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標題: 層狀雙氫氧化物的電荷密度及層間硝酸根離子的排列方式對其吸附除草劑2,4-D的影響
Effects of layer charge density and nitrate orientation of layered double hydroxides on the sorption of 2,4-D
作者: 曹雅芳
Tsao, Ya-Fang
關鍵字: layered double hydroxides;層狀雙氫氧化物;2,4-D;adsorption;ion exchange;2,4-D;吸附作用;離子交換
出版社: 土壤環境科學系所
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Chlorinated phenoxyacetic acid herbicides, such as 2,4-dichlorophenoxyacetic acid(2,4-D), are widely used for controling weeds. Due to its low pKa value of 2.73, 2,4-D exists as an anionic species in the environment and has high mobility in soils and can easily migrate to non-target area by leaching. Layered double hydroxides (LDHs) have high specific surface area and anionic exchange capacity (AEC), so they have high potential in immobilizing inorganic and organic anion contaminants in water. However the adsorption is not specific to 2,4-D, and the existences of other anions may lower the adsorption efficiency of LDHs for 2,4-D. A better understanding of the adsorption mechanisms of LDHs will be essential for selective removal of 2,4-D by LDHs from water. In this study, the effects of the positive charge density and nitrate orientation of LDHs on the adsorption of 2,4-D were investigated. Mg/Al-NO3 LDH with Al3+/(Mg2++Al3+) molar ratios of 1/3 (LDH3), 1/4 (LDH4), 1/5(LDH5) were synthesized and used as the adsorbents. The kinetic study showed that the adsorption could reach equilibrium in 10 minutes. Among the samples, LDH3 has the highest layer charge density and contains nitrate with an orientation perpendicular to the hydroxide sheets, so the maximum adsorption of 2,4-D on LDH3 was as high as 89% of its anionic exchange capacity. The 2,4-D adsorption of LDH3 occurred mainly through ion exchange for interlayer nitrate. On the contrary, LDH5 with a low 2,4-D adsorption capacity due to the low accessibility of 2,4-D to the interlayer space. The accessibility was restricted by the small basal spacing of LDH5 as a result of the parallel orientation of the interlayer nitrate with respect to the hydroxide sheet. Thus, the 2,4-D adsorption occurred mainly on the external surface of the material, and the maximum adsorption of 2,4-D on LDH5 was 16 % of its anionic exchange capacity. For LDH4 that contains interlayer nitrate with both parallel and perpendicular orientations, the adsorption characteristics was between those of LDH3 and LDH5, and the maximum amount of 2,4-D adsorbed on LDH4 was 66% of the anionic exchange capacity. The results of competitive adsorption revealed that the adsorptions of 2,4-D on LDH3 and LDH4 are less affected by the coexistences of other anions, such as Cl-、Br 、NO3-、HCO3-、SO42-, in solution. The kinetic adsorption curves of LDH3 and LDH4 in different temperatures had a good fit with pseudo-second order kinetic model. The rate of the adsorption of 2,4-D on LDHs increasing with temperature, and LDH3 required more activation energy to adsorb 2,4-D then LDH4. The results of this study suggested that LDH3 is a better adsorbent for removing 2,4-D from water.

苯氧基酸系的除草劑2,4-dichlorophenoxyacetic acid(2,4-D)是一種廣為使用的除草劑,其pKa值為2.73,所以在環境中會解離成陰離子型態,因此容易被淋洗或流失到非目標區域並威脅水體。奈米層狀雙氫氧化物(layered double hydroxides, LDHs)具有高比表面積與高陰離子交換容量,而具有移除環境中2,4-D的潛能。但存在於環境中的其他陰離子可能對2,4-D的吸附進行競爭作用,因此必須瞭解影響LDHs 陰離子交換反應的機制以利其自水中移除2,4-D的效率。本研究的目的為利用Mg/Al-NO3 LDH吸附陰離子型除草劑2,4-D,並探討LDHs結構中層間正電荷密度、夾層陰離子的排列方式及溶液中的離子強度對其吸附行為的影響。所使用的Mg/Al-NO3 LDH,其Al3+/(Mg2++Al3+)比例分別為1/3 (LDH3)、1/4 (LDH4)、1/5(LDH5)。由動力吸附實驗中顯示LDHs對2,4-D的吸附速率很快,大約於10分鐘即可達反應平衡,透過等溫吸附實驗並配合XRD及FT-IR的分析結果發現,LDHs對2,4-D的吸附量主要受層間正電荷密度及硝酸根離子排列方式的影響,LDH3具有較大的層間電荷正密度且層間硝酸根離子以垂直的方式排列,致使對2,4-D的最大吸附量可達其陰離子交換容量的89 %,且吸附機制主要為陰離子交換。LDH5的層間電荷正密度較小且層間硝酸根離子以平行的方式排列,所以對2,4-D的最大吸附量遠低於其陰離子交換容量僅達16 %,主要為表面吸附。LDH4的層間電荷正密度介於中間,且層間硝酸根離子同時以垂直和平行的方式排列,對2,4-D的最大吸附量達其陰離子交換容量的66 %,且吸附機制主要為陰離子交換。因此,吸附機制主要為陰離子交換的LDH3及LDH4較不易受溶液中其他陰離子(Cl-、Br-、NO3-、HCO3-、SO42-)的影響。LDH3和LDH4,在不同溫度下的動力吸附曲線較適合以Pseudo-second order kinetic model模擬,溫度越高LDHs對2,4-D的吸附速率越快,且以LDH3對2,4-D的吸附所需之活化能較大。綜合以上結果,在三種不同電荷密度的LDHs中以LDH3較適合作為移除水中2,4-D之吸附劑。
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