中文摘要-1
本研究提出，具優異、簡單製造，低成本效益且具可擴展性的尿素交聯反應來開發出具有超疏水性質的三聚氰胺海綿，作為高效率的吸附材料應用於油水分離及有機溶劑的吸附。首先，本實驗提出一個簡易改質聚二甲基矽氧烷(PDMS)的方法，將兩倍莫爾數的二異氰酸酯(NCO)與尾端兩端具有胺基之PDMS加熱以進行PDMS之尾端封裝反應，再進一步加熱硬化形成交聯網狀結構，得到具柔軟性，疏水和親油性的薄膜，此種利用尾端NCO及二級胺基修飾PDMS，雖為傳統尿素化學，但卻無人注意及加以應用。然而我們選擇在商業化的三聚氰胺海綿上進行塗佈和固化過程，在海綿骨架中二級胺與PDMS尾端封裝NCO形成尿素共價鍵結所得超疏水海綿吸脫附材料來作為油和溶劑與水的分離。獲得的聚脲塗層海綿展現優異的水接觸角153.4o並具有優越的吸油能力及溶劑的可選擇性，特別在體積吸收比上能夠吸附 (1.163 ~ 1.661 m3/m3)的油汙染及溶劑，且具有良好的可回收性，可多達30次吸脫附仍能保持在 85.7~98.7% 的吸附量，原因也取決於所使用之有機溶劑和油的密度。接著，經過各種標準的化學和物理侵蝕，材料仍能完好，且具抗濕性、堅固、可回收性高能有效地分離廢水汙染。因此本研究在現今快速發展綠色化學環境中，提供相當大潛在力、吸引力及前瞻性的材料應用於環境清理及修補上。
中文摘要-2
首先，透過尿素反應將N1,N1二(4-氨基苯基)苯-1,4-二胺(TPA3NH2)和兩種二或三官能基數的異氰酸酯單體在甲苯和四氫呋喃混合溶劑環境下進行交聯製備出具有在水溶液中吸附重金屬離子的新型尿素聚合物多孔洞材料(UPP)，其為U2和U3。在掃描式電子顯微鏡的觀察下，平均直徑為0.3-1.0μm的UPP微球具有均勻皺紋狀的形貌和球型。其表面經尿素鍵修飾後表面穩定，有利於金屬離子的捕獲。通過固態13C NMR、FTIR、XRD、XPS、BET和TGA等技術對其化學組成和熱性質進行分析。以U3為例，其定量結果主要包括異氰酸酯2265 cm-1的消失，比表面積分析(114.2 m2/g)，二氧化碳捕捉(1.89 mmole/g)，孔徑(8.56 nm)和質量損失碳收率(43%)，其代表合成成功，結構明確，熱穩定性好。接著利用U3材料進一步，在不同pH值、吸附時間和初始濃度下進行Pb(II)在水溶液下吸附試驗，且展現出優異的吸附能力。通過配方計算的最大的吸附量為129 mg Pb(II)/g，高於大多數可用的吸附材料吸附量。此外本實驗也提出了幾種和金屬離子可能性的鍵結模式或是吸附位點。此外，我們將UPP進行氫氧化鉀化學活化，進而得到aU3。其整體增強熱穩定性(58%)，比表面積分析(1483.8 m2/g)和高二氧化碳捕捉能力(4.21 mmole/g)的優越效果。總體而言，尿素多孔洞材料不僅具有高比表面積和孔隙體積且在氣體儲存上是具有潛力的環保材料，而對於重金屬離子Pb(II)的吸附性能可以用於廢水淨化，在綠色環保新型材料中嶄露頭角。

