本實驗室在先前的研究中發現氧化亞銅奈米粒子表面經由4-硝基苯乙炔修飾過後，能有效促進氧化亞銅正立方體、八面體以及菱形十二面體對降解甲基橙染料的活性，並利用密度泛函理論計算得出氧化亞銅經過修飾之後能夠產生有效幫助電子轉移，以利於後續電子電洞分離，並讓電洞與水產生氫氧自由基分解甲基橙。
而在本次實驗中，將修飾過的氧化亞銅粒子應用於水相自由基聚合反應中，在共同引發劑的幫助下，修飾過的氧化亞銅粒子能夠使N，N-二甲基丙烯酰胺在六十分鐘內達到百分之九十一的轉換率。在後續的測試中，利用氧化亞銅粒子作為自由基起始劑的作法能夠使得此自由基促進的聚合反應直接在空氣環境下進行並在一小時內達到百分之六十四的轉換率。後續並利用1,4-苯醌以及草酸鈉分別作為電子和電洞捕捉劑，以確認能夠影響反應機制的電子載體種類。

Previously, Cu2O cubes, octahedra, and rhombic dodecahedra have been shown to exhibit greatly enhanced methyl orange photodegradation activities through surface functionalization with 4-nitrophenylacetylene (4-NA). Density functional theory (DFT) calculations reveal emergence of a narrow bands within the band gap of Cu2O to facilitate electron transfer through 4-NA and this likely gives better charge separation. In this work, 4-NA-modified Cu2O particles were applied as photocatalysts for free-radical polymerization reactions in aqueous phase via photoactivating coinitiator. The excellent photocatalytic performance of modified Cu2O catalyst was confirmed by a high N,N-dimethylacrylamide monomer conversion of 91% in thirty minutes. The polymerization reaction was also carried out in ambient air condition, and the conversion reached 64% in one hour. Doing so can simplify the reaction process substantially. Furthermore, 1,4-benzoquinone and sodium oxalate were used as electron and hole scavengers to reveal the major charge carrier to support the proposed reaction mechanism.

論文摘要 i
ABSTRACT ii
LIST OF FIGURES vi
LIST OF SCHEMES xi
LIST OF TABLES xii
1. Introduction 1
1.1 Cuprous oxide 1
1.2 Facet-dependent photocatalytic properties of Cu2O crystals 3
1.2 Photocatalytic activity of decorated and functionalized Cu2O crystals 6
1.3 Polymerization reactions using semiconductor catalysts 11
2. Motivation 19
3. Experimental Section 20
3.1 Chemicals 20
3.2 Synthesis of Cu2O nanoparticles 20
3.3 4-Nitrophenylacetylene-modification for Cu2O crystals 23
3.4 General procedure for Cu2O photocatalyzed polymerization 23
3.5 Active Species Trapping Experiments 24
3.6 Recyclability and Scale-up for Cu2O photopolymerization 25
3.7 Polymerization Tracking and Residual Copper Ions Determination………………………………………………………………………………………………………26
3.8 Instrumentation 26
4. Results and Discussion 30
4.1 Characterization of 4-NA Functionalized Cu2O crystals 30
4.2 Results of Cu2O photocatalytic polymerization 34
4.3 Results of Active Species Trapping 40
4.4 Results of Cu2O recyclability and scale-up for polymerization 43
4.5 Polymerization Tracking and Residual Copper Ions Determination 45
5. Conclusion 48
6. References 49
APPENDIX 58

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