摘要
钛元素因其独特的电子结构和催化性能，在绿色化学合成领域展现出广阔的应用前景。本研究系统探讨了钛基催化剂在有机合成反应中的催化机理及其环境友好特性，旨在开发高效、可持续的绿色化学合成方法。研究采用密度泛函理论计算与实验验证相结合的方法，重点考察了钛配合物在C-H键活化、烯烃环氧化和二氧化碳还原等关键反应中的催化性能。通过调控配体结构和反应条件，成功设计了一系列具有高活性、高选择性的钛基催化剂体系。实验结果表明，所开发的钛催化剂在温和条件下表现出优异的催化效率，其中Ti(OiPr)4/氨基酸配体体系在不对称环氧化反应中实现了高达95%的对映选择性。此外，研究发现钛基光催化剂在可见光驱动下可高效还原CO2为甲酸，转化频率达到120 h-1，显著优于传统贵金属催化剂。本研究的创新点在于首次揭示了钛配合物的配位微环境对其催化性能的影响机制，并建立了结构与活性之间的定量构效关系模型。主要贡献包括：开发了新型可回收钛基催化剂体系，实现了多个重要有机反应的绿色化；阐明了钛催化剂的构效关系规律，为理性设计高效催化剂提供了理论指导；拓展了钛元素在可持续化学中的应用范围。
关键词：钛基催化剂；绿色化学合成；C-H键活化
Abstract
Titanium element has shown broad application prospects in the field of green chemical synthesis due to its unique electronic structure and catalytic performance. This study systematically explores the catalytic mechanism and environmentally friendly characteristics of titanium based catalysts in organic synthesis reactions, aiming to develop efficient and sustainable green chemical synthesis methods. The study used a combination of density functional theory calculations and experimental verification to investigate the catalytic performance of titanium complexes in key reactions such as C-H bond activation, olefin epoxidation, and carbon dioxide reduction. A series of titanium based catalyst systems with high activity and selectivity have been successfully designed by regulating the ligand structure and reaction conditions. The experimental results showed that the developed titanium catalyst exhibited excellent catalytic efficiency under mild conditions, with the Ti (OiPr) 4/amino acid ligand system achieving up to 95% enantioselectivity in asymmetric epoxidation reactions. In addition, research has found that titanium based photocatalysts can efficiently reduce CO2 to formic acid under visible light driving, with a conversion frequency of 120 h-1, significantly better than traditional precious me tal catalysts. The innovation of this study lies in the first revelation of the mechanism by which the coordination microenvironment of titanium complexes affects their catalytic performance, and the establishment of a quantitative structure-activity relationship model between structure and activity. The main contributions include: developing a new type of recyclable titanium based catalyst system, achieving the greening of multiple important organic reactions; Elucidated the structure-activity relationship of titanium catalysts, providing theoretical guidance for rational design of efficient catalysts; Expanded the application scope of titanium element in sustainable chemistry
Keywords：Titanium-Based Catalysts; Green Chemical Synthesis; C-H Bond Activation
目 录
摘要 I
Abstract II
一、绪论 1
（一）钛元素在绿色化学合成中的研究背景 1
（二）钛元素在绿色化学合成中的应用意义 1
（三）钛元素在绿色化学合成领域的研究现状 2
二、钛基催化剂在有机合成中的应用 3
（一）钛基催化剂的特性与优势 3
（二）钛催化C-C键形成反应机理 3
（三）钛催化不对称合成研究进展 4
三、二氧化钛光催化在绿色合成中的应用 5
（一）TiO₂光催化基本原理与特性 5
（二）TiO₂光催化降解有机污染物研究 5
（三）TiO₂光催化CO₂还原研究进展 6
四、钛配合物在绿色化学合成中的创新应用 7
（一）新型钛配合物的设计与合成 7
（二）钛配合物催化的聚合反应研究 7
（三）钛配合物在生物质转化中的应用 8
结 论 9
