| 摘要: | 本論文研究主要分為兩個部分。第一部分是採用奈米模鑄法 (nanocasting)合成具有氮混摻之有序中孔洞碳材 (ordered mesoporous carbons with N-doped, N-OMCs)。首先以非離子型界面活性劑 (nonionic surfactants) P123作為有機模板 (organic template)，和四乙基矽氧烷 (tetraethoxysilane, TEOS)在酸性水溶液中均勻混合，加入低分子量的醇類做為微胞修飾劑 (modifier)，利用多成份共自組裝現象 (multi-component cooperative assembly)合成具立方體Ia3d排列中孔洞氧化矽 (mesoporous silica) KIT-6。之後以KIT-6的奈米級孔洞做為硬膜板(hard-template)，填入含有氮混摻之碳源前驅物(Resorcinol and Melamine)，以900 °C碳化反應 (carbonization) 將前驅物碳化形成碳材，最後移除氧化矽硬模板後，成功合成出N-OMCs。
在材料的應用方面，利用合成之N-OMCs做染料吸附之實驗，藉此探討對不同染料分子吸附能力的影響。依據Langmuir及Freundlich等溫吸附模型的分析，經由實驗結果發現，本研究合成出之N-OMCs較符合Langmuir等溫吸附模式所假設的單層吸附模式，較其他等溫吸附模式更適合描述有序中孔洞碳材吸附染料的狀況。
另一方面，本研究也將N-OMCs做進一步的應用，利用N-OMCs做為載體吸附Sn金屬離子後，再加以高溫鍛燒，成功合成出具二氧化錫之奈米顆粒(Nanoparticles)的金屬氧化物之有序中孔洞碳材；其奈米顆粒的尺寸的大小約為4～5 nm，並將此材料應用做鋰離子電池之陽極材料。
第二部分則為開發新型複合式固態高分子電解質(solid polymer electrolytes, SPEs)。實驗採用三嵌段結構的高分子Jeffamine ED2003、ED900及ED600，分別與做為主鏈段的另一高分子聚丙烯腈 (polyacrylonitrile, PAN)反應，形成梳狀結構之複合式固態高分子電解質。此類型固態電解質的導電度表現以ED900的系列較佳，在30 °C時的最佳離子導電度可達到6.28 × 10-5 S/cm，電化學穩定性可承受在3.0～3.5 V的氧化裂解電壓。
;The focus of this thesis is divided into two parts. The first part is the use of nanocasting synthesis ordered mesoporous carbons with nitrogen-doped (N-OMCs). First, nonionic surfactants (P123) were used as organic templates, and tetraethoxysilane (TEOS) were homogeneously mixed in acidic aqueous solution. Low molecular weight alcohols were added as microcells modifier. KIT-6 with cube Ia3d arrangement was synthesized by multi-component cooperative assembly. Then, the KIT-6 nanoscale porous were used as the hard-template, and filled with a nitrogen-containing carbon precursor (Resorcinol and Melamine). The precursor was treated with 900 °C carbonization to form carbon material, and finally remove the hard template of silicon oxide.
The N-OMCs was successfully synthesized, characterized and employed as adsorbents for dye removal. The equilibrium adsorption capacities were estimated to quantitatively assess the adsorption capacities of the adsorbents using Methylen Blue (MB) and Victoria Blue B (VB-B) etc. as the model dyes respectively. The plots obtained from the Langmuir and Freundlich isotherm models for adsorption of MB and VB-B etc. by the present adsorbents, and the correlation coefficients (R2) deduced from the experimental data by these two isotherm models. According to the value of R2, the Langmuir isotherm model gives a much better fit to the adsorption data than the Freundlich isotherm model. The fitting results suggest that the dye adsorption behavior for MB and VB-B etc., on the N-OMCs surface involves a monolayer adsorption process.
On the other hand, this study will also used N-OMCs for further application. The metal oxide of SnO2 nanoparticles were successfully supported on N-OMCs (denoted SnO2@N-OMCs) via wet impregnation, and the diameter size were around 4~5 nm. Sn2+ metal ions were adsorbed by N-OMCs as carriers and then calcined by high temperature (300 °C) calcination to form the SnO2 metal oxide. These materials will be used as a anode of the Lithium ion battery.
The second part is the development of new composite solid polymer electrolyte. The composite solid polymer electrolytes (SPEs) with comb structure (denoted PEDx, x=6, 9, 20) were successfully synthesized, and characterized. The polymers of the three-block structure Jeffamine ED2003, ED900 and ED600 were used to react with CN triple bond of polyacrylonitrile (PAN) as the main segment to form the composite SPEs with comb structure. The conductivity of the SPEs were the series of ED900 with an optimum ionic conductivity of 6.28 x 10-5 S/cm at 30 °C and electrochemical stability at 3.5~4.0 V for oxidative cracking Voltage. The high ionic conductivity of SPEs will be used in lithium ion batteries charge and discharge test. |
