高級氧化程序是利用氫氧自由基(HO‧)的強氧化力來分解水中的有機物，在各種高級氧化程序中，Fenton試劑 (H2O2/Fe2+) 已經被證實是有效且簡單的方法。但是此方法最大的缺點是在反應過程中產生大量的氢氧化鐵污泥，必需進ㄧ步作固液分離及污泥處置。爲了解決此問題，低濃度鐵離子的加藥量在傳統均相(homogeneous) Fenton和Fenton-like 反應中被嘗試。除此之外，以H2O2為氧化劑，以鐵氧化物作為異相(heterogeneous)光助Fenton觸媒的氧化程序值得進ㄧ步研究。
在均相Fenton和Fenton-like反應中使用低濃度鐵離子的加藥量(≦10 mg l-1)來催化H2O2進而氧化三種商用的偶氮染料，分別是紅色(Red MX-5B)、黑色(Reactive Black 5)和橘色(Orange G)。此實驗結果顯示只要1 mg l-1的鐵離子加藥量下，Fenton和Fenton-like反應兩者皆可以在120分鐘的反應時間下，即可將色度完全移除。然而，在pH 2.5下，使用1 mg l-1 Fe3+和100 mg l-1 H2O2的加藥量，經過反應480分鐘後，總有機碳的移除率對Red MX-5B、Reactive Black 5和Orange G卻分別只有37%、28% 和 31%。上述結果發現，在Fenton-like系統中使用低濃度的鐵離子加藥量對色度的移除方面有很好的效果，但是卻難以礦化偶氮染料。另外，此系統有兩個主要的缺點，第一是此系統必須操作在酸性環境下；第二則是總有機碳的去除率不佳。因此，利用異相的光助Fenton反應觸媒來取代傳統的均相Fenton和 Fenton-like反應並改善上述缺點。
實驗中所使用的新式活性氧化鋁覆膜鐵氧化物(FeAA-25)是利用流體化床結晶技術所製備的，利用此鐵氧化物作為異相光助Fenton觸媒來降解黑色偶氮染料(RB5)。此觸媒表面的主要成分經分析證實為非結晶型鐵氧化物及α-FeOOH。另外覆膜型FeAA-25的表面特性也ㄧㄧ被研究，包括電子顯微鏡觀察表面型態、表面元素分析、總鐵量、草酸可溶解的鐵量、以及比表面積。在pH值2.5到6.0之間，分別對RB5進行降解研究；實驗結果發現RB5的降解可以分成兩個觀點來討論。一個是由鐵氧化物本身所進行的異相催化；另一個是在酸性環境下，由鐵氧化物表面溶出的鐵離子所造成的均相催化。最後發現在pH值3.5以下，主要是以均相催化為主；在pH值4.0到6.0之間，RB5的氧化主要是由異相催化所貢獻。在此研究中亦發現不論是在以異相或均相催化為主的反應中，加入紫外光後皆可將降解速率提高約20%左右。
此外；繼續將反應的pH值提高到7.0，並由實驗結果提出一個簡單的RB5分解機制。實驗結果亦顯示在pH值7.0，加入5.0 g FeAA-25/L、29.4 mM H2O2及紫外光下，經過240分鐘的氧化後，0.1 mM的RB5的色度去除率和總有機碳去除率分別可以達到約70%及45%。在此機制中，RB5在FeAA-25上的吸附及脫附行為亦同時被討論。使用FeAA-25做為異相光助Fenton觸媒來降解有機物的優點是可將操作的pH值提高到7.0，但缺點是降解速率緩慢。
最後，我們希望同時結合均相的光Fenton和異相光助Fenton來對RB5進行降解。爲了降低FeAA-25在酸性環境下的鐵溶出量，我們藉由燒結來改變FeAA-25的表面結構，並使其成為另一個新式的觸媒(FeAA-500)。在pH值2.5下，經過75分鐘的氧化，可將0.1 mM的RB5的色度完全移除，同時總有機碳的移除率亦可達到95%。

Hydroxyl radical (HO‧) is very reactive, underlying the chemistry of advanced oxation processes (AOPs) for degrading organic compounds in water. Among various AOPs, Fenton’s reagent (H2O2/Fe2+) has been known to be an effective and simple oxidant. The major drawback of Fenton’s reaction is the production of substantial amount of Fe(OH)3 sludge that requires further separation and disposal. To solve this problem, using the low concentration of iron ions in conventional homogeneous Fenton and Fenton-like reaction was attempted. Furthermore, the application of iron oxide as the heterogeneous photoassisted Fenton catalyst in oxidizing organic contaminants deserves an in-depth investigation.
