本研究中，微米尺度與奈米尺度方柱之氧化銅铋修飾電極成功被合成並詳盡探討合成條件對於表面形態、晶格成長行為、電催化特性與光電化特性的影響。物理化學特性，包含表面型態、晶相、光學特性、電催化特性，藉由掃描式電子顯微鏡、穿透式電子顯微鏡、X光繞射儀和紫外光至可見光吸收光譜去鑑定，而電催化與光電催化特性是由循環伏安法、線性掃描伏安法、計時電流分析法以及電化學阻抗分析等技術進行分析。
在製備微米與奈米氧化銅铋修飾電極，首先會在參氟氧化錫透明導電玻璃上，藉由旋轉塗佈與熱處理合成出氧化銅铋晶種層，接著將晶種層浸泡在含有醋酸銅與硝酸铋之化學沉積液中，在室溫下進行微米與奈米氧化銅铋的成長。在化學沉積液中含有0.075 mM醋酸銅與0.20 mM 硝酸铋下，長出高寬比1.7之微米尺度方柱之氧化銅铋，而在化學沉積液中含有0.45 mM醋酸銅與1.20 mM 硝酸铋下，長出高寬比10.9之奈米尺度方柱氧化銅铋，此外，在降低化學沉積液的銅铋比例，奈米尺度氧化銅並會以c軸做為優先晶體取向，而這樣的行為被認為和醋酸根的優先吸附在氧化銅铋晶相有關。同時也發現，氧化銅铋的結構對於電催化葡萄糖氧化有很大的影響；在微米、奈米以及c軸面相奈米氧化銅铋之葡萄糖氧化的速率常數分別為 248.81, 1048.23和452.09 L mol-1 s-1。
經熱處理的微米、奈米與c軸面相奈米氧化銅铋遭遇嚴重的光腐蝕，但鍍上氧化鈦薄膜與白金產輕觸媒可以提高光穩定性。

In this study, copper bismuth oxide micron-sized square columns (microCuBi2O4) and nano-sized square columns (nanoCuBi2O4) modified electrodes were prepared and the effects of the synthetic conditions on the surface morphologies, the crystal growth behavior, electrocatalytic properties, and photoelectrocatalytic properties of CuBi2O4 were thoroughly investigated. Physicochemical, including surface morphology, crystal phase, optical properties, electrocatalytic properties, were investigated by scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and uv-vis spectroscopy, whereas the electrocatalytic and photoelectrocatalytic properties were examined using cyclic voltammetry, linear sweep voltammetry, chronoamperometry, and electrochemical impedance spectroscopy.
The microCuBi2O4 and nanoCuBi2O4 modified electrodes were prepared by firstly preparing a CuBi2O4 seed-layer modified fluorine-doped tin oxide coated glass electrode (FTO) using spin-coating method, followed by the growth of microCuBi2O4 and nanoCuBi2O4 onto the seed-layer coated FTO using chemical bath deposition (CBD) in an aqueous solution containing copper acetate and bismuth nitrate at room temperature. It was found that CuBi2O4 was grown in the form of micron-sized square columns with aspect ratio of ~1.7 in the bath containing 0.075 mM copper acetate and 0.20 mM bismuth nitrate, but in the form of nano-sized square columns with aspect ratio of ~10.9 in the bath containing 0.45 mM copper acetate and 1.20 mM bismuth nitrate. In addition, the preferential crystal orientation of nanoCuBi2O4 was tuned to be c-axis by decreasing the Cu2+/Bi3+ molar ratio in the bath solution, and this behavior was found to be related to the preferential adsorption of acetate on to the CuBi2O4 crystal. It was also found that the structure of CuBi2O4 has great influence on the electrocatalytic glucose oxidation; the rate constant of glucose oxidation at microCuBi2O4, nanoCuBi2O4, and c-axis oriented nanoCuBi2O4 (c-nanoCuBi2O4) are 248.81, 1048.23, and 452.09 L mol-1 s-1, respectively.
The annealed microCuBi2O4, nanoCuBi2O4, and c-nanoCuBi2O4 suffered serious photocorrosion, but the photostability can be improved by deposited TiO2 protection layer along with Pt hydrogen evolution catalyst.

[1] C. Henmi and Kusachiite, "CuBi2O4, a New Mineral form Fuka, Okayama Prefecture, Japan," Moneralogical Magazine, vol. 59, no. 3, pp. 545-548, 1995.
