請用此 Handle URI 來引用此文件: http://hdl.handle.net/11455/90143
標題: Study of Electrochemical Reactivity of Phenolic Compounds Affected by Layer Charge of Clay Minerals
作者: Chia-Ying Chu
關鍵字: Clay minerals
Layer charge
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摘要: Phenolic compounds are common compounds of soil and that are catalyzed and transformed by clay minerals to soil humus. The process plays a significant role in soil pedogenesis, the physical, chemical and biological properties of soil and soil fertility. This study investigated the electrochemical behavior of p-nitrophenol, benzenediol and dopamine at different clay-modified screen-printed carbon electrodes coupling with electrochemical method, and study the different electrochemical behavior of phenolic compounds affected by different layer charge of clay minerals. The results indicated the reductive peak current of p-nitrophenol from HOC6H4NO2 to HOC6H4NHOH (R1) was 204 μA for SWy-1 (the highest) and 146 μA for KGa-1 (smallest) among the six clay-modified electrodes studied. Even larger reductive and oxidative peak currents can be detected at the clays modified on 'preanodized' screen-printed carbon electrodes (SPCE*) due to the hydrogen bonding between oxide film and basal surface of tetrahedral sheet and octahedral sheet. The highest reductive peak current (329 μA) was detected at the SHCa-1 SPCE* and next of 317 μA at the SWy-1 SPCE*. Paraquat might affect the redox behavior of p-nitrophenol to cause a change of peak shape and current for reductive peak current without oxidative peak currents. The effect of SPCE* was apparently different from that of paraquat since the oxidative power of paraquat on the redox of p-nitrophenol is different from that of the oxide film at the SPCE*. The results indicated that two reductive peaks (R1, R2) and two oxidative peaks (O1, O2) were observed at all six clay-modified SPCEs with higher R1 peak current from SHCa-1, SWy-1 and SWa-1. Preanodization of SPCE (SPCE*) further makes an increase in the peak currents of R2 and O2. The differences in cyclic voltammograms at six clay-modified SPCEs for hydroquinone and catechol was originated from different bonding sites of two hydroxyl groups on the benzene. The peak shape of R2 in respective solution was broader than those of detected at six clay-modified SPCEs and different reduction potentials and peak currents between p-benzoquinone and o-benzoquinone were affected by different layer charges of clay minerals. The results also indicated the highest peak currents of R1 and O1 (100 μA and 61.9 μA) could be determined by SWy-1 SPCE, and the highest peak currents of R2 (48.5 μA) was SWa-1 SPCE and the highest O2 (61.4 μA) was SHCa-1 SPCE at six clay-modified electrodes. All peak currents of six clay-modified SPCE* were more than that of six clay-modified SPCE due to the oxide film on the electrode surface could improve the transference of second electron more than that of first electron. The peak currents of R2 and O2 for coexist solution were higher than the peak currents of R1 and O1 detected by six clay-modified SPCE*s. The different electrochemical behaviors of phenolic compounds with different structure were affected by different crystal structures and layer charges of clay minerals, and we could understand the interaction between phenolic compounds and clay minerals using different clay-modified electrodes coupling cyclic voltammetry.
酚類化合物普遍存在於土壤中,黏土礦物對酚類化合物的催化聚合與轉化反應常是土壤腐植質先驅物形成的關鍵,其對土壤的形成、物理化性質、生物性質及土壤肥力之影響扮演重要的角色。本論文研究目的以不同黏土礦物修飾網版印刷碳電極 (SPCE) 搭配電化學分析對對硝基苯酚、苯二酚及多巴胺等進行電化學分析,以探討黏土礦物層面電荷對這些化合物在電化學反應行為上的差異,進一步了解其間的交互作用關係。試驗結果指出,六種黏粒修飾SPCE對對硝基苯酚由HOC6H4NO2還原到HOC6H4NHOH所測到的R1波峰電流量以SWy-1為最大 (204 μA),而以KGa-1為最小 (146 μA);六種黏粒修飾預氧化網版印刷碳電極 (SPCE*) 可測到更大的R1還原波峰及氧化波峰電流量。由於SPCE* 表面氧化層膜的羰基和羥基會與黏土礦物四面體層及八面體層表面產生氫鍵,其影響黏土礦物的電場效應與對硝基苯酚的極化,導致所測得之R1波峰形狀較為尖銳且波峰電流量較大,其中以SHCa-1最大 (329 μA),其次是SWy-1 (317 μA)。有巴拉刈存在時,六種黏粒修飾SPCE可測得R1還原波峰,但無法偵測到氧化波峰電流量,顯示巴拉刈的氧化力在對硝基苯酚氧化還原反應上的影響明顯與SPCE* 表面氧化層膜對對硝基苯酚之作用機制不同。 六種黏粒修飾SPCE對對苯二酚均能測到兩個還原波峰 (R1、R2) 與兩個氧化波峰 (O1、O2),且其中以2:1型膨潤石類 (SHCa-1、SWy-1及SWa-1) 測到的R1波峰電流量較大。SPCE經預氧化處理後 (SPCE*) 再修飾六種黏粒對對苯二酚測到的氧化還原波峰電流量均有明顯增大的現象,且其中以R2和O2氧化還原波峰對增大及波峰電位偏移的情形較為明顯。由於兩個羥基在苯環之鍵結位置上的不同,使六種黏粒修飾SPCE對對苯二酚與鄰苯二酚所測到的氧化還原波峰形狀和電流量不同,且其對兩種苯二酚共存溶液測到的R2波峰形狀比兩種苯二酚各別測到的R2波峰形狀更為駝形,且受到不同黏土礦物層面電荷所影響,所以在偵測到的循環伏安圖與波峰電流量上會不同。 六種黏粒修飾網版印刷碳電極對多巴胺進行偵測,結果顯示SWy-1 SPCE所測到的R1、O1氧化還原波峰對電流量為最大 (100 μA、61.9 μA),R2還原波峰電流量則以SWa-1 SPCE所測得的電流量最大 (48.5 μA),而O2氧化波峰電流量則以SHCa-1 SPCE為最大 (61.4 μA)。六種黏粒修飾預氧化網版印刷碳電極所偵測的電流量都明顯大於六種黏粒修飾網版印刷碳電極,且預氧化後電極表面上產生的氧化層促進第二莫耳電子的轉移大於第一莫耳的電子轉移。六種黏粒修飾預氧化電極對多巴胺與鄰苯二酚共存溶液偵測結果也顯示,R2、O2氧化還原波峰電流量均大於R1、O1氧化還原波峰電流量。不同結晶構造與層面電荷之黏土礦物確實會影響不同化學結構之酚類化合物在電化學行為上的表現,且利用黏粒修飾電極搭配循環伏安法的電化學分析能夠探討了解不同酚類化合物與黏土礦物間的交互作用關係。
URI: http://hdl.handle.net/11455/90143
文章公開時間: 2014-07-14

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