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研究生： 蘇布
Thoka, Subashchandrabose
論文名稱： 利用有時間及位置解析能力的小角度X光散射法進行超晶格形成過程的量測並在水溶液中製備銅立方體及超小氧化亞銅奈米立方體和八面體以進行催化反應和光學量測
Supercrystal Formation Process Probed by Small-Angle X-Ray Scattering and Aqueous Phase Synthesis of Cu Cubes and Ultrasmall Cu2O Nanocubes and Octahedra for Catalysis and Optical Characterization
指導教授： 黃暄益
Huang, Hsuan-Yi Michael
口試委員: 林彥谷
Lin, Yan-Gu
陳軍華
Chen, Chun-Hua
鄭有舜
Jeng, U-Ser
呂明諺
Lu, Ming-Yen
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2018
畢業學年度： 106
語文別： 英文
論文頁數： 137
中文關鍵詞： 帶圖 、金 、超晶體 、超晶格 、界面活性劑介導的 、小角度X光散射 、銅 、異相催化 、硼氫化作用 、奈米立方體 、奈米線 、氧化亞銅 、超小 、奈米八面體 、光學特性 、晶面相關 、大小相關
外文關鍵詞： band diagram, Gold, Supercrystals, Superlattice, surfactant mediated, Small-angle X-ray scattering, copper, heterogeneous catalysis, hydroboration, nanocubes, nanowires, Cuprous oxide, ultra-small, nanooctahedra, optical characterization, facet-dependent, size-dependent
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    • 在第一章中，我們藉由表面活性劑擴散法合成金超晶體，同時以小角度/廣角X射線散射與掃描電子顯微鏡確認其成核及生長過程。結果顯示出超晶體的成核作用在具高濃度表面活性劑的金奈米晶液滴頂部形成，此一現象可在垂直向的毛細管中被觀察到。在液體-液體的界面中由於表面活性劑的濃度呈現陡峭梯度，可以瞬間觀察到超晶體的晶核是由數十個金奈米立方體所構成，顯露出了擴散動力學可以控制成核的過程。晶核會沉積在奈米晶體區的下方，並且在100分鐘內有效生長成約1釐米大小的立方體或是四方超晶體。在毛細管內超晶體的完成是由奈米晶體在液滴底部之液體與空氣的界面上大量聚集且以面對面的方式排列沉積而成。超晶體呈現高等向層狀堆疊，包含了大量金奈米立方體排列成高度一致性的晶系方向。
    在第二章中，以十六烷基三甲基氯化銨為表面活性劑，醋酸銅以及還原劑抗壞血酸鈉在100 ºC下反應40分鐘合成粒徑82、95以及108奈米的銅奈米立方體。在此一系統中，也可藉由微調抗壞血酸鈉的量來合成平均長度為25微米的銅奈米線。從粒徑的可調整性可以觀察到表面共振電漿吸收峰的微小偏移。銅奈米立方體被用來催化苯乙炔以及其各種炔類化合物的硼氫化反應，此系統具有100%的(E)產物選擇性以及82~95%的產率。銅奈米立方體的優點在於製造成本較低並有機會用於催化許多的有機反應。
    在第三章中，以十二烷基硫酸鈉為表面活性劑、硫酸銅、氫氧化鈉以及抗壞血酸鈉還原劑，可在室溫下合成出平均粒徑介於16到200奈米的15個不同尺寸的氧化亞銅奈米立方體以及平均粒徑為34、41和49奈米的八面體。本方法具有大量合成尺寸均勻以及形狀一致的優點，八面體的尺寸為目前最小的紀錄，這些氧化亞銅奈米立方體以及八面體的吸收以及放光光譜顯示出隨著粒徑增加其吸收以及放光位置呈現紅位移的現象。這些粒子各自具有相同的體積，立方體顯示出比八面體具有較多的吸收以及放光的紅位移現象，這證明了晶面效應存在於光學特性中。加入胺硼烷可將超小的氧化亞銅奈米晶體轉變成形狀相同的銅奈米晶體。我們也證明了藉由改變銅前驅物的用量可以改變氧化亞銅的形狀由立方體轉成八面體。