[2] Y. Nakabayashi, M. Nishikawa, and Y. Nosaka, "Fabrication of CuBi2O4 photocathode through novel anodic electrodeposition for solar hydrogen production," Electrochimica Acta, vol. 125, pp. 191-198, 2014.
[3] N. T. Hahn, V. C. Holmberg, B. A. Korgel, and C. B. Mullins, "Electrochemical Synthesis and Characterization of p-CuBi2O4 Thin Film Photocathodes," The Journal of Physical Chemistry C, vol. 116, no. 10, pp. 6459-6466, 2012/03/15 2012.
[4] D. Cao et al., "p-Type CuBi2O4: an easily accessible photocathodic material for high-efficiency water splitting," Journal of Materials Chemistry A, vol. 4, no. 23, pp. 8995-9001, 2016.
[5] F. Wang, A. Chemseddine, F. F. Abdi, R. van de Krol, and S. P. Berglund, "Spray pyrolysis of CuBi2O4 photocathodes: improved solution chemistry for highly homogeneous thin films," Journal of Materials Chemistry A, vol. 5, no. 25, pp. 12838-12847, 2017.
[6] F. Wang et al., "Gradient Self-Doped CuBi2O4 with Highly Improved Charge Separation Efficiency," J Am Chem Soc, vol. 139, no. 42, pp. 15094-15103, Oct 25 2017.
[7] J. Li, M. Griep, Y. Choi, and D. Chu, "Photoelectrochemical overall water splitting with textured CuBi2O4 as a photocathode," Chem Commun (Camb), vol. 54, no. 27, pp. 3331-3334, Mar 29 2018.
[8] S. P. Berglund, F. F. Abdi, P. Bogdanoff, A. Chemseddine, D. Friedrich, and R. van de Krol, "Comprehensive Evaluation of CuBi2O4 as a Photocathode Material for Photoelectrochemical Water Splitting," Chemistry of Materials, vol. 28, no. 12, pp. 4231-4242, 2016.
[9] C.-H. Wu, E. Onno, and C.-Y. Lin, "CuO nanoparticles decorated nano-dendrite-structured CuBi2O4 for highly sensitive and selective electrochemical detection of glucose," Electrochimica Acta, vol. 229, pp. 129-140, 2017.
[10] H. S. Park, C. Y. Lee, and E. Reisner, "Photoelectrochemical reduction of aqueous protons with a CuO|CuBi2O4 heterojunction under visible light irradiation," Phys Chem Chem Phys, vol. 16, no. 41, pp. 22462-5, Nov 7 2014.
[11] N. Xu et al., "N,Cu-Codoped Carbon Nanosheet/Au/CuBi2O4 Photocathodes for Efficient Photoelectrochemical Water Splitting," ACS Sustainable Chemistry & Engineering, vol. 6, no. 6, pp. 7257-7264, 2018.
[12] D. Kumar, R. Bai, S. Chaudhary, and D. K. Pandya, "Enhanced photoelectrochemical response for hydrogen generation in self-assembled aligned ZnO/PbS core/shell nanorod arrays grown by chemical bath deposition," Materials Today Energy, vol. 6, pp. 105-114, 2017.
[13] S. Paul, J. Sultana, A. Banerjee, P. Singha, A. Karmakar, and S. Chattopadhyay, "Electrical Characterization of n-ZnO NW/p-CuO Thin Film Hetero-Junction Solar Cell Grown by Chemical Bath Deposition and Vapor Liquid Solid Technique with Varying Reaction Time," vol. 194, pp. 165-171, 2017.
[14] F. Lisco et al., "The structural properties of CdS deposited by chemical bath deposition and pulsed direct current magnetron sputtering," Thin Solid Films, vol. 582, pp. 323-327, 2015.
[15] W.-L. Liu, W.-J. Chen, S.-H. Hsieh, and J.-H. Yu, "Growth Behavior of Nanocrystalline ZnS Thin Films for Solar Cell Using CBD Technique," Procedia Engineering, vol. 36, pp. 46-53, 2012.
[16] J.-w. Ha, J. Oh, H. Choi, H. Ryu, W.-J. Lee, and J.-S. Bae, "Photoelectrochemical properties of Ni-doped CuO nanorods grown using the modified chemical bath deposition method," Journal of Industrial and Engineering Chemistry, vol. 58, pp. 38-44, 2018.
