富含氮奈米碳材製備與拉曼光譜增強基材之應用

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林建甫(Jian-Fu Lin) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

富含氮奈米碳材製備與拉曼光譜增強基材之應用

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摘要(中)

首先本研究以聚4乙烯吡啶(poly(4-vinylpyridine), P4VP)經熱燒結後製備出富含氮碳材，將其應用於作為表面拉曼光譜訊號增強(surface-enhanced Raman scattering, SERS)基材後，觀察到其增強訊號的能力良好。探討聚4乙烯吡啶經一系列熱燒結溫度下製備樣品的氮摻雜組態後，發現氮組態中的四級氮(graphitic-N)比例隨燒結溫度升高而增加，此時最高占據分子軌域和最低未占據分子軌域間能隙(HOMO-LUMO gap)降低，電荷傳遞能力(charge transfer)提升，此時四級氮周圍的碳上有很高的區域電子雲密度(charge density)使富含氮碳材帶有更高的極性，則富含氮碳材與分子間的偶極-偶極力(dipole-dipole interaction)也會提升，最終作為表面拉曼光譜訊號增強基材的能力也跟著提升。

接下來由於聚4乙烯吡啶(P4VP)的熱燒結溫度已達臨界點，為了更進一步製備出具更高表面拉曼光譜訊號增強能力的基材，即以聚苯乙烯－聚4乙烯吡啶(poly(styrene-block-4-vinylpyridine), PS-b-P4VP)製備微胞薄膜後，經熱燒結製備一系列富含氮中孔碳材。期望藉由表面積提升，製備出具更高表面拉曼光譜訊號增強能力的基材。藉由低掠角小角度X光散射儀(grazing-incidence small-angle X-ray scattering, GISAXS)量測平面上X光散射 (1D in-plane)強度，再配合Igor Pro軟體以相對應的X光散射關係式進行擬合後，發現具有更高表面積的富含氮中孔碳材由於吸附表面的分子越多且進行分子與基材間電荷傳遞的表面積越大，表面拉曼光譜訊號增強能力也隨之增強，最終得到具有明顯表面積提升的富含氮中孔碳材其表面拉曼光譜訊號增強能力明顯較富含氮碳材為好的結果。

最後探討碘摻雜於富含氮中孔碳材後提升表面拉曼光譜訊號增強能力的可能性。以聚苯乙烯－聚2乙烯吡啶(poly(styrene-block-2-vinylpyridine), PS-b-P2VP)製備微胞薄膜後，分別以熱燒結前摻雜碘離子與熱燒結後摻雜碘離子兩種製程製備碘摻雜富含氮中孔碳材。發現到碘離子摻雜後形成碘氮鍵結使周圍碳材帶有更強的正電荷密度而更容易吸引電子而提升電荷傳遞能力，同時碘離子的極性也提升了分子與基材間的偶極-偶極力，使表面拉曼光譜訊號增強能力更好。而對於形成碳材前摻雜碘離子的樣品來說，除了碘離子的貢獻外，碘摻雜後的樣品熱裂解溫度下降而導致在相同溫度下燒結時，碳化程度較未摻雜的樣品提升也是使表面拉曼光譜訊號增強能力更好的原因之一。

摘要(英)

Nitrogen-enriched carbon materials could be fabricated by thermal pyrolysis of poly(4-vinylpyridine) thin layers. By using the nitrogen-enriched carbon materials as surface-enhanced Raman scattering substrates, the excellent enhancement of Raman signal is observed. From the analysis of nitrogen configurations for nitrogen species for nitrogen-enriched carbon materials, the proportion of graphitic-N depends on pyrolysis temperature. Due to the fact that the presence of graphitic-N could reduce the band gap, graphitic-N could favor charge transfer between the substrate and the molecule. Due to different electronegativity between carbon and nitrogen, positive high charge densities could be present on the carbons neighboring to graphitic-N, which may result in dipole-dipole interactions between the substrate and the molecule. As a result, the ability of surface-enhanced Raman scattering substrate can be finely determined by pyrolysis temperature.

Considering that porous carbon nanomaterials have high surface areas, nitrogen-enriched porous carbon nanomaterials were fabricated through thermal pyrolysis of poly(styrene-block-4-vinylpyridine) diblock copolymers. With grazing-incidence small-angle X-ray scattering characterizations and model simulations for nitrogen-enriched porous carbon nanomaterials templated by PS-b-P4VP, the surface area of hierachical pores within nitrogen-enriched porous carbon nanomaterials was estimated. The increased surface area of copolymer templated nitrogen-enriched porous carbon could increase the capacity of molecular adsorption. More surface area equals to higher charge transfer ability. As a result, more surface area equals to higher ability of surface-enhanced Raman scattering substrate.

