本研究藉由微藻表面豐富的官能基以及具磁性特性的四氧化三鐵磁性奈米粒子(Fe3O4 MNPs)，製備吸附劑材料，透過紫外光/可見光分光光度計對不同金屬離子所建立出檢量線，對吸附前後的重金屬溶液進行定量分析，以分別探討微藻、Fe3O4 MNPs、不同混合比例的磁性粒子@微藻對Cr(VI)及Cu(II)的吸附效能，並觀察吸附行為的差異及趨勢，以得出適合的吸附條件。
本實驗將分為四個部分：首先，我們分別以培養完成的微藻經乾燥後，研磨製備出微藻生物質；在氮氣的環境下，以化學共沉法製備無修飾之Fe3O4 MNPs；結合磁性粒子@微藻，形成表面具有大量的微藻特性官能基、具磁性的複合型材料，並以FTIR、TGA、SQUID分析證實其表面特徵、重量百分比及其超順磁性。而後，以溶液中型態為陰離子的Cr(VI)及陽離子的Cu(II)分別作探討，為了討論各個環境對吸附過程的影響，改變了初始的pH值、初始的重金屬濃度、不同的接觸時間、不同的吸附劑劑量。再來，探討同時存在Cr(VI)及Cu(II)的二元溶液是否存在競爭反應，找出對兩者皆有良好去除率的條件，於此先以微藻生物質與Fe3O4 MNPs做初步觀察，得出微藻生物質適合去除Cu(II)，而Fe3O4 MNPs適合去除Cr(VI)，並以不同比例的磁性粒子@微藻、初始pH值、初始Cr(VI)濃度、吸附劑劑量此四項影響因子作為自變數，透過反應曲面法（Response surface methodology, RSM）中的Box-Behnken Design(BBD)建構出對不同Cr(VI)濃度與固定Cu(II) 20 mg/L下，分別具88.84、95.6 %可預測性的二次迴歸模型。最終，以0.5M NaOH + 2.5M NaCl及0.2M HCl分別作為對Cr(VI)及Cu(II)的洗脫液，對磁性粒子@微藻進行三次的吸附-解吸附的循環實驗，證實其可重複使用性，並以常見的Langmuir及Freundlich等溫吸附模型和PFO及PSO模型進行擬合，描述吸附行為。
磁性粒子@微藻作為去除重金屬離子的材料，具備了超順磁性，可藉由永久磁鐵在幾秒鐘內實現吸附劑與溶液間的分離，且外加磁場移除後便不具有磁性，大幅度的降低了時間成本並提高其應用價值。

In this study, adsorbent materials were prepared by using abundant functional groups on the surface of microalgae and magnetic nanoparticles with magnetic properties. The calibration lines were established for different metal ions by UV/Vis spectrophotometer. The solution was quantitatively analyzed to investigate the adsorption efficiency of microalgae, Fe3O4 magnetic nanoparticles (MNPs), and magnetic particles @ microalgae with different mixing ratios on Cr(VI) and Cu(II), and to observe the difference in adsorption behavior and trend to obtain suitable adsorption conditions.
This experiment will be divided into four parts: first, we use the cultured microalgae to be dried and ground to prepare the microalgal biomass; in the nitrogen environment, the Fe3O4 MNPs are organized by the chemical co-precipitation method; combined with magnetic particles @ microalgae to form a magnetic composite material with a large number of functional groups characteristic of microalgae on the surface, and its surface characteristics, weight percentage, and superparamagnetic properties were confirmed by FTIR, TGA, and SQUID analysis. Then, the forms of Cr(VI) as anions and Cu(II) as cations in the solution were discussed respectively. To discuss the influence of each environment on the adsorption process, the initial pH value, initial heavy metal concentration, and different contact times, different adsorbent doses.
Next, to explore whether there is a competitive reaction in the binary solution with both Cr(VI) and Cu(II), and find out the conditions that have a good removal rate for both, here we first use microalgal biomass and Fe3O4 MNPs. Preliminary observation shows that microalgal biomass is suitable for removing Cu(II), while Fe3O4 MNPs are suitable for removing Cr(VI). Initial pH value, Cr(VI) concentration, and adsorbent dose, these four influencing factors are used as independent variables, through Box-Behnken Design (BBD) in Response surface methodology (RSM) to construct the different Cr(VI) concentrations. Quadratic regression models with 88.84 and 95.6 % predictability, respectively, with a fixed Cu(II) of 20 mg/L. Finally, 0.5M NaOH + 2.5M NaCl and 0.2M HCl were used as eluents for Cr(VI) and Cu(II), respectively, and the magnetic particles @ microalgae were subjected to three adsorption-desorption cycles to prove it is reusable. Fitted with the common Langmuir and Freundlich isotherm adsorption models and PFO and PSO models to describe the adsorption behavior.
Magnetic particles @ microalgae, as a material for removing heavy metal ions, have superparamagnetic properties, which can be separated from the adsorbent and the solution within a few seconds by a permanent magnet, and will not be magnetic after external magnetic field removal. It reduces the time cost and improves its application value.

