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研究生： 林姮君
Lin, Heng-Jun
論文名稱： 水熱法製備BaTiO3奈米柱陣列薄膜複合光還原Ag奈米粒子在壓電光催化相關應用
Photoreduced Decoration of Ag Nanoparticles on Hydrothermally Grown BaTiO3 Nanorod Array Films and Their Application to Piezo-Photocatalysis
指導教授： 張高碩
Chang, Kao-Shuo
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2024
畢業學年度： 112
語文別： 英文
論文頁數： 101
中文關鍵詞： 水熱法 、光還原 、BaTiO3 奈米柱陣列薄膜 、Ag奈米顆粒 、局部表面電漿共振和壓電光降解
外文關鍵詞： hydrothermal synthesis, photoreduction, BaTiO3 nanorod array film, Ag nanoparticle, localized surface plasmon resonance, and piezo-photodegradation
相關次數： 點閱：104  下載：0 
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    • 本研究使用兩步水熱法在FTO基板上製備BaTiO3(BTO)奈米柱陣列薄膜。第一步水熱法使用鈦酸丁酯(TBOT)前驅物溶液合成TiO2奈米柱陣列薄膜，然後第二步水熱法將其轉化為BTO奈米柱薄膜。調整了多種水熱參數，包括溶劑、添加劑、Ba(OH)2·8H2O的用量和水熱時間。通過優化Ba(OH)2·8H2O的用量和水熱時間，實現了從TiO2到BTO的完全轉化，並維持了奈米柱的形貌。
    對單個BTO奈米柱粗糙表面的TEM分析顯示，三個不同位置來自同一晶粒。這一觀察使我們能夠構建TiO2轉化為BTO的機制。四丁基氫氧化銨 (TBAH) 作為鹼性試劑對此過程至關重要，其中TBAH中的OH-基團腐蝕TiO2奈米柱，使表面變得粗糙，並與TiO2反應形成[Ti(OH)6]2-，促進Ba2+容易擴散進入[Ti(OH)6]2-框架以形成BTO。此外，乙醇和異丙醇增加了鐵氟龍杯中的壓力，使Ba2+更容易擴散進入[Ti(OH)6]2-框架中。
    在BTO奈米柱陣列薄膜（壓電常數約為40 pm/V）上，使用光還原法還原銀粒子，形成Ag/BTO複合物，並用於可見光壓電光降解反應。優質的Ag/BTO樣品對RhB溶液顯示出有前景的壓電光降解效果，反應速率常數為18.3 × 10-3 min-1。壓電性和局部表面電漿共振增強了光降解活性。循環測試和自由基捕捉劑研究分別表明樣品的可靠性和主要反應物·O₂⁻自由基。通過UV-vis、SKPM和UPS結果構建了Ag/BTO複合材料的能帶圖，以闡明相關性能。

    Two-step hydrothermal method was developed to prepare BaTiO3 (BTO) nanorod array films on FTO substrates. The first step used titanium butoxide (TBOT) precursor solutions to grow TiO2 nanorod array films, which were then converted to BTO nanorod films in the second step of the reaction. Various hydrothermal parameters were tuned, including solvents, additives, amounts of Ba(OH)28H2O, and reaction times. A complete conversion from TiO2 to BTO and maintenance the morphology of nanorods were obtained by the optimization of amounts of Ba(OH)2·8H2O and hydrothermal times.
    TEM analysis on rough surfaces of a single BTO nanorod revealed the same grains for three different locations. This observation enables us to construct a potential mechanism for the transformation from TiO2 to BTO. An alkaline agent of tetrabutylammonium hydroxide (TBAH) was crucial for the process, in which OH- in TBAH etched TiO2 nanorods to lead to rough surfaces and also reacted with TiO2 to form [Ti(OH)6]2-, facilitating easy diffusion of Ba2+ into [Ti(OH)6]2− frameworks to form BTO. Furthermore, ethanol and IPA increased the pressure in a Teflon cup, allowing the easy diffusion of Ba2+.
    The resulting BTO nanorod array films (piezoelectric constant of approximately 40 pm/V) were covered by photoreduced Ag nanoparticles for application in visible-light piezophotodegradation reactions. A favorable Ag/BTO sample exhibited promising piezo-photodegradation with a reaction rate constant of 18.3 × 10-3 min-1 for RhB solutions. The activity was synergistically enhanced by piezoelectricity and localized surface plasmon resonance. A cycling and a scavenger study indicated the sample’s reliability and predominant ·O₂⁻ radicals in the reaction, respectively. An energy band diagram of the Ag/BTO composite was constructed through UV-vis, SKPM, and UPS results to elucidate the associated performance.