[17] S. Paul, J. Sultana, A. Bhattacharyya, A. Karmakar, and S. Chattopadhyay, "Investigation of the comparative photovoltaic performance of n-ZnO nanowire/p-Si and n-ZnO nanowire/p-CuO heterojunctions grown by chemical bath deposition method," Optik, vol. 164, pp. 745-752, 2018.
[18] McPeak and K. M, Chemical bath deposition of semiconductor thin films & nanostructures in novel microreactors. Drexel University, 2010.
[19] M. Piryaei, E. Gholami Hatam, and N. Ghobadi, "Influence of pH on the optical, structural and compositional properties of nanocrystalline CdSe thin films prepared by chemical bath deposition," Journal of Materials Science: Materials in Electronics, vol. 28, no. 3, pp. 2550-2556, 2016.
[20] Valenzuela GR, Ponce HE, Trejo D, and V. CG, "Effect of Heat Treatment on Cds Thin Films by Chemical Bath Deposition," Int J Electron Device Phys, vol. 1, 2017.
[21] M. G. O Erkena, D Ozaslanc, and C. Gumusc, "Effect of the deposition time on optical and electrical properties of semiconductor ZnS thin films prepared by chemical bath deposition," Indian Journal of Pure & Applied Physics, vol. 55, pp. 471-477, 2017.
[22] R. Bai, S. Chaudhary, and D. K. Pandya, "Temperature dependent charge transport mechanisms in highly crystalline p -PbS cubic nanocrystals grown by chemical bath deposition," Materials Science in Semiconductor Processing, vol. 75, pp. 301-310, 2018.
[23] T. Cossuet, E. Appert, J.-L. Thomassin, and V. Consonni, "Polarity-Dependent Growth Rates of Selective Area Grown ZnO Nanorods by Chemical Bath Deposition," Langmuir, vol. 33, no. 25, pp. 6269-6279, 2017/06/27 2017.
[24] B. A. Vessalli, C. A. Zito, T. M. Perfecto, D. P. Volanti, and T. Mazon, "ZnO nanorods/graphene oxide sheets prepared by chemical bath deposition for volatile organic compounds detection," Journal of Alloys and Compounds, vol. 696, pp. 996-1003, 2017.
[25] D. Sariket et al., "Temperature controlled fabrication of chemically synthesized cubic In 2 O 3 crystallites for improved photoelectrochemical water oxidation," Materials Chemistry and Physics, vol. 201, pp. 7-17, 2017.
[26] A. Ray et al., "Optimization of photoelectrochemical performance in chemical bath deposited nanostructured CuO," Journal of Alloys and Compounds, vol. 695, pp. 3655-3665, 2017.
[27] J. Y. Yao, L. Yan, G. Y. Peng, M. De Qing, and Z. F. Xin, "Photoelectric properties of Cu2O thin films prepared by room-temperature water bath," Materials Research Express, vol. 4, no. 3, p. 036404, 2017.
[28] Y. B. K. Kumar and V. S. Raja, "Investigations on the growth of Cu 2 ZnSnS 4 thin films for solar cell absorber layer," Surfaces and Interfaces, vol. 9, pp. 233-237, 2017.
[29] G. Hodes, Chemical Solution Deposition of Semiconductor Film. 2002.
[30] Q. Zhang, S.-J. Liu, and S.-H. Yu, "Recent advances in oriented attachment growth and synthesis of functional materials: concept, evidence, mechanism, and future," J. Mater. Chem., vol. 19, no. 2, pp. 191-207, 2009.
[31] Clemens Burda, Xiaobo Chen, Radha Narayanan, and M. A. El-Sayed, "Chemistry and Properties of Nanocrystals of Different Shapes," Chem. Rev., vol. 105, pp. 1025-1102, 2005.
[32] G. Xu et al., "Ethylene glycol (EG) solvothermal synthesis of flower-like LiMnPO4nanostructures self-assembled with (010) nanobelts for Li-ion battery positive cathodes," CrystEngComm, vol. 18, no. 18, pp. 3282-3288, 2016.
[33] S. H. Wu, C. Y. Mou, and H. P. Lin, "Synthesis of mesoporous silica nanoparticles," Chem Soc Rev, vol. 42, no. 9, pp. 3862-75, May 7 2013.
[34] K.-S. Cho, D. V. Talapin, W. Gaschler, and C. B. Murray, "Designing PbSe Nanowires and Nanorings through Oriented Attachment of Nanoparticles," Journal of the American Chemical Society, vol. 127, no. 19, pp. 7140-7147, 2005/05/01 2005.
