地球不可再生能源逐漸短缺，發展乾淨綠色能源是必要的，水分解反應產生的
氫氣及氧氣是潔淨能源之一，但水分解反應所需施加的能量往往大於潔淨能源可生成的能量，而產氧反應(Oxygen evolution reaction, OER)是造成能量耗損過大的主因，所以需要催化劑來促進反應進行。在本研究中利用簡易的氧化還原方法，並透過加熱升溫來合成鈷錳氫氧化物薄膜(Cobalt manganese oxide hydroxide, CMOH)的催化劑，此方法快速以及能大面積鍍膜，且在複雜物體表面上亦能成功鍍膜。
本研究在一開始是使用硫酸鈷前驅物來合成薄膜(CMOH-sulfate, CMOH-S)，但由於用醋酸鈷來合成的薄膜(CMOH-acetate, CMOH-A)擁有更優異的光學性質，因此後續實驗轉而使用醋酸鈷合成。我們對CMOH-S及CMOH-A做了一系列鑑定及研究薄膜的產氧反應催化活性，以及加入以化學氣相沉積法製備的石墨烯對於催化活性的影響。由CMOH-S及CMOH-A薄膜在SEM中的表面形態、紫外-可見光吸收光譜及AFM薄膜透光度的比較中可得知厚度上的差異，CMOH-A(87.15%，於550 nm處) > CMOH-S (60.39%，於550 nm處)；在AFM厚度量測中，CMOH-S (120 nm) > CMOH-A (60 nm)，但CMOH-A薄膜後來由TEM鑑定發現薄膜僅5-10 nm而不是60 nm，經HRTEM可得知CMOH-A薄膜為非晶相。我們也發現不同鈷前驅物合成的薄膜雖然在光學性質上有差異，但在OER催化活性上是沒有改變的，藉由增加CMOH-A薄膜的邊長大小可得知薄膜的活性點是在於FTO導電玻璃與薄膜的交界處，所以薄膜厚度大小才會對於OER活性沒有影響。
最後，經研究後發現單層石墨烯在OER催化上扮演了保護催化劑的角色，只提升非常小的催化活性，而多層石墨烯則會影響氧氣的排出進而影響催化活性。我們也發現將覆蓋單層石墨烯後的CMOH-A-G薄膜在Ar氣體下高溫鍛燒後可使OER穩定度有更大的提升，經3000次循環掃描後電流僅損失7.6%，過電位仍維持在0.47 V (以10 mA cm-2為基準)。

It is necessary to develop clean and green energy because of the shortage of non-renewable energy. The hydrogen and oxygen generated by water splitting is one of the solution for clean energy. However, energy required for water splitting is usually greater than energy generated by water splitting. Oxygen evolution reaction (OER) is the main reason of excessive energy consumption in the splitting process, thus it is necessary to prepare a catalyst to promote the OER. In this research, by a simple redox method with heating, we successfully synthesized cobalt manganese oxide hydroxide (CMOH) catalyst. This method is fast and simple; efficiently deposit catalytic thin film on large area substrate even on complex surfaces.
At first, we used cobalt sulfate as precursor to prepare catalytic films (CMOH-sulfate, CMOH-S) for electrochemical measurement. However, the films (CMOH-acetate, CMOH-A) prepared by cobalt acetate have superior optical properties to CMOH-S, so we chose cobalt acetate for subsequent experiments. To further understand the difference between CMOH-S and CMOH-A, We characterized these two thin film by a series of characterization. The results of UV-visible and AFM show that the thickness of CMOH-A is smaller than CMOH-S thus has higher transmittance. CMOH-A have transmittance of 87.15% with thickness of 60 nm versus CMOH-S having 60.39% transmittance and 120 nm thickness. We further confirmed the thickness of CMOH-A to be 5 to 10 nm by TEM (rather than 60 nm by AFM), and the composition is amorphous. Despite the difference on optical property, CMOH-S and CMOH-A exhibit almost the same on OER activity. To study the reason, we altered the length of CMOH-A films, knowing that the active sites actually lie at the interface of catalyst and FTO glass.
Finally, after covering a layer of graphene on the catalytic thin films and go through 500ºC calcination under Ar, we tremendously raise the stability of OER catalyzing process, with only 7.6% decay of current after 3000 circles scanning and still remain at same over potential (0.47 V at 10 mA cm-2).

