摘要
金属有机骨架（MOFs）是一类包含金属离子和有机配体的多孔材料，由于其具有结构多样性和化学多样性的特点，在化学催化、气体分离、能量储存等领域运用较为广泛。随着过硫酸盐高级氧化技术的迅速发展，一些铁基MOFs在过硫酸盐领域得到关注。本文选取铁基金属有机骨架MIL-101(Fe)为主体，通过合成后修饰法(POSM)制备了催化剂Co-MIL-101(Fe)、Cu-MIL-101(Fe)，并且采用合成前优化法(PRSM)制备了催化剂MIL-101(Fe，Cu)。实验探讨了催化剂MIL-101(Fe)、Co-MIL-101(Fe)和Cu-MIL-101(Fe)以及MIL-101(Fe，Cu)活化过硫酸盐(PS)降解水中有机污染物的催化能力。具体研究内容与研究成果如下：
（1）Co-MIL-101(Fe)与Cu-MIL-101(Fe)的制备、表征与催化性能
全陪以溶剂热法制备MIL-101(Fe)，采用POSM法将Co2+或Cu2+掺杂至MIL-101(Fe)中，分别构建Co-MIL-101(Fe)/PS、Cu-MIL-101(Fe)/PS、MIL-101(Fe)/PS的非均相反应体系降解酸性橙（AO7）。根据催化剂的结构表征分析，Co2+与Cu2+的掺杂改变了MIL-101(Fe)的微观结构，相比Cu2+，Co2+对MIL-101(Fe)的结构影响更大一些。催化剂对AO7去除效果的关系有Co-MIL-101(Fe)> Cu-MIL-101(Fe)> MIL-101(Fe)。根据实验的深入研究，得到金属掺杂量最适值为8%，PS投加量最佳值为8mM/L。SO4-•是催化剂活化PS产生的主要氧化物自由基。催化剂活化PS的非均相反应过程伴随着铁离子的溶出。
（2）MIL-101(Fe，Cu)的制备、表征与催化性能
以Cu2+代替部分Fe3+，采用PRSM法直接制备MIL-101(Fe，Cu)催化剂，构建MIL-101(Fe，Cu)/PS的非均相反应体系降解罗丹明B（RhB）。Cu2+的掺杂也改变了MIL-101(Fe)的微观结构，具体表现在SEM、BET的变化。相比MIL-101(Fe)，MIL-101(Fe，Cu)的催化能力明显增强。pH是MIL-101(Fe，Cu)/PS体系中重要的参数，MIL-101(Fe, Cu)在pH为2.68-4的范围内具有较好的催化能力。
（3）催化剂活化PS降解邻苯二甲酸二丁酯（DBP）的催化性能
基于以上的实验研究基础，探讨了催化剂MIL-101(Fe)、8%wtCo-MIL-101(Fe)、8%wtCu-MIL-101(Fe)和MIL-101(Fe, Cu)-4#对DBP的催化去除能力。其中，最佳催化剂是8%wtCo-MIL-101(Fe)，对DBP的去除率可以达到84.5%。
（4）金属离子掺杂的作用
掺杂至MIL-101(Fe)上的实际金属离子远低于1%。本研究将催化效果得到提高的原
因归结于以下几点：掺杂离子与铁离子的配位竞争，提高了催化剂中不饱和铁离子活性位点的数量；掺杂离子导致的BET、SEM的变化，在一定程度上促进了催化剂的催化效果。
关键词：Co-MIL-101(Fe)；Cu-MIL-101(Fe)；MIL-101(Fe, Cu)；不饱和铁活性位点；过硫酸盐活化sam怎么读
Abstract
Metal-organic framework(MOFs), lf-asmbled with metal ions and organic ligands, are crystalline porous materials with structure diversity and chemical varieties. The characteristics allowed MOFs to be widely ud in chemical catalysis, gas paration and energy storage. With the rapid development of advanced oxidation technologies bad on sulfate radicals, a number of Fe-bad MOFs have gained attention in the field of persulfate activation. In this work, we illustrated the synthesis of Co(Ⅱ) or Cu(Ⅱ) supported MIL-101(Fe). Co-MIL-101(Fe) and Cu-MIL-101(Fe) were prepared by post-synthesis modification(POSM), MIL-101(Fe,Cu) was synthesized via pre-synthesis modification(PRSM). All of catalysts were tested to activate per sulfate(PS) for removal of water contaminants. The main rearch contents and conclusions are as follows:
(1)Preparation, characterization and catalytic performance of Co-MIL-101(Fe) and Cu-MIL-101(Fe)
Co-MIL-101(Fe) and Cu-MIL-101(Fe) were prepared by the means of POSM on the basis of MIL-101(Fe) synthesized with hydrothermal method. Catalysts，Co-MIL-101(Fe), Cu-MIL-101(Fe) and MIL-101(Fe), were employed to catalyze persulfate to oxidize Acid Orange 7(AO7). The addition of Cu2+and Co2+brought about great changes in crystalline structure and morphology appearance. Mo