[35] B. Liu, S. H. Yu, L. Li, Q. Zhang, F. Zhang, and K. Jiang, "Morphology control of stolzite microcrystals with high hierarchy in solution," Angew Chem Int Ed Engl, vol. 43, no. 36, pp. 4745-50, Sep 13 2004.
[36] D. Lincot and G. Hodes, Chemical Solution Deposition of Semiconducting and Non-Metallic Films: Proceedings of the International Symposium. The Electrochemical Society, 2006.
[37] L. Vayssieres, "Growth of arrayed nanorods and nanowires of ZnO from aqueous solutions," Advanced Materials, vol. 15, no. 5, pp. 464-466, 2003.
[38] J. Wang, "Electrochemical Glucose Biosensors," Chemical Reviews, vol. 108, no. 2, pp. 814-825, 2008/02/01 2008.
[39] S. Lee, J. Lee, S. Park, H. Boo, H. C. Kim, and T. D. Chung, "Disposable non-enzymatic blood glucose sensing strip based on nanoporous platinum particles," Applied Materials Today, vol. 10, pp. 24-29, 2018.
[40] C. Zhang et al., "Small Naked Pt Nanoparticles Confined in Mesoporous Shell of Hollow Carbon Spheres for High-Performance Nonenzymatic Sensing of H2O2 and Glucose," ACS Omega, vol. 3, no. 1, pp. 96-105, 2018.
[41] C. Megías-Sayago, L. Bobadilla, S. Ivanova, A. Penkova, M. Centeno, and J. Odriozola, "Gold catalyst recycling study in base-free glucose oxidation reaction," Catalysis Today, vol. 301, pp. 72-77, 2018.
[42] T. Ishida, N. Kinoshita, H. Okatsu, T. Akita, T. Takei, and M. Haruta, "Influence of the support and the size of gold clusters on catalytic activity for glucose oxidation," Angewandte Chemie, vol. 120, no. 48, pp. 9405-9408, 2008.
[43] Q. Yi, F. Niu, and W. Yu, "Pd-modified TiO2 electrode for electrochemical oxidation of hydrazine, formaldehyde and glucose," Thin Solid Films, vol. 519, no. 10, pp. 3155-3161, 2011.
[44] A. Liu, "Towards development of chemosensors and biosensors with metal-oxide-based nanowires or nanotubes," Biosens Bioelectron, vol. 24, no. 2, pp. 167-77, Oct 15 2008.
[45] M. M. Rahman, A. J. Ahammad, J. H. Jin, S. J. Ahn, and J. J. Lee, "A comprehensive review of glucose biosensors based on nanostructured metal-oxides," Sensors (Basel), vol. 10, no. 5, pp. 4855-86, 2010.
[46] L. Liu, W. Qi, X. Gao, C. Wang, and G. Wang, "Synergistic effect of metal ion additives on graphitic carbon nitride nanosheet-templated electrodeposition of Cu@CuO for enzyme-free glucose detection," Journal of Alloys and Compounds, vol. 745, pp. 155-163, 2018.
[47] X. Gou et al., "A very facile strategy for the synthesis of ultrathin CuO nanorods towards non-enzymatic glucose sensing," New Journal of Chemistry, vol. 42, no. 8, pp. 6364-6369, 2018.
[48] X. Wang, C.-y. Ge, K. Chen, and Y. X. Zhang, "An ultrasensitive non-enzymatic glucose sensors based on controlled petal-like CuO nanostructure," Electrochimica Acta, vol. 259, pp. 225-232, 2018.
[49] L. Tang, J. Lv, C. Kong, Z. Yang, and J. Li, "Facet-dependent nonenzymatic glucose sensing properties of Cu2O cubes and octahedra," New Journal of Chemistry, vol. 40, no. 8, pp. 6573-6576, 2016.
[50] M. Long, L. Tan, H. Liu, Z. He, and A. Tang, "Novel helical TiO2 nanotube arrays modified by Cu2O for enzyme-free glucose oxidation," Biosens Bioelectron, vol. 59, pp. 243-50, Sep 15 2014.
[51] S. Cosnier, A. Le Goff, and M. Holzinger, "Towards glucose biofuel cells implanted in human body for powering artificial organs: Review," Electrochemistry Communications, vol. 38, pp. 19-23, 2014.
[52] N. Kannan and D. Vakeesan, "Solar energy for future world: - A review," Renewable and Sustainable Energy Reviews, vol. 62, pp. 1092-1105, 2016.
