新型功能化離子液體的結(jié)構設計及其在調(diào)控酸性氣體捕集的研究
發(fā)布時間：2018-07-26 11:47
【摘要】：人們已經(jīng)意識到,如果不采取任何行動來應對全球氣候變化的話,一場毀滅性的災難遲早會來臨。眾所周知,二氧化碳(CO2)排放是引起全球變暖、海平面上升以及更為嚴峻的氣候問題的主要元兇。實際上,空氣中人為CO2濃度已經(jīng)積累到了前所未有的水平(約為400 ppm),這主要是由于化石燃料的不斷消耗引起的。因此,非常有必要發(fā)展高效的CO2捕集和儲存技術來緩和當前的CO2危機。在這一點上,離子液體憑借其極低的蒸汽壓、良好的熱穩(wěn)定性、不可燃性、寬的液程、幾乎無限的調(diào)節(jié)性、優(yōu)越的CO2親和性等優(yōu)勢,有望成為最為先進的CO2捕集技術之一。在這篇論文中,我主要集中在新型功能化離子液體的設計合成和CO2吸收性能的調(diào)控。在第一部分中,我們將π電子共軛結(jié)構引入到離子液體陰離子中,可實現(xiàn)可逆的CO2捕集,這主要源自于動態(tài)共價碳氧單鍵的形成。π電子共軛陰離子可以雙重調(diào)控CO2的吸收性能,即同時增強CO2的容量和改善CO2的脫附。改善的脫附性能是由于π電子共軛結(jié)構的電荷分散引起的;增強的吸收容量可能是由于陰離子的聚集效應協(xié)同增強所生成的動態(tài)碳氧單鍵。吸收實驗、譜學研究、理論計算和熱重分析都支持了這種雙重調(diào)控作用。不含氘代溶劑的核磁碳譜技術(No-DNMR)顯示,化學吸收的CO2峰明顯增強,提供了一種有效的原位技術來確定離子液體和CO2的相互作用機理。這些離子液體熱穩(wěn)定性高、吸收容量大、CO2脫附性能強,顯示出動態(tài)共價鍵在消除CO2危機中扮演了重要角色。在第二部分中,我們設計一系列氨基功能化吡啶型離子液體,通過CO2吸收過程中的分子內(nèi)質(zhì)子轉(zhuǎn)移來改善CO2的吸收性能。我們的策略是引入一個堿性基團(去質(zhì)子化的羥基)作為質(zhì)子受體來阻止CO2吸收過程中氨基之間的分子間質(zhì)子轉(zhuǎn)移,從而可實現(xiàn)增強的CO2吸收容量和可控的粘度變化。我們知道,通常所報道的氨基功能化離子液體在CO2吸收過程中往往伴隨著粘度的劇烈增加。與之相反的是,也是非常重要的一點,[P66614][2-NH2-3-O-Py]吸收CO2后,體系的粘度下降約40%,表明是一個自身加速的吸收過程。吸收實驗結(jié)果同時顯示,這些氨基功能化離子液體表現(xiàn)出強勁的、快速的、耐水的、以及可逆的CO2吸收。在第三部分中,我們構筑了新型的光響應陰離子功能化離子液體,分別將偶氮苯基接在季擕鹽陽離子上和以1,2,4-三氮唑作為陰離子。與之前的光響應離子液體不同,我們利用離子交換的方法首次將功能化陰離子(1,2,4-三氮唑)引入到光響應離子液體中,并且可以通過下面兩種途徑獲得純的順式離子液體。一種方法是將離子液體溶于四氫呋喃(THF)溶劑中,經(jīng)過紫外光照射后,去除低沸點的THF溶劑即可。另一種方法是將離子液體制成薄膜,用紫外光照射即可。用紫外光和藍光交替照射離子液體的溶液和薄膜都可以實現(xiàn)離子液體的順反可逆互變。下一步的工作在于考察順反異構效應是否對離子液體的CO2吸收有影響。在第四部分中,我們首次報道了SO2氣體能誘導偶氮苯基型離子液體實現(xiàn)順式到反式構型的翻轉(zhuǎn)。而氮氣(N2)和CO2卻幾乎不能。核磁氫譜(NMR)、紫外可見光譜(UV-vis)和紅外光譜(FT-IR)都證實了吸收SO2后順式偶氮苯基型離子液體的構型能完全從順式向反式發(fā)生翻轉(zhuǎn)。設計邏輯實驗,并進行核磁分析可知,高吸收容量的SO2物理溶解是引起順式偶氮苯基型離子液體的最主要原因。由光異構化速率常數(shù)可知,相對于沒有吸收SO2的離子液體稀溶液而言,[P66614][azo-COO]-SO2稀溶液的光異構化過程受到極大的抑制。這個工作取得的結(jié)果也許對構建新型的刺激響應型材料在氣體傳感器上的研究有所幫助�？傊�,我們期望新概念和策略的出現(xiàn)和引入,給離子液體的CO2捕集帶來新的活力。我們也期望在解決科學問題的過程中能收獲新的發(fā)現(xiàn)。我需要謹記一點的是,"要善于打破思維定勢,建立跨學科的思維模式,因為這樣往往有助于獲得一些原創(chuàng)性的新發(fā)現(xiàn)。"
[Abstract]:People have realized that if no action is taken to cope with global climate change, a devastating disaster will come sooner or later. Carbon dioxide (CO2) emissions are known to be the main cause of global warming, sea level rise and more severe climate problems. In fact, the concentration of CO2 in the air has been accumulated. The unprecedented level (about 400 ppm) is mainly due to the continuous consumption of fossil fuels. Therefore, it is very necessary to develop efficient CO2 capture and storage techniques to mitigate the current CO2 crisis. At this point, ionic liquids have a very low vapor pressure, good thermal stability, unflammability, wide liquid range, almost unlimited. In this paper, I mainly focus on the design and synthesis of new functional ionic liquids and the regulation of the performance of CO2 absorption. In the first part, we introduce the pi electron conjugated structure into the ionic liquid anion in the first part, which can be reversible. The CO2 trap mainly derives from the formation of the single bond of dynamic covalent carbon and oxygen. The pion electron conjugated anion can double control the absorption properties of CO2, that is, to enhance the capacity of CO2 and to improve the desorption of CO2. The improved desorption performance is caused by the charge dispersion of the conjugated structure of the pi electron; the enhanced absorption capacity may be due to the anion. The aggregation effect synergistically enhanced the dynamic carbon oxygen single bond. Absorption experiments, spectroscopic studies, theoretical calculations and thermogravimetric analysis supported this dual regulation. The CO2 peak without deuterium