摘要......i
ABSTRACT......iii
致謝......v
表目錄......ix
圖目錄......x
第一章 緒論......1
1.1 研究背景......1
1.2 研究動機......1
1.3 研究目標及內容......3
第二章 文獻回顧......5
2.1 鉻、銅的特性簡介......5
2.2吸附劑......6
2.2.1 微藻......6
2.2.2 磁性粒子......8
2.2.3 藻類複合材料......10
2.3 生物吸附機制......12
2.3.1 活藻類、死生物質的比較......13
2.4 吸附過程的影響因素......15
2.4 吸附劑的再生......17
2.5 重金屬溶液的檢測方法......18
2.5.1 ICP-MS......18
2.5.2 AAS......19
2.5.3 UV-vis......19
第三章 實驗材料及研究方法......21
3.1 實驗流程......21
3.2 實驗所需之儀器......22
3.3 吸附劑的製備......24
3.3.1 微藻生物質的培養與製備......24
3.3.2磁性粒子製備......27
3.3.3磁性粒子@微藻製備......28
3.4 實驗設計......29
3.4.1 Box-Behnken Design(BBD)......29
3.4.2 解吸附及再生研究......31
3.5 重金屬溶液配製與檢測......32
3.5.1 Cr(VI)溶液......32
3.5.2 Cu(II)溶液......34
3.6 吸附行為描述......36
3.6.1 Langmuir等溫吸附模型......36
3.6.2 Freundlich等溫吸附模型......37
3.6.3 吸附動力學......38
第四章 實驗結果與討論......40
4.1 吸附劑的表面官能基鑑定......40
4.2 吸附劑的熱重分析......41
4.3 吸附劑的磁性量測......42
4.3 Cr(VI)的吸附實驗結果......44
4.3.1 初始pH值的影響......44
4.3.2 初始重金屬濃度及接觸時間的影響......45
4.3.3 吸附劑劑量的影響......47
4.4 Cu(II)之吸附實驗結果......48
4.4.1 初始pH值的影響......48
4.4.2 初始重金屬濃度及接觸時間的影響......49
4.4.3 吸附劑劑量的影響......51
4.5 二元(Cr(VI)/Cu(II))之吸附實驗......51
4.5.1微藻生物質及磁性粒子的二元吸附......52
4.5.2磁性粒子@微藻的二元吸附......53
4.5.2.1 迴歸模型及方差分析......54
4.5.2.2 柏拉圖及三維曲面圖......57
4.5.2.3渴望函數......60
4.6 吸附-解吸附循環......61
4.7 等溫吸附模型......62
4.8 吸附動力學模型......64
第五章 結論與未來規劃......65
5.1 結論......65
5.2 未來規劃......67
參考文獻......69

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