[53] D. G. Nocera, "The Artificial Leaf," Accounts of Chemical Research, vol. 45, no. 5, pp. 767-776, 2012/05/15 2012.
[54] S. Bensaid, G. Centi, E. Garrone, S. Perathoner, and G. Saracco, "Towards artificial leaves for solar hydrogen and fuels from carbon dioxide," ChemSusChem, vol. 5, no. 3, pp. 500-21, Mar 12 2012.
[55] A. Fujishima and K. Honda, "Electrochemical photolysis of water at a semiconductor electrode," nature, vol. 238, no. 5358, p. 37, 1972.
[56] S. Masudy-Panah, R. Siavash Moakhar, C. S. Chua, A. Kushwaha, and G. K. Dalapati, "Stable and Efficient CuO Based Photocathode through Oxygen-Rich Composition and Au-Pd Nanostructure Incorporation for Solar-Hydrogen Production," ACS Appl Mater Interfaces, vol. 9, no. 33, pp. 27596-27606, Aug 23 2017.
[57] A. Kushwaha, R. S. Moakhar, G. K. L. Goh, and G. K. Dalapati, "Morphologically tailored CuO photocathode using aqueous solution technique for enhanced visible light driven water splitting," Journal of Photochemistry and Photobiology A: Chemistry, vol. 337, pp. 54-61, 2017.
[58] N. S. Myazin, K. J. Smirnov, V. V. Davydov, and S. E. Logunov, "Spectral characteristics of InP photocathode with a surface grid electrode," Journal of Physics: Conference Series, vol. 929, p. 012080, 2017.
[59] M. Hettick, M. Zheng, Y. Lin, C. M. Sutter-Fella, J. W. Ager, and A. Javey, "Nonepitaxial Thin-Film InP for Scalable and Efficient Photocathodes," J Phys Chem Lett, vol. 6, no. 12, pp. 2177-82, Jun 18 2015.
[60] Y. F. Tay et al., "Solution-Processed Cd-Substituted CZTS Photocathode for Efficient Solar Hydrogen Evolution from Neutral Water," Joule, vol. 2, no. 3, pp. 537-548, 2018.
[61] A. Elaziouti, N. Laouedj, A. Bekka, and R.-N. Vannier, "Preparation and characterization of p–n heterojunction CuBi2O4/CeO2 and its photocatalytic activities under UVA light irradiation," Journal of King Saud University - Science, vol. 27, no. 2, pp. 120-135, 2015.
[62] L. Wei, C. Shifu, Z. Huaye, and Y. Xiaoling, "Preparation, characterisation of p–n heterojunction photocatalyst CuBi2O4/Bi2WO6 and its photocatalytic activities," Journal of Experimental Nanoscience, vol. 6, no. 2, pp. 102-120, 2011.
[63] J. Low, J. Yu, M. Jaroniec, S. Wageh, and A. A. Al-Ghamdi, "Heterojunction Photocatalysts," Adv Mater, vol. 29, no. 20, May 2017.
[64] M. M. Momeni and S. M. Mirhoseini, "ZnO nanorod films fabricated on zinc foil for photoelectrochemical water splitting," Surface Engineering, vol. 31, no. 7, pp. 507-512, 2014.
[65] H. Liu, X. Dong, C. Duan, X. Su, and Z. Zhu, "Silver-modified TiO2 nanorods with enhanced photocatalytic activity in visible light region," Ceramics International, vol. 39, no. 8, pp. 8789-8795, 2013.
[66] X. Pan, Y. Zhao, S. Liu, C. L. Korzeniewski, S. Wang, and Z. Fan, "Comparing graphene-TiO(2) nanowire and graphene-TiO(2) nanoparticle composite photocatalysts," ACS Appl Mater Interfaces, vol. 4, no. 8, pp. 3944-50, Aug 2012.
[67] V. Scuderi et al., "Photocatalytic activity of CuO and Cu2O nanowires," Materials Science in Semiconductor Processing, vol. 42, pp. 89-93, 2016.
[68] F. Pariente, E. Lorenzo, F. Tobalina, and H. D. Abruna, "Aldehyde Biosensor Based on the Determination of NADH Enzymically Generated by Aldehyde Dehydrogenase," Analytical Chemistry, vol. 67, no. 21, pp. 3936-3944, 1995/11/01 1995.
[69] K. Gelderman, L. Lee, and S. Donne, "Flat-band potential of a semiconductor: using the Mott–Schottky equation," Journal of chemical education, vol. 84, no. 4, p. 685, 2007.