    In Chapter 1, the nucleation and growth process of gold supercrystals in a surfactant diffusion approach is followed by simultaneous small- and wide-angle X-ray scattering (SAXS/WAXS), supplemented with scanning electron microscopy. The results indicate that supercrystal nucleation can be initiated upon placing a concentrated surfactant solution on top of a gold nanocrystal solution droplet, trapped in the middle of a vertically oriented capillary tube. Supercrystal nuclei comprised of tens of gold nanocubes are observed nearly instantaneously in the broadened liquid-liquid interface zone of a steep gradient of surfactant concentration, revealing a diffusion-kinetics controlled nucleation process. Once formed, the nuclei can sediment into the lower nanocrystal zone, and grow into cubic or tetragonal supercrystals of ~1 mm size within 100 min. Supercrystals eventually accumulate and face-to-face align at the bottom liquid-air interface of the nanocrystal droplet. This is followed by superpacking of the interface-oriented supercrystals into highly oriented hierarchical sheets with coherent crystallographic orientations.
    In Chapter 2, copper nanocubes with average sizes of 82, 95, and 108 nm have been synthesized in an aqueous mixture of cetyltrimethylammonium chloride (CTAC) surfactant, copper acetate, and sodium ascorbate reductant heated at 100 ºC for 40 min. Copper nanowires with an average length of 25 µm can also be prepared this way by simply increasing the volume of sodium ascorbate introduced. Small shifts in the plasmonic absorption band positions with tunable particle sizes have been observed. The copper nanocubes were employed to catalyze hydroboration of phenylacetylene and various substituted aryl alkynes with 100% (E)-product selectivity and 82‒95% product yields. The copper nanocubes are cheap to make and should catalyze a broad scope of organic coupling reactions.
    In Chapter 3, ultra-small Cu2O nanocubes with 15 sizes between 16 and 200 nm and octahedra with average sizes of 34, 41 and 49 nm have been synthesized in an aqueous mixture of sodium dodecyl sulfate (SDS) surfactant, copper sulphate, sodium hydroxide and sodium ascorbate reductant at room temperature. This approach is highly scalable to large quantities but still yielding uniform size and shape. The octahedral crystals represent the smallest such particles ever reported. Their absorption and emission bands shift steadily to longer wavelengths with increasing particle sizes. For particles having the same volume, cubes show more red-shifted absorption and emission than octahedra indicating the presence of facet effects in optical properties. These ultrasmall Cu2O nanocrystals can be pseudomorphically converted to Cu nanocrystals by using ammonia borane. The shape evolution of Cu2O crystals from cube to octahedra by tuning the copper precursor amount has been demonstrated.

    Table of Contents 論文摘要………………………………………………………………I Abstract of the Dissertation……………………………………III Contents……………………………………………………………VIII List of Figures………………………………………………………XII List of Tables………………………………………………………aXXV List of Schemes……………………………………………………XXVII List of Publications…………………………………………………XXX CHAPTER 1 Tracing the Surfactant-Mediated Nucleation, Growth and Superpacking of Gold Supercrystals Using Time Spatially Resolved X-ray Scattering 1.1 Introduction………………………………………………………………1 1.2 Research Summery…………………………………………………………7 1.3 Experimental Section……………………………………………………9 1.3.1 Sample preparation ……………………………………………………10 1.3.2 Time and spacially resolved SAXS/WAXS……………………………14 1.3.3 Scanning electron microscopy……………………………………………14 1.4 Results and Discussion……………………………………………………15 1.4.1 Nucleation and growth process …………………………………………15 1.4.2 Effects of the surfactant concentration gradient ……………….24 1.4.3 Possible mechanisms for the proposed nucleation-and-growth process......................................................30 1.4.4 Oriented superpacking at an inverted liquid-air interface……34 1.5 Conclusion………………………………………………………………………40 1.6 References………………………………………………………………………41 CHAPTER 2 Aqueous Phase Synthesis of Size-Tunable Copper Nanocubes for Efficient Aryl Alkyne Hydroboration 2.1 Introduction………………………………………………………………51 2.2 Research Summery…………………………………………………………59 2.3 Experimental Section……………………………………………………60 2.3.1 Chemicals ……………………………………………………………….60 2.3.2 Synthesis of Cu nanocubes and nanowires…………………………60 2.3.3 Instrumentation…………………………………………………………61 2.4 Results and Discussion…………………………………………………62 2.5 Conclusion…………………………………………………………………78 2.6 References…………………………………………………………………79 CHAPTER 3 Simple and Highly Scalable Approach to Synthesize Size-Tunable Ultrasmall Cu2O Nanocubes and Nanooctahedra for Their Size- and Facet- Dependent Optical Properties 3.1 Introduction………………………………………………………………86 3.2 Research Summery…………………………………………………………98 3.3 Experimental Section……………………………………………………99 3.3.1 Chemicals ………………………………………………………………..99 3.3.2 Synthesis of size-tunable small Cu2O Nanocubes by tuning SA amount…………………………………………………………………100 3.3.3 Synthesis of size-tunable small Cu2O Nanocubes by tuning NaOH amount....................................................102 3.3.4 Synthesis of small Cu2O octahedra with tunable sizes.....104 3.3.5 Cu2O shape evolution from cube to octahedra…………………106 3.3.6 Synthesis of Cu polyhedra from Cu2O through pseudomorphic conversion……………………………………………107 3.3.7 Instrumentation………………………………………………………109 3.4 Results and Discussion……………………………………………..109 3.5 Conclusion………………………………………………………………129 3.6 References………………………………………………………………130

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