近年來，由於對環保意識的增強，綠色化學引起了相當大的關注，本研究使用以4-硝基苯乙炔修飾的氧化亞銅菱形十二面體做為光催化劑，乙腈作為溶劑，在藍光照射下以及氧氣環境中催化伯胺耦聯反應。4-硝苯乙炔修飾的氧化亞銅催化十二種不同芳香取代基起始物皆能達到高產率以及高選擇性，同時相較於傳統的COF、MOF材料和貴金屬錯合物催化劑，更具有成本效益和製程簡單的優勢。
一系列的活性物質捕捉實驗以及EPR實驗指出當光照到催化劑時，會產生激發態電子、電洞和超氧自由基，這些反應中間體的生成與催化反應的進行密切相關，並藉此提出可能的反應機制。

In recent years, due to the heightened awareness of environmental conservation, green chemistry has garnered significant attention. In this study, copper oxide rhombic dodecahedra modified with 4-nitrophenylacetylene was employed as a catalyst for the coupling reaction of benzylamine in acetonitrile conducted under blue light irradiation in an oxygen atmosphere. High product yields and selectivity were achieved using twelve different aromatic substituents. A series of reactive species trapping experiments and electron paramagnetic resonance experiments indicate the generation of excited state electrons, holes, and superoxide radicals upon light irradiation of the photocatalyst. The reaction mechanisms are proposed from these results. This photocatalyst is simple and cheap to make, compared to metal-organic frameworks and covalent organic frameworks often used for this reaction.

論文摘要…………………………………………………………………………………………………………………..I
Abstract………………………………………………………………………………………………………………..….II
誌謝…………………………………………………………………………………………………………….………...III
List of Schemes…………………………………………………………...……………………………………….VI
List of Figures…………………………………………………………………………………………………...…VII
List of Tables………………………………………………..……………………….……….…………………….IX
List of Spectrum……………………………………………………………………………………………………..X
1. Introduction…………………………………………………………………………………………………………1
1.1 Cu2O properties and facet effect……………………………………………………………………...1
1.2 Functionalized Cu2O crystals………………………………...………………………………...……6
1.3 Cu2O crystals for photocatalysis………………………………………………………..…………….9
1.4 Imines and their synthesis…………………………………………………………………………….10
2. Motivation…………………………………………………………………………………………………………..18 3. Experimental Section………………………………………………………………………………………....19
3.1 Chemicals……………………………………………………………………………………………………..19
3.2 Instrumentation……………………………………………………………………………………………..20
3.3 Synthesis of polyhedral Cu2O crystals………………………………………………………….20
3.4 Functionalization of Cu2O crystals with 4-nitrophenylacetylene…………………..22
3.5 Cu2O-catalyzed amine coupling reaction……………………………………………………….23
3.6 Radical scavenging experiment……………………………….……………………………………..24
3.7 Electron paramagnetic resonance (EPR) experiment……………………………………..25
4. Result and discussion…………………………………………………………………………………….…...27
4.1 Analysis of Cu2O crystals……………………………………………………………………………...27
4.2 Photocatalytic oxidative amine coupling…………………………………….....................33
4.3 Mechanism studies………………………………………………………………………………………..43
5. Conclusion……………………………………………………………………………………………………….…49
6. Reference………………………………………………………………………………..………………………….54

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