目錄
論文審定書 i
誌謝 ii
摘要 iv
Abstract v
目錄 vii
圖目錄 x
表目錄 xv
第一章、緒論 1
1.1 研究動機 2
1.2 研究背景 3
1.2.1 氧化還原方法製備二元金屬氧化物 3
1.2.2 鈷氧化物的應用 3
1.2.3 石墨烯歷史及性質介紹 4
1.2.4 石墨烯拉曼光譜 7
1.2.5 石墨烯合成方法-化學剝離法及化學氣相沉積法 10
1.2.5.1 化學剝離法 10
1.2.5.2 化學氣相沉積法 11
1.2.6 產氧反應 13
第二章、實驗樣品合成與鑑定方法 15
2.1 實驗藥品 15
2.2 於FTO導電玻璃上生成鈷錳氫氧化物薄膜 16
2.2.1 FTO導電玻璃清洗 16
2.2.2 清洗前與清洗後的FTO玻璃個別鋪上石墨烯後的完整性差異 17
2.2.3 生成鈷錳氫氧化物薄膜 18
2.2.4 生成鈷錳氧化物薄膜 18
2.3 製備單層石墨烯 20
2.3.1 三步合成單層石墨烯 20
2.3.1.1 電拋光處理 (electropolish treatment) 20
2.3.1.2 銅箔高溫預處理 21
2.3.1.3 單層石墨烯合成 21
2.3.2 單層石墨烯的轉移 22
2.4 電化學裝置最佳化 23
第三章、研究結果 24
3.1 以硫酸鈷(COSO4‧7H2O)作為前驅物所合成之薄膜鑑定 24
3.1.1 薄膜晶體結構及不同反應溫度下之表面形態 24
3.1.2 薄膜之鈷錳元素間比例變化 29
3.2 CMOH-S薄膜電化學活性 33
3.2.1 改變薄膜反應條件對OER活性的影響 33
3.2.2 改變鈷錳前驅物之莫耳比對OER活性的影響 34
3.3 以醋酸鈷(CO(OAC)2‧4H2O)作為前驅物所合成之薄膜鑑定 38
3.3.1薄膜晶體結構及不同反應溫度下之表面形態 38
3.3.2薄膜之鈷錳元素比例鑑定 42
3.3.3 薄膜鈷與錳的價態判定及厚度量測 45
3.3.4 以穿透式電子顯微鏡鑑定薄膜晶體結構以及厚度量測 50
3.3.4.1 CMOH-A薄膜於穿透式電子顯微鏡下之鑑定 50
3.3.4.2 CMO-A-Air薄膜於穿透式電子顯微鏡下之鑑定 55
3.3.4.3 CMO-A-Ar薄膜於穿透式電子顯微鏡下之鑑定 58
3.4 CMOH-A薄膜電化學活性 61
3.4.1 CMOH-S與CMOH-A薄膜於OER活性的表現 61
3.4.2 使用水熱法合成之CMOH-A薄膜對於OER活性之影響 61
3.4.3 薄膜OER活性點的探討 63
3.4.4 增加OER的活性點：合成不同面積大小的薄膜 66
3.4.5 於不同酸鹼環境下合成CMOH-A薄膜對於OER活性的影響 69
3.4.6 CMOH-A與CMO-A-Ar薄膜分別覆蓋石墨烯對於OER穩定性的影響 72
3.4.7 研究大面積CMOH-A的pattern薄膜合成方法及OER活性之測量 77
3.4.7.1 研究大面積CMOH-A的pattern薄膜合成方法 77
3.4.7.2 大面積CMOH-A的pattern薄膜OER活性之測量 82
四、討論 84
4.1 陰離子效應 84
4.2 以LSV掃描CMOH-A薄膜OER穩定度及在表面形態上的改變 85
4.3 CMOH-A薄膜與FTO界面對於活性點的影響 88
4.4 於任意複雜物體、軟性基板上鍍膜 94
五、結論 95
參考文獻 96

參考文獻
(1) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Science 2004, 306, 666-668.
(2) Kuo, C.-C.; Lan, W.-J.; Chen, C.-H. Nanoscale 2014, 6, 334-341.
(3) Lan, W.-J.; Kuo, C.-C.; Chen, C.-H. Chem. Commun. 2013, 49, 3025-3027.
(4) Lan, W.-J.; Chen, C.-H. Electrochim. Acta. 2015, 180, 1014-1022.
(5) Bian, W.; Yang, Z.; Strasser, P.; Yang, R. J. Power Sources 2014, 250, 196-203.