solvent (No-DNMR) showed that the peak of chemical absorption was obviously enhanced, and an effective in-situ technique was provided to determine the ionic liquid and CO2. These ionic liquids have high thermal stability, high absorption capacity and strong CO2 desorption performance, showing that dynamic covalent bonds play an important role in the elimination of the CO2 crisis. In the second part, we designed a series of amino functional pyridine ionic liquids to improve CO2 through the transfer of intramolecular intron in the CO2 absorption process. Our strategy is to introduce an alkaline group (deprotonated hydroxyl) as a proton receptor to prevent the intermolecular proton transfer between amino groups during CO2 absorption, thus achieving enhanced CO2 absorption capacity and controllable viscosity changes. We know that the commonly reported amino functional ionic liquids have been absorbed in CO2. When [P66614][2-NH2-3-O-Py] absorbs CO2, the viscosity of the system decreases by about 40%, indicating that it is a self accelerating absorption process. The results of absorption experiments show that these amino functional ionic liquids show strong, fast, and water resistant. As well as reversible CO2 absorption, in the third part, we constructed a new type of photoresponse anion functionalized ionic liquid, which respectively connected azo phenyl on quaternary ammonium salt and 1,2,4- three azole as anions. Unlike the previous photoresponse ionic liquids, we used the separation method for the first time to function anions (1,2,4 Three azolol is introduced into the light response ionic liquid and can be obtained by two ways to obtain pure CIS ionic liquids. One way is to dissolve the ionic liquid in the tetrahydrofuran (THF) solvent and remove the low boiling point THF solvent after ultraviolet light. The other is to make the ionic liquid film and irradiate with ultraviolet light. In the fourth part, we first report that the SO2 gas can induce the azo phenyl type ionic liquid. In the fourth part, we report that the SO2 gas can induce the azo phenyl type ionic liquid. However, nitrogen (N2) and CO2 are almost impossible. Nuclear magnetic hydrogen spectrum (NMR), ultraviolet visible spectrum (UV-vis) and infrared spectroscopy (FT-IR) all confirm that the configuration of the CIS diazo phenyl ionic liquid can completely turn from cis to trans form after absorption of SO2. The physical dissolution of the SO2 capacity is the main cause of the CIS type azo phenyl ionic liquid. It is known from the rate constant of the photoisomerization that the photoisomerization process of the [P66614][azo-COO]-SO2 dilute solution is greatly suppressed relative to the dilute solution of the ionic liquid without absorption of SO2. In short, we expect the emergence and introduction of new concepts and strategies to bring new vitality to the CO2 capture of ionic liquids. We also expect to reap new discoveries in the process of solving scientific problems. Interdisciplinary thinking mode, because this often helps to get some original new discoveries. "
【學位授予單位】：浙江大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O645.1