reover, Co doping caud greater changes in comparison with Cu doping. The quence of catalytic performance from high to low was: Co-MIL-101(Fe), Cu-MIL-101(Fe), MIL-101(Fe). Catalysts exhibited better catalytic performance: the addition amount of metal ions was 8%, the dosage amount of persulfate was 8mM/L. The AO7 degradation was mainly ascribed to the sulfate radicals. What’s more, there was the loss of iron ion form catalysts during persulfate activation.
(2)Preparation, characterization and catalytic performance of MIL-101(Fe, Cu)
The MIL-101(Fe, Cu) catalyst was prepared by the method of PRSM, with substitute Cu2+ for Fe3+. MIL-101(Fe, Cu) was tested to activate persulfate(PS) for removal of Rhodamine B in water. Cu doping also altered structure characteristics of MIL-101(Fe). The catalytic performance of MIL-101(Fe, Cu) was superior to that of MIL-101(Fe).pH value was an important parameter, and MIL-101(Fe, Cu) could showed better catalytic ability in the
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range of pH=2.68-4.
(3)Catalysts on the removal of Dibutyl phthaate(DBP)
In view of the above rearches, MIL-101(Fe), 8%wtCo-MIL-101(Fe), 8%wtCu-MIL-101(Fe) and MIL-
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101(Fe, Cu)-4# were investigated to the degradation of DBP. The best removal rate of 84.5% was achieved by 8%Co-MIL-101(Fe).
(4)The role of metal doping
The loaded content of metal was below 1wt% actually. Such an enhancement in activity may be attributed to the main reasons: an increa number of active Fe sites produced by Co and Cu doping; the alteration of BET and SEM could promoted the catalytic ability.
Keywords: Co-MIL-101(Fe); Cu-MIL-101(Fe); MIL-101(Fe, Cu); active iron sites; persulfate activation
目录
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摘要......................................................................................................................................... I Abstract .................................................................................................................................. III 第一章绪论. (1)
1.1 前言 (1)
1.2 高级氧化技术 (1)
1.2.1 高级氧化技术概述 (1)
1.2.2 基于羟基自由基传统高级氧化技术 (2)
1.2.3 基于硫酸根自由基新型高级氧化技术 (3)
1.3 金属有机骨架MOFs材料 (5)
1.3.1 MOFs的发展历程 (5)
花的种类1.3.2 MOFs的结构特点 (6)
英汉翻译器下载1.3.3 几种典型的MOFs的介绍 (6)
1.3.4 MOFs的修饰 (7)
1.4 MOFs在高级氧化技术方面的应用 (8)
1.5 论文选题思路、研究内容与创新点 (8)
1.5.1 论文选题思路 (8)
1.5.2 研究内容 (9)
1.5.3 创新点 (10)
第二章Cu-MIL-101（Fe）与Co-MIL-101（Fe）的制备及其非均相PS反应降解酸性橙溶液的研究 (11)
2.1 实验试剂与仪器 (11)
2.1.1 实验试剂 (11)
我爱美女网2.1.2 实验仪器 (11)
2.2 实验方法 (12)
2.2.1 催化剂的制备方法 (12)addle
cur2.2.2 催化剂的表征方法 (13)
2.2.3 催化剂催化性能的试验方法 (13)
2.3 结果与讨论 (14)