(6) Chen, S.; Duan, J.; Ran, J.; Jaroniec, M.; Qiao, S. Z. Energy Environ. Sci. 2013, 6, 3693-3699.
(7) Du, J.; Chen, C.; Cheng, F.; Chen, J. Inorg. Chem. 2015, 54, 5467-5474.
(8) Guo, S. X.; Liu, Y.; Bond, A. M.; Zhang, J.; Esakki Karthik, P.; Maheshwaran, I.; Senthil Kumar, S.; Phani, K. L. Phys. Chem. Chem. Phys. 2014, 16, 19035-19045.
(9) Long, X.; Li, J.; Xiao, S.; Yan, K.; Wang, Z.; Chen, H.; Yang, S. Angew. Chem. Int. Ed. 2014, 53, 7584-7588.
(10) Mao, S.; Wen, Z.; Huang, T.; Hou, Y.; Chen, J. Energy Environ. Sci. 2014, 7, 609-616.
(11) Zhao, Y.; Chen, S.; Sun, B.; Su, D.; Huang, X.; Liu, H.; Yan, Y.; Sun, K.; Wang, G. Sci. Rep. 2015, 5, 7629-7635.
(12) Xiong, S.; Chen, J. S.; Lou, X. W.; Zeng, H. C. Adv. Funct. Mater. 2012, 22, 861-871.
(13) Zhu, X.; Ning, G.; Ma, X.; Fan, Z.; Xu, C.; Gao, J.; Xu, C.; Wei, F. J. Mater. Chem. A 2013, 1, 14023-14046.
(14) Zhang, Y.; Ma, M.; Yang, J.; Su, H.; Huang, W.; Dong, X. Nanoscale 2014, 6, 4303-4308.
(15) Hosono, E.; Fujihara, S.; Honma, I.; Ichihara, M.; Zhou, H. J. Power Sources 2006, 158, 779-783.
(16) Wang, J.; Yang, N.; Tang, H.; Dong, Z.; Jin, Q.; Yang, M.; Kisailus, D.; Zhao, H.; Tang, Z.; Wang, D. Angew. Chem. Int. Ed. 2013, 52, 6417-6420.
(17) Liu, D.; Wang, X.; Wang, X.; Tian, W.; Bando, Y.; Golberg, D. Sci. Rep. 2013, 3, 2543-2549.
(18) Li, W.-Y.; Xu, L.-N.; Chen, J. Adv. funct. mater. 2005, 15, 851-857.
(19) Su, C.-Y.; Lan, W.-J.; Chu, C.-Y.; Liu, X.-J.; Kao, W.-Y.; Chen, C.-H. Electrochim. Acta. 2016, 190, 588-595.
(20) Hamdani, M.; Singh, R. N.; Chartier, P. Int. J. Electrochem. Sci. 2010, 5, 556-577.
(21) Liang, Y.; Li, Y.; Wang, H.; Zhou, J.; Wang, J.; Regier, T.; Dai, H. Nat. Mater. 2011, 10, 780-786.
(22) Xiao, J.; Kuang, Q.; Yang, S.; Xiao, F.; Wang, S.; Guo, L. Sci. Rep. 2013, 3, 2300-2308.
(23) Liu, S.; Li, L.; Ahn, H. S.; Manthiram, A. J. Mater. Chem. A 2015, 3, 11615-11623.
(24) Ma, T. Y.; Dai, S.; Jaroniec, M.; Qiao, S. Z. J. Am. Chem. Soc. 2014, 136, 13925-13931.
(25) Jagadeesh, R. V.; Junge, H.; Pohl, M. M.; Radnik, J.; Bruckner, A.; Beller, M. J. Am. Chem. Soc. 2013, 135, 10776-10782.
(26) wallace, P. R. Phys. Rev. 1947, 71, 622-634.
(27) McClure, J. W. Phys. Rev. 1956, 104, 666-671.
(28) Slonczewski, J. C.; Weiss, P. R. Phys. Rev. 1958, 109, 272-279.
(29) Fradkin, E. Phys. Rev. B 1986, 33, 3263-3268.
(30) Geim, A. K.; Novoselov, K. S. Nat. Mater. 2007, 6, 183-191.
(31) Lee, C.; Wei, X.; Kysar, J. W.; Hone, J. Science 2008, 321, 385-388.
(32) Balandin, A. A.; Ghosh, S.; Bao, W.; Calizo, I.; Teweldebrhan, D.; Miao, F.; Lau, C. N. Nano Lett. 2008, 8, 902-907.
