兰州大学机构库 >化学化工学院
光敏钌配合物 MOFs 的合成、 结构调控及其光催化反应研 究
Alternative TitleSynthesis, Structure Modulation and Photocatalytic Reaction of Photosensitizing Ruthenium Complexes MOFs
白东杰
Subtype博士
Thesis Advisor唐晓亮
2023-09-02
Degree Grantor兰州大学
Place of Conferral兰州
Degree Name理学博士
Degree Discipline化学
Keyword光敏 MOFs photosensitizing MOFs 光催化 photocatalysis 还原 CO2 reduction of CO2 C-N 偶联反应 C-N coupling reaction C-C 偶联反应 C-C coupling reaction
Abstract

开发和充分利用天然清洁能源已经引起了极大的关注,其中,太阳光被认为是最好的清洁能源之一。由于可持续性和环境友好的优点,光催化还原CO2和光催化有机物的转化已成为了光催化领域重点研究方向。在已报道的不同种类的光催化剂中,MOFs材料由于具有结构的丰富多样性、孔道的可修饰性、功能的可调性等优点,在光催化方面显示极为重要的研究价值。基于此,本论文重点围绕光敏配合物来研究基于钌基MOFs材料的结构设计及其光催化性能研究,分别设计合成了三个钌光敏羧酸配体(H3LRu、H3L2Ru和H6L3Ru),进而配位自组装得到四例光敏MOFs材料(H3LRu-CoMOF、H3LRu-NiMOF、H3LRu-ZnMOF和H3LRu-ZrMOF)。根据光敏MOFs材料的结构特性,分别考察了光敏MOFs的光催化还原CO2和光催化有机物转化的性能。

论文共分为六章:

第一章:简要介绍了光敏MOFs材料的结构特性、合成策略和相应的性能研究,重点调研了光敏MOFs材料在光催化领域的应用研究。

第二章:基于光敏剂[Ru(Phen)3](PF6)设计合成了一例光敏羧酸配体H3LRu,分别与Co(II)﹑Ni(II)、Zn(II)﹑Zr(Ⅳ)离子配位自组装得到了四例光敏MOFs材料,并且都得到了单晶结构。从调控“连接”的策略出发,在配体H3LRu的基础上通过延长配体尺寸和增加配体上的配位点,分别设计合成了两例光敏配体H3L2Ru和H6L3Ru。对合成的配体和光敏MOFs材料均进行了基本的表征。

第三章:鉴于光敏H3LRu-CoMOF具有强的可见光吸收能力、相对较负的LUMO能级、良好的光生电子-空穴分离效率以及较好的CO2吸附能力,详细考察了光敏H3LRu-CoMOF光催化还原CO2反应的应用研究,确定了光催化还原CO2过程中的反应活性位点,并通过合成新的光敏H3LRu Me-CoMOF证明了所确定的反应机理。

第四章:为拓展光敏MOFs材料光催化应用范围,结合光敏H3LRu-NiMOF在可见光照射下对分子氧的活化能力,详细考察了H3LRu-NiMOF光催化氧化C-N偶联反应的光催化性能。研究发现H3LRu-NiMOF可在1h内以接近100 %的产率得到相应4-甲基苯甲胺的催化产物。值得注意的是,H3LRu-NiMOF还可应用于光催化氧化4-甲基苯甲胺C-N偶联反应的克级反应。

第五章:进一步拓展了H3LRu-NiMOF的光催化性能,详细考察了H3LRu-NiMOF对马来酰亚胺类化合物与N,N-二甲基苯胺的C-C氧化偶联反应的光催化性能。研究结果表明,H3LRu-NiMOF表现出了高的光催化活性和广泛的底物普适性。此外,研究发现H3LRu-NiMOF可以继续光催化双-N-取代马来酰亚胺与N,N-二甲基苯胺的反应。

第六章:利用高价态金属离子Zr4+与H3LRu构筑了H3LRu-ZrMOF,其结构不同于由其他+2价金属离子构筑的光敏MOFs。鉴于H3LRu-ZrMOF独特的三维结构以及框架中富含的Zr6氧团簇次级结构单元,初步考察了H3LRu-ZrMOF对马来酰亚胺类化合物与N,N-二甲基苯胺的C-C氧化偶联反应的光催化作用。

