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研究生: 劉育芳
Liou, Yu-Fang
論文名稱: 單構太陽能驅動雙氧水燃料電池併同有機廢水處理
Simultaneously solar-driven H2O-to-H2O2 and treatments of organic wastewater in a single-compartment fuel cell
指導教授: 王鴻博
Wang, H. Paul
學位類別: 碩士
Master
系所名稱: 工學院 - 環境工程學系
Department of Environmental Engineering
論文出版年: 2021
畢業學年度: 109
語文別: 英文
論文頁數: 138
中文關鍵詞: 水分解雙氧水四環素雙氧水燃料電池三電極模組光燃料電池鉍碘氧化物銅鉍氧化物
外文關鍵詞: H2O splitting, tetracycline, antibiotic contaminate water, H2O2 fuel cell, triple-photoelectrode, PFC, BiOI, Bismuth copper oxide
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  • 在化石能源枯竭及極端氣候之壓力下,綠色能源的發展成為重要議題。太陽能可產生電力與動力屬再生能源,不僅含無盡能量,亦能降低地理條件的限制,有高度適應性,此種綠色能源具廣泛商業應用潛力。利用仿光合作用之光電催化(photoelectrocatalysis)技術,可將太陽能轉換成化學能與電力,尤其,工業快速發展,導致水污染日趨嚴重,有機廢水大多採生物處理與高級氧化處理程序(AOP),若能以太陽能驅動還原H2O生成H2O2應用於AOP,則可大幅降低二次污染,以取代傳統蒽醌法生產H2O2,伴隨之工業安全及二次污染的問題。因此,本研究之重點是開發光驅動雙氧水燃料電池,將有機廢水視為化學燃料,透過雙PEC降解有機物質併同產電,關鍵技術含:(1)合成磷化鎳或磷化鈷參雜異質結構(NiP or CoP on g-C3N4/BiOI composites)光驅動分解H2O生成H2O2;(2)合成平面硫化鉬及銅鉍氧化物(MoS2/CuBi2O4)應用於可見光分解新興汙染物四環素(不適生物處理,易成抗藥性基因傳播與轉移的溫床);及(3)技術整合,開發單構光驅動燃料電池,應用雙光電極同時氧化有機污染物(四環素)及產電。
    合成磷化鎳及磷化鈷參雜的異質結構(NiP或CoP on g-C3N4/BiOI composites)能提升約八倍的光驅動分解H2O生成H2O2效率,藉由調控異質結構的能隙及參雜磷化鎳及磷化鈷以增加電子-電洞對的利用,屬可逆反應,生成及分解動力參數分析結果指出NiP/g-C3N4/BiOI具相對較佳之反應速率。另外,為處理新興有機污染物例如:四環素,合成平面硫化鉬及銅鉍氧化物(MoS2/CuBi2O4)應用於可見光分解四環素,藉超氧自由基及電洞的氧化作用,使四環素分解為其他低碳的羥基醛類衍生物,可在 2 h 內達到 85% 之去除效率。再者,透過技術整合設計之三電極雙氧水燃料電池模組,利用光驅動水分解生產H2O2作為燃料,經由雙光電極產電,可有效產生1300 A光電流,且在 1 h 的可見光驅動下,可去除80%的四環素(10 ppm),併產出700 A光電流。此新開發之單構光驅動燃料電池組,具有可攜性及簡易安裝的特性,期能提供一種兼具能源自主之新穎廢水處理方法與設備,以供產業提升技術參考。

