此研究首先利用密度泛函理論來分析設計不同的光電陽極材料，了解其在光電化學燃料電池中的電子傳遞過程。使用量子計算分析方法，研究不同奈米結構光電陽極、生物染料和電解質之間的電子傳遞。光電陽極使用氧化鋅結構，原因為氧化鋅在工業界具有較低的成本，高染料吸附率以及高材料可變性。氧化鋅奈米結構分為奈米線，奈米管兩種結構，計算其基態能量可以得到穩定最佳化結構。模擬結果發現氧化鋅奈米管具有較低的導帶，可以成功將矢車菊花青素(cyanidin)、葉綠素a (chlorophyll a)及其衍生分子二氫卟吩(chlorin)染料激發後的以電子傳遞到氧化鋅奈米管光電陽極。
研究第二部分研究葉綠素a (chlorophyll a)及其衍生分子二氫卟吩(chlorin)在光電化學燃料電池中影響其產電效率的主要因素。同樣利用第一原理計算，以密度泛函理論搭配B3LYP（Becke, Lee-Yang-Parr）, CIS (configuration interaction with singles)交換相關泛函和6-31G基組，經由量子化學計算照光光譜以及電子軌域等，來預測其整體光電性能。置換二氫卟吩的中心金屬原子可以得到不同的光電性質，包含中心金屬原子和周圍氮原子的電負度差異。電負度可以影響電子雲的分布情形，進而影響照光光譜的吸收範圍。故使用不同的中心金屬原子，可以調整染料的吸收頻率。
研究最後利用鈣鈦礦材料當作光電化學燃料的陰極，並分析其產氫效能和鈣鈦礦中的電子傳遞。使用密度泛函理論計算分析鈣鈦礦陰極與[鐵-鐵]產氫酵素的電子密度、分態密度(PDOS)、電子雲和之間的電子傳遞。結果顯示鈣鈦礦陰極材料可以成功有效製造氫氣。電子雲從鈣鈦礦結構中的氨(NH3)有機分子傳遞到產氫酵素的鐵原子之上。研究最後使用RRKM理論計算產氫酵素在不同溫度下的反應速率常數，其結果與文獻實驗的數值相同。

This thesis first employed the density functional theory (DFT) to evaluate the effect of different photoanode designs on the electron transport in photoelectrochemical biofuel cells. The electron transfer between different nano structures of the photoanode, various sensitizers, and bio-electrolytes are analyzed via this computational quantum mechanics technique. The photoanode material used zinc oxide semiconductors, which could have a great potential in many ways including cost reduction, higher dye absorption ability and feasibility in the industry. Several molecular models, such as ZnO nanowires, ZnO nanotubes, and some novel biological pigments have been set up using minimum energy principles. Simulation results reveal that ZnO nanotubes possess lower conduction bands which potentially easier to transfer electrons from biopigments (e.g., chlorin, chlorophyll a and cyanidin) to the anode. As the preliminary conclusion, this first-principles technique is able to determine the photoelectrochemical properties of nano designs and screen different novel design ideas.
Secondly, it is intended to find out the main factors that affect the power conversion efficiency of chlorin derivatives. By employing the first principles calculation again with density functional theory (DFT) plus hybrid exchange-correlation functional B3LYP, CIS and 6-31G basis set, this research calculated the photoelectronic properties, such as energy gaps, molecular orbital and UV/VIS absorption spectroscopy, of chlorin derivatives. The chlorin was used as a basic structure and the central ring was substituted by different metals. The difference in electronegativity between the central metal ion and the adjacent nitrogen atoms causes changes in distribution of electron clouds, which indirectly affect the molecule absorbance magnitude in ultraviolet and long wavelength range. By alternating the central metals with different electronegativities, the absorption spectra can be controlled.
Finally, this research focused on the electron transmitting path and the reaction rate at the perovskite cathode of the photoelectrochemical cell for hydrogen production. The field of electron density, projected density of states (PDOS), electron distribution and electron transfer path between the [Fe-Fe] hydrogenase and the peroskite cathode can be obtained. Simulation results reveal that the perovskite cathode is better than traditional cathodes for hydrogen production. Before transmission to the [Fe-Fe] hydrogenase, electron clouds mainly aggregate at the periphery of NH3 organic molecules. Then, electrons are transmitted to the hydrocarbon structural chain, finally reaching Fe atoms. Rice, Ramsperger, Kassel and Marcus (RRKM) theory was used to predict the reaction rates at different temperatures. It was found that the reaction rates coincide perfectly with the experimental results from other literatures. This research provides more physical insight into the electron transfer mechanism during the hydrogen production process. It also proves that photoelectrochemical biofuel cells can play the role as a dye sensitized solar cell during daytime, work as a biofuel cell in the evening. Also they can be designed as a part of hydrogen production system during day and night.

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