In the last part, iodine doping was applied to improve the ability of surface-enhanced Raman scattering substrate. Iodine-doped nitrogen-enriched porous carbon nanomaterials were fabricated by two approaches. The first approach is that nitrogen-enriched and iodine-doped porous carbon nanomaterials were fabricated by pyrolyzing poly(styrene-block-2-vinylpyridine) followed by iodine doping. The second approach is that the two processes were switched; iodine doping was first imposed on PS-b-P2VP block copolymers and then thermal pyrolysis was carried out. Both approaches could successfully generate nitrogen-enriched and iodine-doped porous carbon nanomaterials, which show improved Raman scattering intensity enhancement. From the analysis of nitrogen configurations, iodine-nitrogen bonds were found. The iodine-nitrogen bonds could induce more positive charges on carbons that promote the charge transfer ability between substrate and molecule. The polarity of iodine promotes dipole-dipole interactions between substrate and molecule. As a result, iodine doping indeed improves the ability of surface-enhanced Raman scattering substrate. Besides, for the second approach, carbonization could generate nanomaterials with high crystallinity. As a result such carbon nanomaterials show improvement of Raman scattering intensity of adsorbed dye molecules.

關鍵字(中)

★ 富含氮奈米碳材
★ 拉曼光譜增強基材

關鍵字(英)

論文目次

摘要 I
Abstract III
致謝 VI
目錄 VII
圖目錄 X
表目錄 XVI
第1章序論 1
1-1 拉曼光譜學 1
1-2 表面拉曼光譜訊號增強原理 3
1-2-1 電磁場增強機制 4
1-2-2 化學增強機制 5
1-3 石墨烯作為表面拉曼光譜訊號增強基材 7
1-4 以氮摻雜石墨烯作為表面拉曼光譜訊號增強基材 10
1-4-1 氮摻雜石墨烯作為表面拉曼光譜訊號增強基材能 10
1-4-2 氮組態對表面拉曼光譜訊號增強影響 12
1-5 含氮高分子製備氮摻雜石墨 14
1-6 表面積與其他元素摻雜對表面拉曼光譜訊號增強影響 18
1-6-1 表面積對表面拉曼光譜訊號增強影響 18
1-6-2 其他元素摻雜對表面拉曼光譜訊號增強影響 20
1-7 實驗動機 22
第2章實驗方法 25
2-1 實驗藥品與基材 25
2-2 樣品製備 28
2-2-1 基材清潔 28
2-2-2 製備富含氮碳材 28
2-2-3 製備富含氮中孔碳材 28
2-2-4 製備碘摻雜富含氮中孔碳材 29
2-3 實驗使用儀器 30
2-3-1 顯微影像觀察 31
2-3-2 低掠角小角度X光散射訊號分析與擬合結構資訊 32
2-3-3 熱重分析儀量測燒結過程重量變化 32
2-3-4 紫外光可見光光譜儀 33
2-3-5 拉曼光譜儀 33
2-3-6 X射線光電子能譜儀 34
2-3-7 拉曼光譜儀訊號計算增強因子分析 34
2-3-8 從紫外光可見光光譜儀量測結果計算HOMO-LUMO gap 35
第3章結果與討論 37
3-1 富含氮碳材製備與表面拉曼光譜訊號增強能力 37
3-1-1 富含氮碳材製備與組成 37
3-1-2 富含氮碳材作為表面拉曼光譜訊號增強基材能力 44
3-1-3 各富含氮碳材中四級氮比例與電荷傳遞能力關係 47
3-1-4 燒結溫度與表面拉曼光譜訊號增強能力關係 51
3-2 富含氮中孔碳材製備與表面拉曼光譜訊號增強能力 56
3-2-1 富含氮中孔碳材製備與形貌 56
3-2-2 富含氮中孔碳材作為表面拉曼光譜訊號增強基材能力 60
3-2-3 表面積與表面拉曼光譜訊號增強能力關係 62
3-3 碘摻雜富含氮中孔碳材與表面拉曼光譜訊號增強能力 73
3-3-1 碘摻雜富含氮中孔碳材製備 73
3-3-2 碘摻雜富含氮中孔碳材作為表面拉曼光譜訊號增強基材能力 78
3-3-3 碘摻雜富含氮中孔碳材組成與表面拉曼光譜訊號增強能力關係 82
結論 91
參考資料 93
附錄 100

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指導教授

孫亞賢(Ya-Sen Sun)

審核日期

2016-7-29

推文