锆基超稳多孔材料的功能化、表征和催化/吸附应用研究
发布时间：2021-06-14 06:31
催化/分离科学技术的发展对国民经济社会的可持续发展至关重要,其核心是开发清洁经济的高性能催化剂/吸附剂。近年来,锆基多孔功能材料因具有稳定性高、比表面积大、环境友好而且易于功能化修饰等特性在众多新型催化/吸附材料中备受关注。材料的组成、微观结构与形貌决定其催化/吸附性能,而材料的组成、微观结构与形貌又与合成方法与结晶过程密不可分。因此,本论文探索了多种策略合成超稳锆基功能多孔材料以及其在付克酰基化、铃木交叉耦联反应吸附脱硫及催化氧化深度脱硫中的应用,系统地研究了材料合成-结构-性能多层次的构效关系,取得了系列创新性成果,具体介绍如下:（1）.采用溶剂热一锅法直接合成了高比表面积（1065-2058 m2/g）和高磷钨酸（HPW）负载量（32.3 wt.%）的酸性锆基功能MOF材料(HPW@Zr（BTC）。研究表明适量HPW的引入不仅在合成过程中起到模板作用提高了锆基MOF材料的结晶度和热稳定性而且赋予其超强酸的酸性。该功能材料在苯甲酰氯与茴香醚的付克酰基化反应中展现了良好的催化活性,其中HPW负载量为28.2 wt.%的HPW@Zr（BTC）催化活性最好,苯甲醚的转化率可达99.4%,...
【文章来源】：中国科学院大学(中国科学院过程工程研究所)北京市
【文章页数】：184 页
【学位级别】：博士
【文章目录】：
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
【参考文献】：
期刊论文
[1]12-Tungstophosphoric acid niched in Zr-based metal-organic framework:a stable and efficient catalyst for Friedel-Crafts acylation[J]. Latif Ullah,Guoying Zhao,Zichen Xu,Hongyan He,Muhammad Usman,Suojiang Zhang. Science China（Chemistry）. 2018(04)
[2]Zirconium-containing UiO-66 as an efficient and reusable catalyst for transesterification of triglyceride with methanol[J]. Fan Zhou,Ningyue Lu,Binbin Fan,Huigang Wang,Ruifeng Li. Journal of Energy Chemistry. 2016(05)
[3]Recent advances in multi-layer composite polymeric membranes for CO2 separation: A review[J]. Zhongde Dai,Luca Ansaloni,Liyuan Deng. Green Energy & Environment. 2016(02)
[4]Regulating sulfur removal efficiency of fuels by Lewis acidity of ionic liquids[J]. Yi Nie,Yuxiao Dong,Hongshuai Gao,Xiangping Zhang,Suojiang Zhang. Science China（Chemistry）. 2016(05)
[5]多酸阴离子对金属有机骨架纳米晶生长的调控（英文）[J]. 徐晓斌,陆言,杨勇,Farhat Nosheen,王训. Science China Materials. 2015(05)
本文编号：3229262
【文章来源】：中国科学院大学(中国科学院过程工程研究所)北京市
【文章页数】：184 页
【学位级别】：博士
【文章目录】：
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
【参考文献】：
期刊论文
[1]12-Tungstophosphoric acid niched in Zr-based metal-organic framework:a stable and efficient catalyst for Friedel-Crafts acylation[J]. Latif Ullah,Guoying Zhao,Zichen Xu,Hongyan He,Muhammad Usman,Suojiang Zhang. Science China（Chemistry）. 2018(04)
[2]Zirconium-containing UiO-66 as an efficient and reusable catalyst for transesterification of triglyceride with methanol[J]. Fan Zhou,Ningyue Lu,Binbin Fan,Huigang Wang,Ruifeng Li. Journal of Energy Chemistry. 2016(05)
[3]Recent advances in multi-layer composite polymeric membranes for CO2 separation: A review[J]. Zhongde Dai,Luca Ansaloni,Liyuan Deng. Green Energy & Environment. 2016(02)
[4]Regulating sulfur removal efficiency of fuels by Lewis acidity of ionic liquids[J]. Yi Nie,Yuxiao Dong,Hongshuai Gao,Xiangping Zhang,Suojiang Zhang. Science China（Chemistry）. 2016(05)
[5]多酸阴离子对金属有机骨架纳米晶生长的调控（英文）[J]. 徐晓斌,陆言,杨勇,Farhat Nosheen,王训. Science China Materials. 2015(05)
本文编号：3229262
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