第七章:对本论文的工作做了系统的总结和展望。

Other Abstract

The development and full utilization of natural clean energy has attracted great attention. Among them, sunlight is considered to be one of the best clean energy sources. Due to the advantages of sustainability and environmental friendliness, photocatalytic reduction of CO2 and photocatalytic conversion of organic matter have become the focus of research in the field of photocatalysis. Among the different types of photocatalysts that have been reported, MOFs materials have shown extremely important research value in photocatalysis due to their rich diversity of structures, modifiability of pores, and adjustability of functions. Based on this, this paper focuses on the photosensitizing complexes to study the structural design and photocatalytic performance of ruthenium-based MOFs materials. Three ruthenium photosensitizing carboxylic acid ligands (H3LRu, H3L2Ru and H6L3Ru) were designed and synthesized, and then four photosensitizing MOFs materials (H3LRu-CoMOF, H3LRu-NiMOF, H3LRu-ZnMOF and H3LRu-ZrMOF) were obtained by coordination self-assembly. According to the structural characteristics of photosensitizing MOFs, the photocatalytic reduction of CO2 and photocatalytic conversion of organic matter were investigated.

The thesis is divided into six chapters:

Chapter 1: The structural characteristics, synthetic strategies and corresponding properties of photosensitizing MOFs are briefly introduced. The application of photosensitizing MOFs in the field of photocatalysis was mainly investigated.

Chapter 2: A photosensitizing carboxylic acid ligand H3LRu was designed and synthesized based on the photosensitizer [Ru(Phen)3](PF6). Three photosensitizing MOFs were obtained by self-assembly with Co(II), Ni(II), Zn(II) and Zr(IV) ions, respectively, and single crystal structures were obtained. Two photosensitizing ligands H3L2Ru and H6L3Ru were designed and synthesized by extending the ligand size and increasing the coordination sites based on the ligand H3LRu. The synthesized ligands and photosensitizing MOFs were characterized.

Chapter 3: Inspired by the photosensitizing H3LRu-CoMOF have strong visible light absorption, relatively negative LUMO energy level, excellent photogenerated charge-separation efficiency and well CO2 adsorption capacity, investigated the application of H3LRu-CoMOF in the photocatalytic CO2 reduction. The reaction active sites in the process of photocatalytic reduction of CO2 were determined, and the reaction mechanism was proved by the synthesis of new photosensitive H3LRu Me-CoMOF.

Chapter 4: In order to expand the photocatalytic application range of photosensitizing MOFs, and molecular oxygen can be activated into reactive oxygen species under visible light irradiation in the existence of H3LRu-NiMOF. The photocatalytic performance of H3LRu-NiMOF for photocatalytic oxidation C-N coupling reaction was investigated. The results showed that H3LRu-NiMOF can obtain the corresponding catalytic product of 4-methylaniline in nearly 100% yield within 1h. It is worth noting that H3LRu-NiMOF can also be applied to the gram-scale reaction of photocatalytic oxidation of 4-methylaniline C-N coupling reaction.

Chapter 5: The photocatalytic performance of H3LRu-NiMOF was further expanded. The results showed that H3LRu-NiMOF exhibited high photocatalytic activity and wide substrate universality. In addition, after expanding the reaction, H3LRu-NiMOF can still photocatalytic reaction of bis-N-substituted maleimide and N,N-dimethylaniline.

Chapter 6: H3LRu-ZrMOF was constructed by using high valence metal ions Zr4+ and H3LRu, which is different from the photosensitizing MOFs constructed by other +2 valence metal ions. In view of the unique three-dimensional structure of H3LRu-ZrMOF and the rich Zr6-oxygen cluster SBU in the framework, the photocatalytic performance of H3LRu-ZrMOF for the C-C oxidative coupling reaction of maleimide and N,N-dimethylaniline was investigated .

Chapter 7: The work of this paper is systematically summarized and prospected.

MOST Discipline Catalogue理学 - 化学 - 无机化学
URL查看原文
Language中文
Other Code262010_120180902381
Document Type学位论文
Identifierhttps://ir.lzu.edu.cn/handle/262010/539777
Collection化学化工学院
Affiliation
兰州大学化学化工学院
Recommended Citation
GB/T 7714
白东杰. 光敏钌配合物 MOFs 的合成、 结构调控及其光催化反应研 究[D]. 兰州. 兰州大学,2023.
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