(33) Nair, R. R.; Blake, P.; Grigorenko, A. N.; Novoselov, K. S.; Booth, T. J.; Stauber, T.; Peres, N. M.; Geim, A. K. Science 2008, 320, 1308.
(34) Meyer, J. C.; Girit, C. O.; Crommie, M. F.; Zettl, A. Nature 2008, 454, 319-322.
(35) Schedin, F.; Geim, A. K.; Morozov, S. V.; Hill, E. W.; Blake, P.; Katsnelson, M. I.; Novoselov, K. S. Nat. Mater. 2007, 6, 652-655.
(36) Bonaccorso, F.; Sun, Z.; Hasan, T.; Ferrari, A. C. Nat. Photonics 2010, 4, 611-622.
(37) Schwierz, F. Nat. Nanotechnol. 2010, 5, 487-496.
(38) Wu, Y.; Yang, B.; Zong, B.; Sun, H.; Shen, Z.; Feng, Y. J. Mater. Chem. 2004, 14, 469-477.
(39) Eda, G.; Fanchini, G.; Chhowalla, M. Nat. Nanotechnol. 2008, 3, 270-274.
(40) Wang, X.; Zhi, L.; Mullen, K. Nano Lett. 2007, 8, 323-327.
(41) Liang, Q.; Yao, X.; WeiWang; Liu, Y.; Wong, C. P. ACS Nano 2011, 5, 2392-2401.
(42) Stoller, M. D.; Park, S.; Zhu, Y.; An, J.; Ruoff, R. S. Nano Lett. 2008, 8, 3498-3502.
(43) Chandler, D. L. http://news.mit.edu/2012/graphene-water-desalination-0702 2012.
(44) Miao, X.; Tongay, S.; Petterson, M. K.; Berke, K.; Rinzler, A. G.; Appleton, B. R.; Hebard, A. F. Nano Lett. 2012, 12, 2745-2750.
(45) Nasrollahzadeh, M.; Babaei, F.; Fakhri, P.; Jaleh, B. RSC Adv. 2015, 5, 10782-10789.
(46) Maiti, R.; Manna, S.; Midya, A.; Ray, S. K. Opt. Express 2013, 21, 26034-26043.
(47) Ni, Z. H.; Wang, H. M.; Kasim, J.; Fan, H. M.; Yu, T.; Wu, Y. H.; Feng, Y. P.; Shen, Z. X. Nano Lett. 2007, 7, 2758-2763.
(48) Hummers, W. S.; Offeman, R. E. J. Am. Chem. Soc. 1957, 80, 1339.
(49) Shin, H.-J.; Kim, K. K.; Benayad, A.; Yoon, S.-M.; Park, H. K.; Jung, I.-S.; Jin, M. H.; Jeong, H.-K.; Kim, J. M.; Choi, J.-Y.; Lee, Y. H. Adv. Funct. Mater. 2009, 19, 1987-1992.
(50) Schniepp, H. C.; Li, J.-L.; McAllister, M. J.; Sai, H.; Herrera-Alonso, M.; Adamson, D. H.; Prud'homme, R. K.; Car, R.; Saville, D. A.; Aksay, I. A. J. Phys. Chem. B 2006, 110, 8535-8539.
(51) Bonaccorso, F.; Lombardo, A.; Hasan, T.; Sun, Z.; Colombo, L.; Ferrari, A. C. Mater. Today 2012, 15, 564-589.
(52) Kumar, A.; Lee, C. H. Synthesis and Biomedical Applications of Graphene: Present and Future Trends, 2013.
(53) Li, X.; Cai, W.; An, J.; Kim, S.; Nah, J.; Yang, D.; Piner, R.; Velamakanni, A.; Jung, I.; Tutuc, E.; Banerjee, S. K.; Colombo, L.; Ruoff, R. S. Science 2009, 324, 1312-1314.
(54) Kim, K. S.; Zhao, Y.; Jang, H.; Lee, S. Y.; Kim, J. M.; Kim, K. S.; Ahn, J. H.; Kim, P.; Choi, J. Y.; Hong, B. H. Nature 2009, 457, 706-710.
(55) Kwon, S.-Y.; Ciobanu, C. V.; Petrova, V.; Shenoy, V. B.; Baren˜o, J.; Gambin, V.; Petrov, I.; Kodambaka, S. Nano Lett. 2009, 9, 3985-3990.