Abstract-1
A facile, cost-effective, and scalable “urea cross-linking reaction” was developed to fabricate superhydrophobic melamine sponge (SMS) as efficient oils- and organic solvents-absorbent material. Primarily, a readily-available key intermediate of isocyanate-terminated poly(dimethyl siloxane) (iPD) was heated to proceed crosslinking reaction, generating flexible, hydrophobic films with urea cross-linking points. Moreover, this key iPD can be used to modify melamine sponge (MS), by heating to have its isocyanate terminals react with the secondary amine groups of MS, rendering covalent urea bonds over the surface of MS skeleton. The resultant SMS exhibits a high water contact angle (WCA) of 153.4o and excellent volumetric absorption capacity (1.163 ~ 1.661 m3/m3) for different oils and organic solvents and can be repeatedly used for 30 sorption-squeezing cycles with high absorption capacity retention (85.1 ~ 98.7 %), depending on the polarity and density of the employed organic solvents and oils, and high selectivity. This property of the material remains intact even after various standard chemical and physical insults. The fabrication procedure of SMS is simple and cost-effective and the anti-wetting, robust, recyclable SMS is efficient in the separation of various oils and organic solvent/water mixtures, therefore, this study provides attractive and potential methodology for use in scalable environmental cleanup and remediation.
Abstract-2
A novel adsorbent, urea porous polymer (UPP), for uptake of heavy metal ions from aqueous solutions was first fabricated via cross-linking reaction N1,N1-Bis(4-aminophenyl)benzene-1,4-diamine (TPA3NH2) and two or three functional isocyanate groups into toluene and tetrahydrofuran (THF) co-solutions, U2 and U3. The UPP microspheres of 0.3-1.0 μm in mean diameter were of uniformly wrinkle-like topography and sphere-like sketched out by SEM, whose surface after decoration by urea linkage was stable and beneficial to metal ion capture. Its chemical composition, microstructure, and thermal property were characterized by solid state 13C NMR, FTIR, XRD, XPS, BET, and TGA techniques, take U3 for example, the achieved quantitative results mainly included disappearance of isocyanate 2265 cm-1, specific surface area (114.2 m2/g), CO2 capture (1.95 mmole/g) pore diameter (8.56 nm), and mass loss at the char yield (43%), which indicated a successful synthesis, well-defined structure, and good thermos ability. Adsorption tests of U3 were performed in Pb(II) solutions at various pH values, contact time, and initial concentrations, exhibiting an excellent adsorption capability. Its maximum adsorption capacity calculated by formula was 129.7 mg Pb(II)/g, which was higher than those of most available adsorbents. Additionally, several potential bonding modes and adsorption sites for both metal ions were also proposed. Furthermore, the aU3 exhibited excellent thermal properties (58%), BET analysis (1483.8 m2/g) and CO2 capture (4.21 mmole/g). Overall, UPP materials not only with large surface areas and pore volumes are environmentally friendly materials having great potential in gas storage (CO2) applications but also with outstanding adsorption performance toward Pb(II) might serve as a new absorbent for wastewater purification.

論文審定書…………………………………………………. i
誌謝…………………………………………………. ii
Chinese Abstract-1…………………………………………………. iii
English Abstract-1…………………………………………………………………….iv
Chinese Abstract-2……………………………………………… vi
English Abstract-2………………………………………………………………….. vii
Outline of contents…………………………………………………………………...vii
List of Figure……………………………………………………………………... ...ix
List of Scheme……………………………………………………………………... xvi
List of Table…………….…………………………………………………..............xvii
Chapter 1. Superhydrophobic Melamine Sponge Modified by Cross-Linked Urea Network as Recyclable Oil Absorbent Materials 1
1-1. Introduction 2
1-2. Experimental Section 6
1-2-1. Materials 6
1-3. Characteristic 8
1-4. Result and Discussion 11
1-5. Conclusion 32
1-6. References 33
Chapter 2. Effective CO2 Capture and Lead(II) Uptake of Porous Materials Derived from Cross-linked Urea Networks 43
2-1. Introduction 44
2-2. Experimental Section 49
2-2-1. Materials 49
2-3. Characteristic 52
2-4. Result and Discussion 56
2-5. Conclusion 78
2-6. References 80
Supporting information 89

