鉍催化淚滴狀磷化錫奈米粒子是以雙[雙(三甲基矽烷基)氨基]錫(II)及三辛基膦分別作為錫與磷的前驅物，經由鉍晶種催化在超臨界流體甲苯中所合成而得。2-乙基己酸鉍以溶於油胺的形式添加於系統中，從而產生鉍奈米粒子做為晶種，而使其晶體以超臨界流體-液-固(SFLS, supercritical fluid-liquid-solid)的機制在超臨界流體環境中成長。一般而言，晶種催化晶體經此機制生長通常會獲得奈米線，而其淚滴狀形貌與無添加晶種之文獻類似，此現象如同晶種催化奈米錐，根據文獻，此例是由於磷與錫不只能由晶種進入以SFLS機制進行晶體成長，也能從磷化錫表面進入使晶體成長，而使晶體傾向於如此形貌。故以不同變因進行了多次合成實驗探討其前驅物物種、濃度、界面活性劑、合成方法將如何影響其產物的外貌及晶體結構。磷化錫奈米粒子作為陽極材料與鋰金屬組成了鈕扣型(CR2032)半電池，並在0.01與1.5伏特區間以0.1C速率進行等電流充放電測試，其放電電容在五十循環後仍能保持在815 mA h g-1，以及在5C高速率下也仍有412 mA h g-1的不錯表現，優於其他使用磷化錫作為鋰離子電池或鈉離子電池文獻。
矽在鹼催化下與水進行化學蝕刻而產生矽酸根離子與氫氣，表示可將矽視為能量載體，然而矽作為主要反應物，為節省成本而需要大量低價矽，同時也需要達到高速及高產率生產才能滿足工業化所需條件。本研究是以從太陽能級矽晶圓切割所產生並回收之微米級矽粉(切片損失矽，kerf loss silicon)經由濕式化學蝕刻進行氫氣生產。加入不同比例的矽酸以及矽酸鈉等添加劑，加速水分解反應而加強其產氫表現，其最佳化產率達92%，而其產氫速率則達4.72×10-3 g(H2) s-1 g-1(Si)，是微米級矽文獻中的最佳速率值。除此之外，為實際展現kerf loss silicon作為能量載體的便利性，將其置於耐高壓之不銹鋼反應器中與水反應產氫，可與燃料電池搭配將氫氣轉化為電能或是與另一高壓槽連接作為儲氫之用。
關鍵字：磷化錫、鋰離子電池、矽、鹼蝕刻、產氫

Bi-seeded teardrop-shaped SnP0.94 nanoparticles were synthesized in supercritical fluid toluene with bis[bis(trimethylsilyl)amino]tin(II) (Sn[N(TMS)2]2) and trioctylphosphine (TOP) as the precursors of tin and phosphorus, respectively. The addition of bismuth 2-ethylhexanoate which was dissolved in oleylamine (OLA) resulted in the formation of bismuth nanoparticles acting as crystal seed, causing the crystal growth follow the SFLS (supercritical fluid-liquid-solid) mechanism in supercritical fluid environment. Generally, seeded growth mechanism usually leads to the formation of nanowires. The teardrop-shaped morphology, which is similar to the case in the absence of crystal seed in the previous report, could be attributed to the diffusing of tin and phosphorus into SnP0.94 via the sidewall, allowing SnP0.94 to grow freely, which made this morphology favorable like those reported nanocones. Several experiments were carried out to investigate how different precursors, concentrations, and synthetic methods would affect the morphology and the crystallinity of the resulting product. Nanowires accompanied with many particles with two tin phosphide phases were found in the product from reacting tin(II) acetate dissolved in oleylamine (OLA) with trioctylphosphine with the presence of bismuth precursor through the hot-injection method. The electrochemical performance of SnP0.94 nanoparticles was explored with charge/discharge galvanostatic cycles in a CR2032 coin cell using lithium metal as the counter electrode between 0.01 and 1.5 V, showing a discharge capacity of 815 mA h g-1 at a rate of 0.1 C after 50 cycles and a good discharge capacity of 412 mA h g-1 at the 5 C rate, which is better than other tin phosphides in LIBs or SIBs.
The chemical etching of silicon catalyzed by base in water can produce hydrogen and dissociated orthosilicic acid (SiO2(OH)22-), suggesting silicon can be qualified as an energy carrier. However, large amount of low-priced silicon is needed as the essential reactive material for cost saving and faster and high-yield hydrogen production, making this process agreeable for industrialization. In this study, high-performance hydrogen production via wet chemical etching of micrometer-sized kerf loss silicon recovered from the sawing process of solar-grade wafer is reported. Additives including sodium metasilicate (Na2SiO3) and metasilicic acid (H2SiO3) were employed to accelerate the water splitting reaction, resulting in an optimized hydrogen production rate of 4.72×10-3 g(H2) s-1 g-1(Si) and a yield of 92% that ranks the best performance in the reported literature on a micrometer-sized silicon basis. In addition, a proof-of-concept example is conducted by using a kerf loss silicon-based hydrogen production reactor in coordinate with either a fuel cell converting the supplied hydrogen to electricity or a high-pressure tank for hydrogen storage, showing kerf loss silicon is a convenient energy carrier. The silicate salt existing in the resulting solution can be separated by adding coagulant, which forms precipitates with silicate salt, and then it can be removed from the solution simply by filtration or centrifugation.
Keywords: tin phosphide, lithium-ion batteries, silicon, base-catalyzed etching, hydrogen production

中文摘要 I
Abstract II
Contents IV
List of Tables VI
List of Figures VII
Chapter 1 Synthesis of Bi-Seeded Teardrop-Shaped SnP0.94 Nanoparticles and Its Performance as Anode of Lithium-Ion Batteries 1
1-1 Introduction 1
1-2 Experimental 7
1-2-1 Materials 7
1-2-2 Characterization 7
1-2-3 Preparation of 0.02M bismuth precursor solution 8
1-2-4 Synthesis of tin phosphide in solution phase 8
1-2-5 Synthesis of tin phosphide in supercritical fluid toluene in a batch manner 9
1-2-6 Synthesis of tin phosphide in supercritical fluid toluene in a semi-batch manner 10
1-2-7 Fabrication of LIBs 11
1-3 Results and Discussion 12
1-4 Conclusion 23
1-5 References 24
Chapter 2 Additive-Mediated Rapid Hydrogen Production by the Base-Catalyzed Etching of Kerf Loss Silicon 30
2-1 Introduction 30
2-2 Experimental 35
2-2-1 Materials 35
2-2-2 Characterization 35
2-2-3 Hydrogen generation process using kerf loss silicon as a reactant 36
2-2-4 Large-scale hydrogen generation process 37
2-2-5 Hydrogen generation system integrated as electricity generator 37
2-2-6 Hydrogen generation system integrated for hydrogen storage 38
2-3 Results and Discussion 38
2-4 Conclusion 51
2-5 References 52

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