(56) Sutter, P. W.; Flege, J. I.; Sutter, E. A. Nat. Mater. 2008, 7, 406-411.
(57) Coraux, J.; N'Diaye, A. T.; Busse, C.; Michely, T. Nano Lett. 2008, 8, 565-570.
(58) Li, X.; Cai, W.; Colombo, L.; Ruoff, R. S. Nano Lett. 2009, 9, 4268-4272.
(59) Reece, S. Y.; Hamel, J. A.; Sung, K.; Jarvi, T. D.; Esswein, A. J.; Pijpers, J. J. H.; Nocera, D. G. Science 2011, 334, 645-648.
(60) Louie, M. W.; Bell, A. T. J. Am. Chem. Soc. 2013, 135, 12329-12337.
(61) Song, F.; Hu, X. J. Am. Chem. Soc. 2014, 136, 16481-16484.
(62) Trotochaud, L.; Ranney, J. K.; Williams, K. N.; Boettcher, S. W. J. Am. Chem. Soc. 2012, 134, 17253-17261.
(63) Wu, X.; Li, F.; Zhang, B.; Sun, L. J. Photochem. Photobiol. C: Photochem. Rev. 2015, 25, 71-89.
(64) Suntivich, J.; May, K. J.; Gasteiger, H. A.; Goodenough, J. B.; Shao-Horn, Y. Science 2011, 334, 1383-1385.
(65) Tiwari, S. K.; Singh, S. P.; Singh, R. N. J. Electrochem. Soc. 1996, 143, 1505-1510.
(66) 李尉勤 (2015)‧化學氣相沉積法製備高品質單層石墨烯之研究
(67) Kwon, G. D.; Kim, Y. W.; Moyen, E.; Keum, D. H.; Lee, Y. H.; Baik, S.; Pribat, D. Appl. Surf. Sci. 2014, 307, 731-735.
(68) Fabiane, M.; Khamlich, S.; Bello, A.; Dangbegnon, J.; Momodu, D.; Charlie Johnson, A. T.; Manyala, N. AIP Adv. 2013, 3, 112126.
(69) Wei-Chen Chang, Y.-Y. C., Wan-Chin Yu, Yih-Chun Yao, Chia-Hua Lee and Hung-Han Ko Nanoscale Res. Lett. 2012, 7:166, 1-7.
(70) Yang, J. K.; Liang, B.; Zhao, M. J.; Gao, Y.; Zhang, F. C.; Zhao, H. L. Sci. Rep. 2015, 5, 15001-15007.
(71) Tian, Z.-Y.; Tchoua Ngamou, P. H.; Vannier, V.; Kohse-Höinghaus, K.; Bahlawane, N. Appl. Catal. B 2012, 117-118, 125-134.
(72) Liu, X.-S.; Jin, Z.-N.; Lu, J.-Q.; Wang, X.-X.; Luo, M.-F. Chem. Eng. J. 2010, 162, 151-157.
(73) Njagi, E. C.; Chen, C.-H.; Genuino, H.; Galindo, H.; Huang, H.; Suib, S. L. Appl. Catal. B 2010, 99, 103-110.
(74) Zhong-Ai Hu, Y.-L. X., Yao-Xian Wang, Li-Jing Xie, Guo-Rui Fu, Xiao-Qing Jin,; Zi-Yu Zhang, Y.-Y. Y., and Hong-Ying Wu J. Phys. Chem. C 2009, 113, 12502-12508.
(75) Gautier, J. L.; Rios, E.; Gracia, M.; Marco, J. F.; Gancedo, J. R. Thin Solid Films 1997, 311, 51-57.
(76) Gao, M.; Sheng, W.; Zhuang, Z.; Fang, Q.; Gu, S.; Jiang, J.; Yan, Y. J. Am. Chem. Soc. 2014, 136, 7077-7084.
(77) He, C.; Wu, X.; He, Z. J. Phy. Chem. C 2014, 118, 4578-4584.
(78) Lu, X.; Zhao, C. Nat. Commun. 2015, 6, 6616-6623.
(79) Jeon, H. S.; Jee, M. S.; Kim, H.; Ahn, S. J.; Hwang, Y. J.; Min, B. K. ACS Appl. Mater. Interfaces 2015, 7, 24550-24555.
(80) Smith, R. D.; Prevot, M. S.; Fagan, R. D.; Trudel, S.; Berlinguette, C. P. J. Am. Chem. Soc. 2013, 135, 11580-11586.