List of Figure
Figure 1-1. (a) 1H-NMR spectra of aPD5K and iPD5K (CDCl3) and (b) FTIR spectra of iPD5K and cPD5K (panel: magnified amide carbonyl bands). 13
Figure 1-2. (a) Water droplets on the surfaces of cPD5K and cPD27K films and the resolved WCAs, and (b) the 2D and 3D AFM images of cPD5K and cPD27K films. 16
Figure 1-3. (a) XPS spectra of the unmodified MS, SMS27K and SMS27K after 30 compression cycles and (b) TGA curves of MS, SMS27K and cPD27K (heating rate = 10 oC/min). 18
Figure 1-4. SEM images of (a, b) unmodified MS and (c, d) SMS27K. 21
Figure 1-5. (a) Unmodified MS (white color) and modified SMS27K (light orange color) after being forced into contact with water (inset: partially-immersed SMS27K with silver mirror-like appearance), (b) acidic, salty and alkali water droplets on the surface of SMS27K (all water droplets had been placed on SMS27K for over 12 hr) and (c) water droplets of different temperatures and trace of lubricant oil on the surface of SMS27K. 23
Figure 1-6. (a, b) Snapshots showing the absorption of oil (dyed in red) from water, the extruded liquids from (c) SMS27K and (d) MS saturated with absorbed oil/water… 25
Figure 1-7. (a) SMS27K as filter for continuous separation of hexane/water emulsion in a vacuum suction apparatus. Photographs of (b) surfactant-stabilized and (c) surfactant-free water-in-hexane emulsions. The distinct appearance between the feed emulsion and the hexane filtrate under normal and optical images. 27
Figure 1-8. (a) Gravimetric absorption capacities (g/g) of SMS27K for different oils and organic solvents and (b) the corresponding gravimetric absorption capacities at 30 sorption-squeezing cycles. 30
Figure 2-1. FTIR spectra of (a) U2, MDI and TPA3NH2, (b) U3, TPA3NCO, TPANH2, (c) U2 and aU2 and (d) U3 and aU3. 59
Figure 2-2. The Raman spectra of the aU2 and aU3. 60
Figure 2-3. TGA of the U2, U3, aU2 and aU3 under a N2 atmosphere. (heating rate 20 oC/min) 61
Figure 2-4. (a) XPS spectra of C 1s, N 1s and O 1s orbitals. (b, c) deconvolution of N 1s and O 1s for aU2, (d, e) for aU3. 63
Figure 2-5. Comparison of the N2 adsorption isotherms at 77K (a) U2, U3, aU2 and aU3. (b) pore size (inset: aU2 and aU3 micropore sizes detected by CO2 adsorption.)… 65
Figure 2-6. CO2 capture using the U2, U3, aU2 and aU3 at 298 K. 66
Figure 2-7. (a) Effects of initial pH, (b) contact time, (c) initial concentration and (d) results of five adsorption−desorption cycles on adsorption of U2 and U3 for Pb(II). (a: initial ion concentration 250 mg/L, contact time 6hr, sample dosage 1g/L, temperature 25 oC, stirring speed 200 rpm; b: initial ion concentration 250 mg/L, initial pH 6.0, sample dosage 1g/L, temperature 25 oC stirring speed 200 rpm; c: initial pH 6.0, contact time 6hr, sample dosage 1g/L. d: initial concentration 250 mg/L, initial pH 6.0, contact time 6hr, sample dosage 1 g/L, temperature 25 °C, stirring speed 200 rpm.)……. 71
Figure 2-8. High-resolution XPS spectra survey of primitive UPP and Pb(II) adsorption surface. (b) Pb 4f spectra of Pb(II) adsorbed UPP and Pb(II). (c), (d) N 1s spectra of U2-Pb(II) and U3-Pb(II). (e), (f) O 2p spectra of U2-Pb(II) and U2-Pb(II)….. 74
Figure 2-9. (a) FTIR spectra of U2 and U3 before adsorption and after five-time absorption for Pb(II) at C=O-NH amide II bonding and (b) secondary amino group on urea linkage.. 76
