以均苯四甲酸合成鈦金屬有機框架應用於二氧化氮感測器之研製
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2022
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氣體感測器（Gas sensor）是透過感測材料和目標氣體接觸，導致感測材料之電性產生變化，再將電訊號轉化為響應值。在這個物聯網的時代，對於感測器的需求十分龐大，且空氣汙染的問題也日趨嚴重，故氣體感測器的發展也備受矚目。金屬有機框架（Metal organic framework, MOF）是使用金屬離子和有機配體（Organic ligand）所合成之高比表面積材料，其高比表面積和金屬離子的氧化還原能力，十分有利於MOF材料與空氣中的氣體分子進行反應，故非常適合作為氣體感測元件之感測材料。目前氣體感測領域的研究已廣泛使用各種MOF作為氣體感測材料，但沒有文獻使用Ti-MOF進行氣體感測元件的開發，而且目前在Ti-MOF的研究中廣泛使用對苯二甲酸（Terephthalic acid, TPA）進行合成，卻沒有文獻使用均苯三甲酸(Trimesitinic acid, TMA)和均苯四甲酸(Pyromellitic acid, PMA)進行Ti-MOF的開發。因此，本研究致力於研發新型態的Ti-MOF材料，利用一步驟水熱法搭配Ti離子與均苯三甲酸和均苯四甲酸有機配體進行Ti-MOF(TMA)與Ti-MOF(PMA)的開發，同時合成文獻常見之Ti-MOF(TPA)一同進行比較。本研究開發的Ti-MOF(PMA)在室溫下對於200 ppm的NO2具有48.5的高響應，高於Ti-MOF(TPA)的13.5和 Ti-MOF(TMA)的1.7，且在50、100和150 ppm濃度的NO2下，分別具有6.4、16.1和35.6的響應值。Ti-MOF(PMA)在五次的連續循環下也具有15.9、15.7、16.1、15.6和15.9的穩定響應，且在100 ppm的丙酮、甲醇、乙醇和氨氣環境下，響應值分別僅有0.33、0.27、0.41與0.26，證明Ti-MOF(PMA)對NO2具有不錯的感測選擇性。最後也對氣體感測機制進行探討，且將本實驗結果與文獻進行比較，證實本研究所開發的Ti-MOF(PMA)有機會能成為氣體感測器有潛力的感測材料。關鍵詞：氣體感測器、金屬有機框架、均苯四甲酸、水熱法、響應值
The gas sensor changes the electrical properties of the sensing material through the contact between the sensing material and the target gas, and then translates the electrical signal into a response. In the era of the Internet of Things, there is a great demand for sensors, and air pollution is becoming more and more serious. Therefore, the development of gas sensors has also attracted much attention. Metal organic framework (MOF) is a high specific surface area material synthesized by using metal ions and organic ligands. Its high specific surface area and redox ability of metal ions are beneficial for MOF materials to react with gas molecules in the air. Therefore, it is very suitable as a sensing material for gas sensing device. Research in the field of gas sensing has widely used various MOFs as gas sensing materials at present, but there is no literature using Ti-MOFs to develop gas sensing device. In addition, terephthalic acid (TPA) is widely used in the research of Ti-MOF at present, but there is no literature using trimesitinic acid (TPA) and pyromellitic acid (PMA) to synthesize Ti-MOF.Therefore, this research is devoted to development of new types of Ti-MOFs. Development of Ti-MOF(TMA) and Ti-MOF(PMA) by one-step hydrothermal method with Ti ions and organic ligands of trimesic acid and pyromellitic acid. At the same time, the Ti-MOF (TPA) common in the literature was synthesized for comparison. The Ti-MOF(PMA) developed in this study has a high response of 48.5 for 200 ppm NO2, which is higher than 13.5 for Ti-MOF(TPA) and 1.7 for Ti-MOF(TMA). Ti-MOF (PMA) had a response of 6.4, 16.1 and 35.6 under NO2 concentrations of 50, 100 and 150 ppm, respectively. There are stable responses of 15.9, 15.7, 16.1, 15.6 and 15.9 over five cycles. The responses were only 0.33, 0.27, 0.41 and 0.26 at 100 ppm of acetone, methanol, ethanol and ammonia. It is proved that Ti-MOF (PMA) has good sensing selectivity for NO2. Finally, the gas sensing mechanism is discussed, and the experimental results are compared with the literature, proving that Ti-MOF (PMA) has the opportunity to become a potential sensing material for gas sensors.Keywords: Gas sensor, Metal organic framework, Pyromellitic acid, Hydrothermal method, Response
The gas sensor changes the electrical properties of the sensing material through the contact between the sensing material and the target gas, and then translates the electrical signal into a response. In the era of the Internet of Things, there is a great demand for sensors, and air pollution is becoming more and more serious. Therefore, the development of gas sensors has also attracted much attention. Metal organic framework (MOF) is a high specific surface area material synthesized by using metal ions and organic ligands. Its high specific surface area and redox ability of metal ions are beneficial for MOF materials to react with gas molecules in the air. Therefore, it is very suitable as a sensing material for gas sensing device. Research in the field of gas sensing has widely used various MOFs as gas sensing materials at present, but there is no literature using Ti-MOFs to develop gas sensing device. In addition, terephthalic acid (TPA) is widely used in the research of Ti-MOF at present, but there is no literature using trimesitinic acid (TPA) and pyromellitic acid (PMA) to synthesize Ti-MOF.Therefore, this research is devoted to development of new types of Ti-MOFs. Development of Ti-MOF(TMA) and Ti-MOF(PMA) by one-step hydrothermal method with Ti ions and organic ligands of trimesic acid and pyromellitic acid. At the same time, the Ti-MOF (TPA) common in the literature was synthesized for comparison. The Ti-MOF(PMA) developed in this study has a high response of 48.5 for 200 ppm NO2, which is higher than 13.5 for Ti-MOF(TPA) and 1.7 for Ti-MOF(TMA). Ti-MOF (PMA) had a response of 6.4, 16.1 and 35.6 under NO2 concentrations of 50, 100 and 150 ppm, respectively. There are stable responses of 15.9, 15.7, 16.1, 15.6 and 15.9 over five cycles. The responses were only 0.33, 0.27, 0.41 and 0.26 at 100 ppm of acetone, methanol, ethanol and ammonia. It is proved that Ti-MOF (PMA) has good sensing selectivity for NO2. Finally, the gas sensing mechanism is discussed, and the experimental results are compared with the literature, proving that Ti-MOF (PMA) has the opportunity to become a potential sensing material for gas sensors.Keywords: Gas sensor, Metal organic framework, Pyromellitic acid, Hydrothermal method, Response
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氣體感測器, 金屬有機框架, 均苯四甲酸, 水熱法, 響應值, Gas sensor, Metal organic framework, Pyromellitic acid, Hydrothermal method, Response