開發醛酮類化合物與金屬有機骨架材料應用於周界揮發性有機物檢測方法;Development of aldehydes and ketones and metal-organic framework materials for the detection of volatile organic compounds in the air

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/89115

Title:	開發醛酮類化合物與金屬有機骨架材料應用於周界揮發性有機物檢測方法;Development of aldehydes and ketones and metal-organic framework materials for the detection of volatile organic compounds in the air
Authors:	陳芳翊;Chen, Fang-I
Contributors:	化學學系
Keywords:	醛酮類化合物;金屬有機骨架;臭氧前驅物;Carbonyls;MOF;PAMS
Date:	2022-07-14
Issue Date:	2022-10-04 10:58:32 (UTC+8)
Publisher:	國立中央大學
Abstract:	本篇論文主旨為針對環境空氣中兩項重要有機物質，醛酮類化合物及 54 項光化臭氧前驅物 (PAMS)，論文架構包含兩部份，第一部分為開發醛酮類化合物檢測方法與收集環境實測數據；第二部分為利用新穎金屬有機骨架 (MOFs) 材料並應用於光化臭氧前驅物吸附研究。第一部分開發醛酮類化合物吸附匣檢測方法，我國現行醛酮類化合物檢測方法為吸收瓶法，方法偵測極限較高 (數個 ppb)，以三大石化性質特殊性工業區定期採樣監測為例，數據常為「未檢出」 (ND)，無法應用於臭氧減量評估。本研究參考美國標準方法，開發優化之醛酮類檢測方法，搭配自製衍生試劑，方法偵測極限 (MDL) 為 (0.09- 0.15 ppbv)，為現行方法之 1/60 倍。實測地點挑選萬華光化站 (移動源)、六輕工業區站與仁大工業區站 (固定源)。研究結果顯示萬華光化站甲醛測值 < 0.6 ppbv、乙醛多為 ND；在一天的濃度趨勢中，中午時段濃度比上、下班時段高，顯示此區醛酮類排放以二次光化生成為主。六輕工業區監測結果顯示甲醛、乙醛大多數時間 < 1 ppbv，與吸收瓶法比對結果顯示兩方法數據大致相符，但吸附匣法 MDL 較低，相較於吸收瓶法可測得環境低濃度。仁大工業區結果顯示甲醛最高值為 11.23 ppbv，風向推估可能來自位於採樣地點東南方某工廠；乙醛監測結果< 1 ppbv。論文的第二部分探討新穎 MOFs 材料應用於 54 項 PAMS 吸附研究，主要使用之 MOFs 為 UiO-66，其架構由無機金屬鹽離子或金屬團簇提供中心點，並與有機配位體橋接，形成孔洞結晶聚合材料，具有可調控的孔徑、孔隙率高、高比表面積、可重複使用的優勢，而被廣泛應用於各種領域。對於微量氣體分析研究則鮮少有文獻發表。 UiO-66 屬於高穩定性、疏水性材料，本研究使用 100 ppbC 之 54 項 PAMS 標準氣體進行 UiO-66 吸附能力測試，並與傳統多重床碳吸附劑相比較。研究結果顯示單一材料 UiO-66 即可吸附範圍涵蓋 C2- C11 之 54 項 PAMS，與多重床碳吸附劑效果相似，檢量線線性良好， R2> 0.9950。在熱脫附溫度與氣體吸附量測試中，結果顯示 250℃即可達到大約 99%完全熱脫附。若以單位碳感度計算，UiO-66 之吸附結果也與多重床碳吸附劑一致。為了探討 UiO-66 在多次吸、脫附後之材料結構差異，以 X 光繞射儀 (XRD) 量測結果發現 UiO-66 在高溫後晶體已破壞不均，導致材料孔洞產生大小不一致的改變，大、小孔洞分別益於大、小分子之有機物吸附，以碳數廣泛之 PAMS 為例，單一材料即可吸附 C2-C11 PAMS。最後將 UiO-66 實際應用於周界實測，每日執行查核與空白測試，連續實測五天查核回收百分率為 78%- 109%之間，RSD < 7%，符合標準方法查核規範 (回收率 < ±25%)，顯示單一 UiO-66 適合作為有機物質周界實測之吸附材料。;This study aimed to focus on two critical organic substances, which were 15 carbonyls and 54 photochemical ozone precursors (54 PAMS) in ambient air. This study consists of two parts; the first part is to develop the analytical method to detect the ambient carbonyls and collect the field data from various emission sources. The second part is to utilize the novel metal-organic frameworks (MOFs) materials that apply to the adsorption investigation of 54 PAMS. The first section is to develop the cartridge method for detecting ambient carbonyls, which provides a lower MDL (method detection limit) option than the current method (impinger method). The data collected from the three petrochemical designated industrial zones (DIZs) were often shown as "Non-Detected" (ND), which is unable to provide sufficient information for ozone reduction assessment. By referencing the USEPA TO-11A compendium method, an optimized method for detecting carbonyls as well as the self-made cartridges were developed for ambient monitoring. The MDL for cartridge method was sub ppbv level (0.09-0.15 ppbv), which was 1/60 fold compared with the current method. Field measurement sites were selected from Wan-hua PAMS (mobile sources), the sixth naphtha cracker DIZ, and Renda Industrial complex (stationary sources). The results show that the measurement for formaldehyde in Wanhua PAMS is below 0.6 ppbv, and acetaldehyde is mostly ND. The diurnal trend showed that the mixing ratio is the highest at noon, indicating that the carbonyls mainly came from the secondary photochemical reaction. According to the data collected from the sixth naphtha cracker DIZ,formaldehyde and acetaldehyde are below 1 ppbv, and the impinger method show ND, which is roughly consistent. The lower MDL for the cartridge method provides lower mixing ratios which can be used to investigate the photochemical reaction of the ozone precursors. The results from Renda Industrial complex showed the highest mixing ratio for formaldehyde was 11.23 ppbv, which indicated that the source was from a formaldehyde-process factory in the southeast. Acetaldehyde was below 1 ppbv through the whole monitoring period. The second section of the thesis is the application of the novel MOFs used to investigate the 54 PAMS adsorption studies. The main MOF is used in UiO-66, a porous crystalline polymeric material with adjustable pore size, high porosity, high specific surface area, and reusability, and is widely used in various fields. However, very little literature has been published on VOC studies′ adsorption. UiO-66 is a highly stable and hydrophobic material. In this study, 54 PAMS of mixing ratio 100 ppbC, were used to investigate the adsorption capability of UiO-66, compared with the traditional multiple-bed carbon adsorbents. The research results show that a single material, UiO-66 could adsorb 54 PAMS covering C2-C11, similar to the multi-bed carbon adsorbents. The calibration curve has good linearity (R2 > 0.9950), and the thermal desorption ability could achieve 99% at 250°C. To test the per carbon response, the adsorption results of UiO-66 are highly consistent with the multiple carbon adsorbents. After repeated cold trap and thermal desorption of the UiO-66 adsorbents, the Xray diffractometer (XRD) results show that the crystal of UiO-66 has collapsed unevenly, resulting in the formation of different size surface holes. The uneven size pore of the single UiO-66 provides the adsorption capability for the wide range of 54 PAMS. As a result, UiO-66 is applied to the five-days continuous measurement calibration and blank test. The recovery is 78%-109%, and RSD (relative standard deviation) is below 7%, which meets the regulation of the standard method. The results showed that a single UiO-66 is a suitable adsorbent for ambient monitoring.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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