Figure 2-10. SEM images of (a) U2, (b) U3. (c) U2-Pb(II) and (d) U3-Pb(II) after five-time adsorption... 77
Figure S1-1. Schematic illustrations of (a) coordination interactions between the “Urea chemistry” and secondary amine group in SMS and (b) corresponding hydrophilic to hydrophobic transition of the melamine sponge. 90
Figure S1-2. (a) Appearance of uncured iPD5K slurry and the homogeneous cured cPD5k film and (b) UV-vis spectra of cPD5K and cPD27K films, and photographs of cPD5K and cPD27K films showing the flexibility and transparency of the films. 91
Figure S1-3. Stress/strain curves of cured (a) cPD5K and (b) cPD27K. 92
Figure S1-4. Gravimetric absorption capacities G (g/g) of cPD5K and cPD27K films for different organic solvents (left) and oils (right) by its swelling property. 92
Figure S1-5. Appearances and WCAs of modified SMS5K and SMS27K films. 93
Figure S1-6. Variations in WCA on the SMS27K with immerse time in hexane at ambient time. (inset: The water sliding angle (= 10o) of SMS27K.) 93
Figure S1-7. The WCA hysteresis of SMS27K. 94
Figure S1-8. Snapshots showing the process of selective absorption of chloroform (dyed in red) from water. 95
Figure S1-9. Transmittance of feed emulsion solution and hexane filtrate from the continuous separation of surfactant-stabilized/free hexane-in-water emulsion. 96
Figure S1-10. Photographs of after 30 sorption-squeezing cycles for (a) chloroform (b) hexane, (c) hexadecane, (d) toluene, (e) lubricant oil, (f) motor oil and (g) edible oil droplets (all water droplets are dyed in yellow) on the surfaces of SMS27K. 96
Figure S2-1. Synthesis process, (a) 1H NMR spectra and (b) FTIR spectra of TPA3NO2, TPA3NH2 and TPA3NCO. 98
Figure S2-2. MALDI-TOF mass spectra of TPA3NH2 and TPA3NCO. 98
Figure S2-3. Solid state 13C NMR of U2, U3, aU2 and aU3. 99
Figure S2-4. SEM image of KOH-activation of (a) aU2 and (b) aU3. 100
Figure S2-5. (a) FTIR spectra (b) XRD spectra of U2 and U3 and after adsorption of Pb(II), U2-Pb(II) and U3-Pb(II). 100
Figure S2-6. (a) the absorbance of Pb(II) at 200 nm (b) The calibration curve for Pb(II) in deionized water. 101

List of Scheme
Scheme 1-1. Synthesis of iPD as key intermediate for the preparations of (a) crosslinked cPD and (b) SMS sorbent material. 10
Scheme 2-1. Synthesis of derivative TPA monomers and (b)U2 and U3 for Pb(II) uptake; KOH-activation of the aU2 and aU3 for CO2 capture.. 48

List of Table
Table 1-1. Absorption capacity and retention after 30 cycles of sorption-squeezing of SMS27K for various oils and organic solvents. 26
Table 1-2. Comparison of sponge and sponge-like sorbent materials. 31
Table 2-1. Area fractions of N1s and O1s spectra, based on the curve fitting data. 63
Table S1-1. Water advancing contact angle, receding contact angle and hysteretic angel of sample SMS27K. 94
Table S2-1. Elemental analysis of UPP and after KOH-activation aU2 and aU3. 99

Chapter 1. Superhydrophobic Melamine Sponge Modified by Cross-Linked Urea Network as Recyclable Oil Absorbent Materials

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Chapter 2. Effective CO2 Capture and Lead(II) Uptake of Porous Materials Derived from Cross-linked Urea Networks

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