    Under the burden of the extreme weather and fossil energy exhaustion, green energy technology development has attracted a great attention. Solar energy, being a renewable energy, poses an endless energy and high adaptability which is not limited by geographical restrictions. The new photoelectrochemical methods which can convert solar energy to chemical energy have promising applications and commercialization. Particularly, due to the rapid globalization and industrialization, water contamination becomes severe. Organic wastewaters are commonly treated by biological and advanced oxidation processes (AOPs). H2O2, being a green oxidant, can be used for treatments of organic wastewater by AOPs. However, H2O2 relies on the anthraquinone process that suffers from high safety risk and pollution problems. Therefore, a solar-driven H2O-to-H2O2 for fuel cell integrated with a double-photoelectrode PEC in a single-compartment fuel cell for simultaneous electricity generation and organic wastewater treatments would be of great importance and interest. The major objectives of this research include: (1) Synthesis of NiP or CoP promoter on g-C3N4/BiOI composites for photocatalytic splitting of H2O to H2O2; (2) Visible-light driven MoS2/CuBi2O4 heterojunctions for degrading emerging contaminants of tetracycline (TC) which has metabolism resistance; and (3) Simultaneous solar-driven H2O-to-H2O2 and treatments of organic wastewater in a single-compartment fuel cell.
    The new promoter NiP or CoP dispersed on g-C3N4/BiOI heterojunction were prepared for photocatalytic H2O-to-H2O2. The reaction potential for the two-electron reduction of O2 to H2O2 (0.30 eV @ pH 7) is within the band gap region. In addition, the H2O2 yields by the NiP and CoP promoted composites are increased by 3.0-8.4 times. Furthermore, under the visible-light (>400 nm) irradiation for 2 h, 50-85% of tetracycline was degraded photocatalytically by the pristine CuBi2O4 and MoS2/CuBi2O4 heterojunctions through hydroxylation, dealkylation and ring cleavage reactions. Through the integration of double-photoelectrode PEC with the H2O2 fuel cell, a triple-photoelectrode PFC compartment was designed and assembled. The NiP/g-C3N4/BiOI composites also played the role in the photogeneration of H2O2 from H2O (H2O-to-H2O2), and the dual-photoelectrode (photoanode: NiP/g-C3N4/BiOI; photocathode: 5%MoS2/CuBi2O4) are worked for H2O2 fuel cell. Note that under visible light irradiation for 1 h, the novel triple-photoelectrode PFC that comprises a H2O2 fuel cell generated a stable photocurrent of 1300 A and 700 A with the TC feed at the concentration of 10 ppm. Subsequently, a portable triple-photoelectrode PFC device was designed and assembled for generation electricity with additional functions of providing safer drinking water. It is expected to provide a new method for water treatment with self-supporting energy for scale-up and commercialization.

    摘要 II ABSTRACT III 致謝 V CONTENTS VI LIST OF TABLES VIII LIST OF FIGUTES IX Chapter 1 INTRODUCTION 1 Chapter 2 LITERATURE STUDIES 4 2.1 Solar Energy 4 2.1.1 Photoelectrocatalysis 5 2.1.2 Water Splitting 7 2.1.3 Photocatalyst Preparations and Characterization 10 2.2 Principle and Applications of PC/PV-EC/PEC 22 2.2.1 Photocatalysis (PC) 22 2.2.2 Photovoltaic-Electrolysis (PV-EC) 23 2.2.3 Photoelectrochemical (PEC) 24 2.3 Photoelectrocatalytic Fuel Cell (PFC) 28 2.3.1 Liquid Fuel Cell 29 2.3.2 Solar-driven H2O2 Fuel Cell 33 Chapter 3 EXPERIMENT METHODS 35 3.1 Experimental overview 35 3.2 Preparations of photocatalyst electrode 38 3.2.1 Graphitic carbon nitride 38 3.2.2 Modified bismuth oxy-iodide electrode 38 3.3 Photocatalytic performance studies 39 3.3.1 H2O-to-H2O2 photocatalytic reaction 39 3.3.2 Photodegradation of tetracycline (TC) 40 3.3.3 Photo(electro)catalyst performance 41 3.4 Characterization 46 Chapter 4 RESULT AND DISCUSSION 50 4.1 Solar-driven H2O-to-H2O2 effected by promoters NiP and CoP on g-C3N4/BiOI composites 50 4.2 Visible-light photocatalytic degradation of tetracycline by MoS2/CuBi2O4 74 4.3 Simultaneously solar-driven H2O-to-H2O2 and treatments of organic wastewater in a single-compartment fuel cell 98 Chapter 5 Conclusion 122 REFERENCE 123 APPENDIX 137

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