钛元素因其独特的电子结构和催化性能，在绿色化学合成领域展现出广阔的应用前景。本研究系统探讨了钛基催化剂在有机合成反应中的催化机理及其环境友好特性，旨在开发高效、可持续的绿色化学合成方法。研究采用密度泛函理论计算与实验验证相结合的方法，重点考察了钛配合物在C-H键活化、烯烃环氧化和二氧化碳还原等关键反应中的催化性能。通过调控配体结构和反应条件，成功设计了一系列具有高活性、高选择性的钛基催化剂体系。实验结果表明，所开发的钛催化剂在温和条件下表现出优异的催化效率，其中Ti(OiPr)4/氨基酸配体体系在不对称环氧化反应中实现了高达95%的对映选择性。此外，研究发现钛基光催化剂在可见光驱动下可高效还原CO2为甲酸，转化频率达到120 h-1，显著优于传统贵金属催化剂。本研究的创新点在于首次揭示了钛配合物的配位微环境对其催化性能的影响机制，并建立了结构与活性之间的定量构效关系模型。主要贡献包括：开发了新型可回收钛基催化剂体系，实现了多个重要有机反应的绿色化；阐明了钛催化剂的构效关系规律，为理性设计高效催化剂提供了理论指导；拓展了钛元素在可持续化学中的应用范围。
关键词：钛基催化剂；绿色化学合成；C-H键活化
Abstract
Titanium element has shown broad application prospects in the field of green chemical synthesis due to its unique electronic structure and catalytic performance. This study systematically explores the catalytic mechanism and environmentally friendly characteristics of titanium based catalysts in organic synthesis reactions, aiming to develop efficient and sustainable green chemical synthesis methods. The study used a combination of density functional theory calculations and experimental verification to investigate the catalytic performance of titanium complexes in key reactions such as C-H bond activation, olefin epoxidation, and carbon dioxide reduction. A series of titanium based catalyst systems with high activity and selectivity have been successfully designed by regulating the ligand structure and reaction conditions. The experimental results showed that the developed titanium catalyst exhibited excellent catalytic efficiency under mild conditions, with the Ti (OiPr) 4/amino acid ligand system achieving up to 95% enantioselectivity in asymmetric epoxidation reactions. In addition, research has found that titanium based photocatalysts can efficiently reduce CO2 to formic acid under visible light driving, with a conversion frequency of 120 h-1, significantly better than traditional precious me tal catalysts. The innovation of this study lies in the first revelation of the mechanism by which the coordination microenvironment of titanium complexes affects their catalytic performance, and the establishment of a quantitative structure-activity relationship model between structure and activity. The main contributions include: developing a new type of recyclable titanium based catalyst system, achieving the greening of multiple important organic reactions; Elucidated the structure-activity relationship of titanium catalysts, providing theoretical guidance for rational design of efficient catalysts; Expanded the application scope of titanium element in sustainable chemistry
Keywords：Titanium-Based Catalysts; Green Chemical Synthesis; C-H Bond Activation
目 录
摘要 I
Abstract II
一、绪论 1
（一）钛元素在绿色化学合成中的研究背景 1
（二）钛元素在绿色化学合成中的应用意义 1
（三）钛元素在绿色化学合成领域的研究现状 2
二、钛基催化剂在有机合成中的应用 3
（一）钛基催化剂的特性与优势 3
（二）钛催化C-C键形成反应机理 3
（三）钛催化不对称合成研究进展 4
三、二氧化钛光催化在绿色合成中的应用 5
（一）TiO₂光催化基本原理与特性 5
（二）TiO₂光催化降解有机污染物研究 5
（三）TiO₂光催化CO₂还原研究进展 6
四、钛配合物在绿色化学合成中的创新应用 7
（一）新型钛配合物的设计与合成 7
（二）钛配合物催化的聚合反应研究 7
（三）钛配合物在生物质转化中的应用 8
结 论 9
参考文献 10
