 29
3.1 實驗設計與流程 29
3.1.1 實驗藥品 30
3.1.2 Au/Cu2O的製備 30
3.1.3 奈米顆粒鈀的鍍製 31
3.1.4 檸檬酸鈉鈍化層的鍍製 32
3.2 量測及分析方式 32
3.2.1 電化學量測方式 34
3.2.2 微結構分析(SEM/TEM/XRD) 38
3.2.3 光譜分析(UV-Visible/PL) 38
3.2.4 X-Ray 光電子能譜儀(XPS)分析 39
4 第四章 結果與討論 40
4.1 奈米顆粒鈀作為共催化劑(cocatalyst)的影響 40
4.1.1 奈米顆粒鈀尺寸與形貌 40
4.1.2 鈀鍍製時間的調整 43
4.1.3 Au/Cu2O/Pd光電流提升機制 45
4.2 檸檬酸鈉(Trisodium citrate, TSC)作為鈍化膜(passivation)的影響 49
4.2.1 Au/Cu2O/TSC表面形貌 49
4.2.2 TSC鍍製時間調整 51
4.2.3 Au/Cu2O/TSC 光電流提升機制 53
4.3 Au/Cu2O/Pd/TSC複合結構光電性質與文獻比較 57
5 第五章 結論與未來展望 59
6 參考資料 60

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