【作者】 王刚；

【导师】 刘伟生；

【作者基本信息】 兰州大学 ， 化学·无机化学， 2019， 博士

【摘要】 CO₂既是主要的温室气体,又是一种宝贵的可再生C1资源,开发高效、绿色、廉价的催化剂将CO₂转化为具有高附加值的绿色化工产品,不仅可以有效缓解“温室效应”变废为宝,还可以得到有应用价值的工业化产品。制备具有高活性、低成本、可循环使用的多功能催化剂,探索结构构筑与催化剂活性的关系,筛选高性能的催化剂,可以为CO₂的固定和转化为高附加值的有机化工产品提供重要的理论依据。因此,本工作具有重要的理论和实际应用研究价值。本论文中,我们以多核稀土配合物和天然纳米矿物-凹凸棒为主要研究对象,探索了不同类型催化剂的催化活性及应用性能。本文主要分六章论述:（1）主要介绍了现有文献已报到的环碳酸酯合成方法及应用领域,综述了当前环碳酸酯合成研究的最新进展,对天然纳米矿物-凹凸棒进行了系统的简介,并对其综合利用和改性研究进行了归纳;最后对催化剂的设计、合成的思路进行了简要介绍。（2）基于功能导向的设计理念,设计、合成了一系列新型酰腙配体,构筑了多核基元的稀土配合物,将其用于催化CO₂和环氧化合物偶联合成环碳酸酯的反应中,系统考察了不同稀土金属（La、Nd和Sm）对催化剂结构和活性的影响,并阐述了其可能存在的催化反应机理。（3）利用杂金属间协同催化的作用机理,设计构筑了两个多核M-Dy（M=Zn,Cd）基元的3d/4d-4f杂金属配位聚合物,将其用于催化CO₂和环氧化合物偶联制备环碳酸酯的反应中,系统的考察了不同金属对催化剂结构和活性的影响,并深入探讨了催化剂的催化机理。（4）在理解了CO₂与环氧化合物加成反应的机理后,首次成功的利用天然一维纳米多孔材料-凹凸棒作为天然纳米催化剂,用于催化CO₂与环氧化合物偶联反应制备环碳酸酯。系统的研究了凹凸棒对CO₂的吸附机理,阐述了结构中多金属协同催化的作用,并进一步探讨了不同处理方法制备的催化剂的催化性能,最后研究了纳米催化剂对不同环氧底物的适用性、选择性和催化活性,并讨论了该催化体系可能存在的催化机理。（5）将凹凸棒作为多功能载体,设计、构筑了ZIF-8/ATP的纳米复合催化剂,将其用于催化CO₂和环氧化合物偶联反应合成环碳酸酯的反应中,系统的研究了ZIF-8的负载量对复合催化剂催化性能的影响,并对催化剂的稳定性和可循环使用性能进行了评估,最后阐述了其可能存在的催化反应机理。（6）基于凹凸棒特殊的孔道结构与优异的载体性能,设计、制备了Ag/ATP纳米复合催化剂,用于催化CO₂和炔丙醇反应制备环碳酸酯,通过调控AgNO₃的加入量来控制Ag⁰的负载量,制备了一系列不同载银量的纳米复合催化剂,系统的研究了不同催化剂稳定性和在催化反应中的催化活性,并深入讨论了该催化体系的催化机理。更多还原

【Abstract】 CO₂ is not only a major greenhouse gas,but also a valuable renewable C₁ resource.Developing high-efficiency,green and cheap catalysts to convert CO₂ into high-value-added green chemical products can not only effectively alleviate the“greenhouse effect”and turn waste into treasure,and can also get industrial products with application value.The preparation of multi-functional catalysts with high activity,low cost and recyclability,exploring the relationship between structural structure and catalyst activity,screening high performance catalysts,can provide important theory for the fixation and conversion of CO₂ to high value-added organic chemical products.Therefore,this work has important theoretical and practical application research value.In this paper,we use multi-nuclear rare earth complexes and natural nano-mineral-attapulgite as the main research objects,and explore the catalytic activity and application performance of different types of catalysts.This article is divided into six chapters:（1）The synthesis methods and applications of cyclic carbonates are mainly introduced.The recent progress in the synthesis of cyclic carbonates is reviewed.The comprehensive utilization and modification of natural nano-mineral-attapulgite rods are further summarized.Finally,the design and synthesis of the catalyst are briefly introduced.（2）Based on the functionally oriented design concept,a series of novel hydrazide ligands were designed and synthesized,and a rare earth complexes of multinuclear elements was constructed,which was used to catalyze the reaction of coupling CO₂ and epoxy compounds to synthesize cyclic carbonates.The effects of different rare earth metals（La,Nd and Sm）on the structure and activity of the catalyst were investigated,and the possible catalytic reaction mechanism was described.（3）Using the mechanism of synergistic catalysis between hetero-metals,we designed two 3d/4d-4f heterometallic coordination polymers with multi-nuclear M-Dy（M=Zn,Cd）motifs,which were used to catalyze CO₂ and ring.In the reaction of oxygen compound coupling to prepare cyclic carbonate,the effects of different metals on the structure and activity of the catalyst were systematically investigated,and the catalytic mechanism of the catalyst was discussed in depth.（4）After understanding the mechanism of the addition reaction of CO₂ and epoxy compounds,the natural one-dimensional nano-porous material-attapulgite was successfully used as a natural nano-catalyst for the first time to catalyze the coupling of CO₂ and epoxy compounds to prepare cyclic carbonate.The mechanism of adsorption of CO₂ by attapulgite was studied systematically.The role of multi-metal synergistic catalysis in the structure was expounded.The catalytic performance of the catalyst prepared by different treatment methods was further discussed.Finally,the nano-catalysts for different epoxy substrates were studied.Applicability,selectivity and catalytic activity,and discussed the possible catalytic mechanism of the catalyst system.（5）Using attapulgite as a multifunctional carrier,a nanocomposite catalyst based on attapulgite and ZIF-8 was designed and constructed,which was used to catalyse the reaction of CO₂ and epoxy compound coupling to synthesize cyclocarbonate.The system research the effect of ZIF-8 loading on the catalytic performance of the composite catalyst was discussed,and the possible catalytic reaction mechanism was discussed.（6）Based on the special pore structure of attapulgite and excellent carrier properties,Ag/ATP nanocomposite catalyst was designed and prepared to catalyze the reaction of CO₂ and propargyl alcohol to prepare cyclic carbonate.The amount of AgNO₃ was controlled to control the loading of Ag⁰.A series of nanocomposites with different loadings of silver were prepared.The stability of the catalysts and the catalytic activities in the catalytic reactions were systematically studied.The catalytic mechanism of the catalysts was discussed in depth.更多还原