催化/分離科學技術(shù)的發(fā)展對國民經(jīng)濟社會的可持續(xù)發(fā)展至關(guān)重要,其核心是開發(fā)清潔經(jīng)濟的高性能催化劑/吸附劑。近年來,鋯基多孔功能材料因具有穩(wěn)定性高、比表面積大、環(huán)境友好而且易于功能化修飾等特性在眾多新型催化/吸附材料中備受關(guān)注。材料的組成、微觀結(jié)構(gòu)與形貌決定其催化/吸附性能,而材料的組成、微觀結(jié)構(gòu)與形貌又與合成方法與結(jié)晶過程密不可分。因此,本論文探索了多種策略合成超穩(wěn)鋯基功能多孔材料以及其在付克�；�、鈴木交叉耦聯(lián)反應吸附脫硫及催化氧化深度脫硫中的應用,系統(tǒng)地研究了材料合成-結(jié)構(gòu)-性能多層次的構(gòu)效關(guān)系,取得了系列創(chuàng)新性成果,具體介紹如下:（1）.采用溶劑熱一鍋法直接合成了高比表面積（1065-2058 m2/g）和高磷鎢酸（HPW）負載量（32.3 wt.%）的酸性鋯基功能MOF材料(HPW@Zr（BTC）。研究表明適量HPW的引入不僅在合成過程中起到模板作用提高了鋯基MOF材料的結(jié)晶度和熱穩(wěn)定性而且賦予其超強酸的酸性。該功能材料在苯甲酰氯與茴香醚的付克酰基化反應中展現(xiàn)了良好的催化活性,其中HPW負載量為28.2 wt.%的HPW@Zr（BTC）催化活性最好,苯甲醚的轉(zhuǎn)化率可達99.4%,... 

【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)】：184 頁

【學位級別】：博士

【文章目錄】：
摘要
Abstract
CHAPTER 1. Introduction
    1.1 Porous Silica
    1.2 Zeolites
    1.3 Activated Carbon
    1.4 Zirconia
    1.5 Metal-organic Frameworks
        1.5.1 Advantages of MOFs
        1.5.2 MOF Synthesis
        1.5.3 Modulated Synthesis of MOFs
        1.5.4 Functionalization of MOFs
        1.5.5 MOFs as Catalysts
        1.5.6 MOFs as Adsorbents
        1.5.7 Metal-Nanoparticles Hybrid MOFs
        1.5.8 MOF-Heteropoly Acid Composites
        1.5.9 Zirconium MOFs
    1.6 Solid Acid Catalysis
        1.6.1 Heteropoly Acids
        1.6.2 Keggin Structure
        1.6.3 Supported HPA Catalysis
        1.6.4 Mechanism of Heteropoly Acid Catalysis
    1.7 Research Objectives/ Scope of Work
CHAPTER 2. Materials, Instrumentation and Characterization
    2.1 Materials
    2.2 Instrumentation and Characterization
        2.2.1 Elemental Analysis
        2.2.2 Powder X-ray Diffraction
        2.2.3 Surface Area Analysis
        2.2.4 Thermogravimetric Analysis
        2.2.5 Transmission Electron Microscopy
        2.2.6 Scanning Electron Microscopy
        2.2.7 Energy Dispersive X-ray Analysis
        2.2.8 Infrared Spectroscopy
        2.2.9 X-ray Photoelectron Spectroscopy
        2.2.10 Acidity Determination Studies
        2.2.11 Nuclear Magnetic Resonance Spectroscopy
CHAPTER 3. Phosphotungstic Acid Niched in Zr-MOF: A Stable and EfficientCatalyst for Friedel-Crafts Acylation
    3.1 Introduction
    3.2 Experimental
        3.2.1 Preparation of Zr(BTC)
        3.2.2 Preparation of HPW@Zr(BTC)
        3.2.3 Catalytic Tests
    3.3 Results and Discussions
        3.3.1 Catalyst Characterization
        3.3.2 Catalytic Tests
    3.4 Conclusions
CHAPTER 4. MOF-driven Pd-Nanoparticles Efficient Catalysis of Suzuki-MiyauraCross-Coupling Reactions in Aqueous Solvent
    4.1 Introduction
    4.2 Experimental
        4.2.1 Modulated Synthesis of Zr(BTC)
        4.2.2 Loading of Palladium Nanoparticles on Zr(BTC)
        4.2.3 General Procedure for Suzuki-Miyaura Cross-coupling Reactions
    4.3 Results and Discussions
        4.3.1 Catalyst Characterization
        4.3.2 Catalytic Reactions
    4.4 Conclusions
CHAPTER 5. Highly Efficient Adsorption of Benzothiophene from Model Fuel on aMOF Modified with HPW
    5.1 Introduction
    5.2 Experimental
        5.2.1 Synthesis of Zr(BTC)
        5.2.2 Post-synthetic HPW Loading
        5.2.3 Adsorbate Solutions Preparation
        5.2.4 Adsorption Experiments
        5.2.5 Reusability of the Adsorbents
        5.2.6 Quantum Chemical Calculations
    5.3 Results and Discussions
        5.3.1 Adsorbents Characterization
        5.3.2 Benzothiophene Adsorption
    5.4 Conclusions
CHAPTER 6. Pd-Promoted Molybdovanadophosphoric Acid Supported onMesoporous Zirconia:A Stable Bifunctional Catalyst for Oxidative Deep-Desulfurization of Model Fuel
    6.1 Introduction
    6.2 Experimental
        6.2.1 Synthesis of Mesoporous Zirconia (mZrO_2)
        6.2.2 Synthesis of Molybdovanadophosphoric Acid
        6.2.3 Supporting molybdovanadophosphoric acid on mZrO_2
        6.2.4 Palladium doping of PMV/mZrO_2 catalysts
        6.2.5 Oil Preparation
        6.2.6 CODS Catalytic Reactions
        6.2.7 Catalyst Recycling
    6.3 Results and Discussions
        6.3.1 Catalyst Characterization
        6.3.2 Catalytic Tests
    6.4 Conclusions
CHAPTER 7. General Research Conclusions and Outlook
    7.1 General Research Conclusions
    7.2 General Research Outlook
Nomenclature in Alphabetical Order
References
Resume
Acknowledgements


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期刊論文
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本文編號：3229262