催化臭氧氧化是一種有效去除水和廢水中有機污染物的處理方法,文獻報道氧化錳材料催化分解臭氧活性較高,但在催化臭氧氧化中還缺乏系統(tǒng)研究。本文合成了一系列不同形貌、相態(tài)、價態(tài)和組成的氧化錳材料,應用于催化臭氧氧化降解酚類污染物。發(fā)現(xiàn)了不同條件下酚類污染物降解的活性自由基差異,及不同取代基對酚類污染物的降解速率及主要活性物種的影響關(guān)系,揭示了處理酚類混合溶時各組分的相互影響關(guān)系。并通過中間產(chǎn)物定性分析,提出了酚類污染物礦化時可能的反應路徑。首先合成α,p,γ,6,ε和λ六種相態(tài)的MnO2,發(fā)現(xiàn)α-MnO2催化4-硝基苯酚降解活性最高。催化劑表面羥基及化學吸附的水分子是催化臭氧分解產(chǎn)自由基的活性位,采用叔丁醇（t-BA）、對苯醌（p-BQ）和疊氮化鈉（NaN3）進行自由基抑制實驗,發(fā)現(xiàn)臭氧氧化和催化臭氧氧化過程中,主要是超氧自由基對4-硝基苯酚降解起作用,而不是羥基自由基。采用兩種表面活性劑十六烷基三甲基溴化銨（CTAB）和十二烷基硫酸鈉（SDBS）合成了兩種α-MnO2。采用0.2 M濃度CTAB溶液制備得介孔α-MnO2比表面積為387.7 m2/g,并在4-硝基苯酚降解和TOC去除中顯示很... 

【文章來源】：中國科學院大學(中國科學院過程工程研究所)北京市

【文章頁數(shù)】：151 頁

【學位級別】：博士

【文章目錄】：
摘要
Abstract
1. Introduction
    1.1 Water pollution and phenolic compounds contained wastewater
    1.2 Phenolic compounds as pollutants
    1.3 Treating method for phenols contained wastewater
        1.3.1 Biological Treatments
        1.3.2 Physical Treatments
        1.3.3 Chemical Treatments
    1.4 Ozonation
    1.5 Catalytic ozonation
        1.5.1 Homogeneous catalytic ozonation
        1.5.2 Heterogeneous catalytic ozonation
        1.5.3 Manganese based polymorphs and composites materials
    1.6 Goal
    1.7 Thesis Stracture
2. Materials synthesis and characterization
    2.1 Matrials and catalyst preparation methods
        2.1.1 Materials
        2.1.2 Catalyst preparation methods
    2.2 Catayst structure characterization
        2.2.1 X-ray diffraction（XRD）
        2.2.2 Scanning electron microscopy（SEM）
        2.2.3 Transmission electron microscopy（TEM）
        2.2.4 Energy dispersed x-ray spectroscopy（EDS）
        2.2.5 Inductively coupled plasma optical emission spectrometry（ICP）
2 physical adsorption">        2.2.6 N₂ physical adsorption
        2.2.7 Attenuated total reflectance Fourier transforms infrared spectroscopy （ATR-FTIR）
        2.2.8 Electron paramagnetic resonance（EPR）
        2.2.9 Cyclic Voltammetry（CV）
pzc)">        2.2.10 Point of zero charge(pH_pzc)
        2.2.11 Average oxidation state （AOS）
    2.3 Catalytic ozonation
2 and their activities for 4-NP ozonation">3. Synthesis of different phases of MnO₂ and their activities for 4-NP ozonation
    3.1 Synthesis and characterization
2">        3.1.1 Synthesis of α-,β-,δ-,γ-, λ-and ε-MnO2

        3.1.2 Characterization of α-, β-,δ-,γ-,λ- and ε-MnO₂

        3.1.3 Catalytic activity test
    3.2 Results and discussion
2">        3.2.1 p-nitrophenol degradation with MnO₂

        3.2.2 Reactive species and reaction mechanism
    3.3 Summary
2 for catalytic ozonation of 4-NP">4. Preparation of high surface area mesoporous α-MnO₂ for catalytic ozonation of 4-NP
    4.1. Catalyst synthesis
        4.1.1 Catalyst Characterization
        4.1.2 p-nitrophenol degradation
    4.2 Results and discussion
        4.2.1 Materials Characterization
        4.2.2 Catalytic degradation of 4-NP
        4.2.3 Impact of ozone dosage
        4.2.4 Catalytic stability
        4.2.5 Reaction mechanism
    4.3 Summary
x and catalytic ozoantion of phenolic mixture">5. Synthesis of different valences of MnO_x and catalytic ozoantion of phenolic mixture
    5.1. Materials and methods
2, Mn₂O₃ and Mn₃O₄">        5.1.1 Synthesis of MnO₂, Mn₂O₃ and Mn₃O₄

        5.1.2 Characterization of MnO₂, Mn₂O₃ and Mn₃O₄

        5.1.3 Catalytic activity experiment
    5.2 Results and discussion
        5.2.1 Materials characterization
        5.2.2 Mixture of phenolic compounds degradation
        5.2.3 Phenol degradation
        5.2.4 p-chlorophenol degradation
        5.2.5 p-cresol degradation
        5.2.6 TOC removal phenolic mixture
        5.2.7 Reaction kinetics in ozonation and catalytic ozonation
        5.2.8 The interaction of phenols in the mixed solution
        5.2.9 Reactive species and attacking patterns
    5.3 Summary
3O₄/MnO₂ composite and degradation mechanism">6. Phenolic mixture degradation with Fe₃O₄/MnO₂ composite and degradation mechanism
    6.1 Materials and methods
2,Fe₃O₄ and Fe₃O₄/MnO₂">        6.1.1 Synthesis of MnO₂,Fe₃O₄ and Fe₃O₄/MnO₂

        6.1.2 Characterization of MnO₂, Fe₃O₄ and Fe₃O₄/MnO₂

        6.1.3 Catalytic activity experiment
    6.2 Results and discussion
        6.2.1 Structural characterization of catalysts
        6.2.2 Catalytic ozonation of phenolic mixture
        6.2.3 Effective pH for stability of catalyst
        6.2.4 Catalyst activity for phenolic mixture
3O₄/MnO₂ catalytic ozonation">    6.3 Reaction mechanism of Fe₃O₄/MnO₂ catalytic ozonation
        6.3.1 ATR-FTIR
        6.3.2 CV
        6.3.3 Quenching Experiments
        6.3.4 Reaction pathway of phenolic mixture
    6.4 Summary
7. Conclusions and prospects
    7.1 General conclusions
    7.2 Prospects
List of abbreviations
REFERENCES
CURRICULAM VITA
ACKNOWLEDGEMENTS



本文編號：2935251

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