This study investigated Fenton and Fenton-like reactions at low iron concentration (≦10 mg l-1) to oxidize three commercial azo dyes, namely Red MX-5B, Reactive Black 5 (RB5) and Orange G. This investigation reveals that both of these methods can remove the color of these dyes completely after 120 min of reaction in the presence of only 1 mg l-1 iron concentration. However, only 37%, 28% and 31% TOC of 0.1 mM Red MX-5B, Reactive Black 5 and Orange G can be eliminated after 480 min of reaction in the presence of 1 mg l-1 Fe3+, and 100 mg l-1 H2O2 at pH 2.5. This result is also found that it is easily to decolorize but hardly to mineralize the azo dyes in Fenton-like system at low iron concentration. In addition, this system has two major shortcomings. The first is that the system must be operated at low pH value. The second is that the TOC removal of this system is low. Therefore, heterogeneous catalysts of the photoassisted Fenton reaction instead of conventional homogeneous Fenton and Fenton-like reaction.
A novel activated alumina-supported iron oxide (denoted as FeAA-25), prepared using a fluidized-bed reactor (FBR), and was utilized as a catalyst of the heterogeneous photoassisted Fenton degradation of azo-dye RB5. The major components coated on the surface were identified as amorphous iron oxide and α-FeOOH. The characteristics of supported FeAA-25 including the particle morphology, surface atomic compositions, total and oxalate-soluble Fe contents and the specific surface area were determined. Photooxidation of RB5 by H2O2 was performed with FeAA-25 in a batch reactor in the range of pH 2.5–6.0. The degradation of RB5 comes from two perspectives. One is the catalysis from the iron oxide (hetergeneous reaction). The other is the catalysis from the Fe ions leaching form the catalyst to solution (homogeneous reaction). Conclusively, although the homogeneous catalysis is primarily below pH 3.5, heterogeneous catalysis contributes increasing importance to the oxidation of RB5 at pH 4.0–6.0. It has been found that the presence of UVA light, both for homogeneous and heterogeneous reactions shows that the efficiency of degradation of RB5 could be raised about 20%.
Furthermore, a simplified mechanism of RB5 decomposition that is consistent with the experimental findings for a solution with a pH of up to 7.0 is proposed. About 70% decolorization was measured and 45% of the total organic carbon was eliminated on the surface of the iron oxide at pH 7.0 after 240 min in the presence of 0.1 mM RB5, 5.0 g FeAA-25/L, 29.4 mM H2O2, under 15W UVA. In this mechanism, the adsorption and desorption behaviours of RB5 on FeAA-25 were also studied. The advantage of the use of the FeAA-25 as the heterogeneous photoassisted Fenton catalyst is that the degradation up to pH 7.0. However, the degradation rate of the system is slow.
Finally, we hope to combine the homogeneous photo-Fenton with heterogeneous photoassisted Fenton for degradation of RB5. For reducing the amount of Fe leaching from the FeAA-25 catalyst in an acidic environment, we modify the structure of the FeAA-25 catalyst surface by calcining. After calcining, the FeAA-25 became another novel photo-catalyst (denoted as FeAA-500). The photo-catalytic activity of the FeAA-500 was evaluated in the photooxidative degradation of 0.1 mM RB5 in the presence of H2O2 and UVA light (λ = 365 nm) in a solution with a pH of 2.5. Complete decolorization of the model pollutant RB5 was achieved; the total organic carbon (TOC) removal ratio was 95% after 120 min of reaction.

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