    摘要 I Abstract II 致謝 III Contents IV Figure Contents VIII Chapter 1 Introduction 1 1.1 Barium titanate (BaTiO3) 1 1.1.1 Crystal structure and property 1 1.1.2 Synthesis method 2 1.1.2.1 Hydrothermal reaction 2 1.1.2.2 Sol-gel synthesis 12 1.1.2.3 Chemical solution deposition 13 1.1.3 Application of BTO 15 1.1.3.1 Piezo-photodegradation 15 1.1.3.2 PEC water splitting 19 1.1.3.3 Nanogenerators 21 1.2 Silver (Ag) 22 1.2.1 Crystal structure and property 22 1.2.2 Surface plasmon resonance (SPR) 23 1.2.3 Synthesis method 24 1.2.3.1 Photoreduction 24 1.2.3.2 Chemical reduction 26 1.3 BTO/Ag composite 27 1.3.1 Piezo-photodegradation 27 1.4 Motivation 31 Chapter 2 Experimental method 32 2.1 Materials 32 2.1.1 Chemicals for hydrothermal method 32 2.1.2 Chemicals for photoreduction 32 2.1.3 Chemicals for substrate cleaning 33 2.1.4 Substrate 33 2.2 Hydrothermal method 33 2.2.1 Substrate cleaning 33 2.2.2 Fabrication of BTO nanorod 33 2.2.2.1 First step hydrothermal synthesis 33 2.2.2.2 Second step hydrothermal synthesis 35 2.2.2.3 Fabrication Ag/BTO heterostructure 35 2.3 Characterization 36 2.3.1 X-ray diffraction (XRD) analysis 36 2.3.2 Scanning electron microscopy (SEM) 37 2.3.3 Transmission Electron Microscopy (TEM) 37 2.3.4 UV-vis spectrometry 39 2.3.5 X-ray photoelectron spectroscopy (XPS) 39 2.3.6 Ultraviolet Photoelectron Spectroscopy (UPS) 40 2.3.7 Photodegradation 40 2.3.8 Piezoresponse force microscopy (PFM) 42 Chapter 3 Results and discussion 43 3.1 BTO synthesis 43 3.1.1 TiO2 nanorod array film (First-step hydrothermal reaction) 43 3.1.2 BTO nanorod array film (Second-step hydrothermal reaction) 46 3.1.2.1 Solvent effect 48 3.1.2.2 Additive effect 50 3.1.2.3 Ba(OH)2·8H2O precursor effect 51 3.1.2.4 Hydrothermal time effect 52 3.2 Growth mechanism of BTO nanorod 56 3.3 Ag/BTO result 57 3.3.1 Photoreduction time 57 3.3.2 AgNO3 concentration 58 3.3.3 TEM result 60 3.4 EDS result of Ag/BTO 62 3.5 XPS result of Ag/BTO 63 3.6 PFM 65 3.7 Band Diagram of Ag/BTO 68 3.7.1 UV-vis spectrum 68 3.7.2 Scanning Kelvin Probe Microscopy (SKPM) 69 3.7.3 UPS results 70 3.7.4 Band diagram position 71 3.8 Photodegradation 72 3.8.1 Photodegradation study 72 3.8.2 Cycling test 75 3.8.3 Scavenger test 75 3.8.4 Working mechanism 76 Chapter 4 Conclusions and future work 78 4.1 Conclusions 78 4.2 Future work 80 Chapter 5 References 81

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