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http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/84397
標題: | 表面和界面改質對增強光化學二氧化碳還原的影響 Effect of Surface and Interface Modification for Enhanced Photochemical Carbon Dioxide Reduction |
作者: | Fang-Yu Fu 符芳裕 |
指導教授: | 吳志毅(Chih-I Wu) 吳志毅(Chih-I Wu | chihiwu@ntu.edu.tw | 0000-0003-3613-7511), |
關鍵字: | 人工光合作用,光觸媒,二氧化碳還原機制,表面修飾,光電子能譜, artificial photosynthesis,photocatalyst,CO2 reduction mechanism,surface modification,photoemission spectroscopy, |
出版年 : | 2022 |
學位: | 博士 |
摘要: | 金屬氧化物及金屬硫化物半導體的表面和界面改質,是提高電荷傳輸動力學和光化學轉換效率的關鍵策略,在本論文中,將使用不同的改質策略來調變半導體表面性質並提出反應機制上的見解。主要內容將分為兩個部分,首先,無機偶極分子硫氰酸鉀(KSCN)被證實可以增強於帶有缺陷的二氧化鈦(即黑色二氧化鈦)的光催化二氧化碳還原反應以及光穩定性,結合實驗和理論模擬方法,得知SCN 配位基的化學吸附會改變黑色二氧化鈦的表面電位和電子能帶邊緣能量,這使得太陽能燃料的產量提升2.8倍,同時,在連續反應40個小時後,其產率仍保持在88%左右,此光學反應機制的增強歸因於界面偶極子效應。第二部分,將採用離子交換法在二硫化錫奈米片上修飾磷酸銀量子點,進而形成直接Z型異質結構,由於具有磷酸鹽空缺的磷酸銀,其光還原特性、Z型電荷載子轉移和高效的激子解離,在最佳化的異質結構顯示出高選擇性(約95%)二氧化碳還原為一氧化碳,產率相比於原始的磷酸銀和二硫化錫,顯著提升約3倍和47.8倍,此部分也揭示了磷酸銀/二硫化錫的異質界面特性,並提出光化學二氧化碳還原反應途徑。新穎且優秀的配位基誘發偶極子效應及直接Z型異質結構的概念,可能會在未來的太陽能燃料或光化學水分解應用中帶來重大突破。 Surface and interface modification on metal-oxide/sulfide-based semiconductors are crucial strategies to improve charge transport kinetic and photochemical conversion efficiency. In this thesis, we used different modification strategies to modulate the surface properties and provide insights into the reaction mechanism. The main content will be divided into two parts. First, the inorganic dipolar molecule potassium thiocyanate (KSCN) has been demonstrated to enhance the defective titanium dioxide (i.e., black TiO2) photochemical CO2 reduction reaction and photostability. Combining experimental and theoretical simulation approaches, the chemisorption of the SCN ligands has altered the surface potential and electronic band edge energy of black TiO2, resulting in a 2.80-fold increase in the yield of solar fuel. At the same time, the production rate remained around 88% after 40 hours of continuous reaction. The enhancement of the photochemical reaction mechanism is attributed to the interfacial dipole effect. The second part used the ion exchange method to decorate silver orthophosphate (Ag3PO4) quantum dots over SnS2 nanosheets to form the direct Z-scheme heterojunction. Owing to the photoreduction properties of Ag3PO4 with orthophosphate vacancies, Z-scheme charge carrier transfer, and efficient exciton dissociation, an optimized heterojunction shows a highly selective (~95%) CO2–to–CO reduction with an illustrious yield enhancement near 3.0 and 47.8 times higher than Ag3PO4 and SnS2, respectively. This section revealed the heterointerface properties of Ag3PO4/SnS2 and proposed the photochemical CO2 reduction pathway. The novel and fabulous concepts of ligand-induced dipole effect and direct Z-scheme heterojunction may lead to significant breakthroughs in future solar fuels or photochemical water-splitting applications. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/84397 |
DOI: | 10.6342/NTU202202792 |
全文授權: | 同意授權(限校園內公開) |
電子全文公開日期: | 2027-09-23 |
顯示於系所單位: | 光電工程學研究所 |
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