- 學位論文
以電活性苯胺三聚體修飾鐵金屬有機骨架複合材之合成、鑑定及其在硫化氫氣體感測元件上之應用研究
Synthesis and characterization of electroactive aniline trimer decorated iron metal-organic framework composites in hydrogen sulfide gas sensing devices application
摘要
本研究主要目標為探討所製備含鐵有機金屬骨架材料 (MIL-88B(Fe)) 及具有苯胺三聚體之電活性含鐵有機金屬骨架材料 (ACAT-MIL-88B(Fe)) 之結構差異，並研究苯胺三聚體的導入對 MIL-88B(Fe) 應用在硫化氫氣體感測上之影響。 首先利用「氧化偶合法」合成胺基封端苯胺三聚體 (ACAT)，並利用紅外光譜儀 (FTIR)、高性能液相層析串聯質譜儀 (HPLC-MS)、液態核磁共振儀 (NMR) 等儀器進行化學結構鑑定。 再進一步透過溶劑熱法和高壓釜高溫加熱製備中心金屬為鐵之 MIL-88B(Fe) 和加入合成的 ACAT 製備 ACAT-MIL-88B(Fe)。 進一步透過X光粉末繞射儀 (PXRD)、掃描式電子顯微鏡 (SEM) 等儀器對材料做結構鑑定，並利用比表面積和孔隙度分析儀 (BET) 進行表面積鑑定材料表面積及孔洞大小。 由 BET 的數據顯示，MIL-88B(Fe) 的表面積為 205.8 m2/g 遠大於 ACAT-MIL-88B(Fe) 的 51.8 m2/g。 另一方面，由 FTIR 光譜的結果顯示: ACAT-MIL-88B(Fe) 可觀察到苯胺三聚體的醌環特徵峰，暗示此材料提供更多硫化氫氣體感測位置。 在氣體感測之應用方面，利用所合成之材料塗佈於ITO指叉式電極並進行硫化氫氣體的應用感測。 由於 MIL-88B(Fe) 具有氧化還原之性質，其初步對硫化氫氣體敏感度測試，將硫化氫氣體感測濃度範圍設定在 1 ppm ~ 10 ppm 之間，可發現 MIL-88B(Fe) 具有良好的響應值，再對 ACAT-MOF 進行硫化氫感測測定，發現 ACAT-MIL-88B(Fe)對硫化氫氣體敏感度大約是 MIL-88B(Fe) 的 2 倍。 可以推測: 苯胺三聚體的導入雖然降低了 MOF 材料的整體表面積，但同時也提供了更多的醌環位置增強硫化氫氣體的應用感測。 在「表面積下降」及「增加醌環位置」的兩個因素競爭之下，發現在硫化氫感測靈敏度的應用上，ACAT-MIL-88B(Fe) 為 MIL-88B(Fe) 的 2倍，且比原先材料穩定性更加優異。
並列摘要
The main objective of this study is to investigate the structural differences between the as-prepared iron-containing organometallic framework (MIL-88B(Fe)) and the electroactive iron-containing organometallic framework with aniline trimer (ACAT-MIL-88B(Fe)) , and studied the effect of the introduction of aniline trimer on the application of MIL-88B(Fe) in hydrogen sulfide gas sensing. Firstly, the amine-terminated aniline trimer (ACAT) was synthesized by the "oxidative coupling method", and the infrared spectroscopy (FTIR), high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS), liquid nuclear magnetic resonance (NMR) and other instruments for chemical structure identification. Further, MIL-88B(Fe) whose central metal is iron was prepared by solvothermal method and high-temperature autoclave heating, and ACAT-MIL-88B(Fe) was prepared by adding synthesized ACAT. The structure of the material is further identified by X-ray powder diffraction (PXRD), scanning electron microscope (SEM) and other instruments, and the surface area and pore size of the material are identified by the specific surface area and porosity analyzer (BET). According to the data of BET, the surface area of MIL-88B(Fe) is 205.8 m2/g which is much larger than that of ACAT-MIL-88B(Fe) which is 51.8 m2/g. On the other hand, the results of FTIR spectroscopy show that the characteristic peaks of the quinone ring of the aniline trimer can be observed in ACAT-MIL-88B(Fe), suggesting that this material provides more hydrogen sulfide gas sensing sites. In terms of gas sensing applications, the synthesized materials are used to coat ITO interdigitated electrodes for application sensing of hydrogen sulfide gas. Due to the redox properties of MIL-88B(Fe), its initial sensitivity test to hydrogen sulfide gas, the detection concentration range of hydrogen sulfide gas is set between 1 ppm and 10 ppm, it can be found that MIL-88B(Fe) has With a good response value, ACAT-MOF was tested for hydrogen sulfide sensing, and it was found that ACAT-MIL-88B(Fe) is about twice as sensitive to hydrogen sulfide gas as MIL-88B(Fe). It can be speculated that although the introduction of aniline trimer reduces the overall surface area of the MOF material, it also provides more quinone ring positions to enhance the application sensing of hydrogen sulfide gas. Under the competition of the two factors of "decreased surface area" and "increased quinone ring position", it was found that ACAT-MIL-88B(Fe) was twice as sensitive as MIL-88B(Fe) in the application of hydrogen sulfide sensing sensitivity, And it is more stable than the original material.