[Abstract]:People have realized that if no action is taken to cope with global climate change, a devastating disaster will come sooner or later. Carbon dioxide (CO2) emissions are known to be the main cause of global warming, sea level rise and more severe climate problems. In fact, the concentration of CO2 in the air has been accumulated. The unprecedented level (about 400 ppm) is mainly due to the continuous consumption of fossil fuels. Therefore, it is very necessary to develop efficient CO2 capture and storage techniques to mitigate the current CO2 crisis. At this point, ionic liquids have a very low vapor pressure, good thermal stability, unflammability, wide liquid range, almost unlimited. In this paper, I mainly focus on the design and synthesis of new functional ionic liquids and the regulation of the performance of CO2 absorption. In the first part, we introduce the pi electron conjugated structure into the ionic liquid anion in the first part, which can be reversible. The CO2 trap mainly derives from the formation of the single bond of dynamic covalent carbon and oxygen. The pion electron conjugated anion can double control the absorption properties of CO2, that is, to enhance the capacity of CO2 and to improve the desorption of CO2. The improved desorption performance is caused by the charge dispersion of the conjugated structure of the pi electron; the enhanced absorption capacity may be due to the anion. The aggregation effect synergistically enhanced the dynamic carbon oxygen single bond. Absorption experiments, spectroscopic studies, theoretical calculations and thermogravimetric analysis supported this dual regulation. The CO2 peak without deuterium solvent (No-DNMR) showed that the peak of chemical absorption was obviously enhanced, and an effective in-situ technique was provided to determine the ionic liquid and CO2. These ionic liquids have high thermal stability, high absorption capacity and strong CO2 desorption performance, showing that dynamic covalent bonds play an important role in the elimination of the CO2 crisis. In the second part, we designed a series of amino functional pyridine ionic liquids to improve CO2 through the transfer of intramolecular intron in the CO2 absorption process. Our strategy is to introduce an alkaline group (deprotonated hydroxyl) as a proton receptor to prevent the intermolecular proton transfer between amino groups during CO2 absorption, thus achieving enhanced CO2 absorption capacity and controllable viscosity changes. We know that the commonly reported amino functional ionic liquids have been absorbed in CO2. When [P66614][2-NH2-3-O-Py] absorbs CO2, the viscosity of the system decreases by about 40%, indicating that it is a self accelerating absorption process. The results of absorption experiments show that these amino functional ionic liquids show strong, fast, and water resistant. As well as reversible CO2 absorption, in the third part, we constructed a new type of photoresponse anion functionalized ionic liquid, which respectively connected azo phenyl on quaternary ammonium salt and 1,2,4- three azole as anions. Unlike the previous photoresponse ionic liquids, we used the separation method for the first time to function anions (1,2,4 Three azolol is introduced into the light response ionic liquid and can be obtained by two ways to obtain pure CIS ionic liquids. One way is to dissolve the ionic liquid in the tetrahydrofuran (THF) solvent and remove the low boiling point THF solvent after ultraviolet light. The other is to make the ionic liquid film and irradiate with ultraviolet light. In the fourth part, we first report that the SO2 gas can induce the azo phenyl type ionic liquid. In the fourth part, we report that the SO2 gas can induce the azo phenyl type ionic liquid. However, nitrogen (N2) and CO2 are almost impossible. Nuclear magnetic hydrogen spectrum (NMR), ultraviolet visible spectrum (UV-vis) and infrared spectroscopy (FT-IR) all confirm that the configuration of the CIS diazo phenyl ionic liquid can completely turn from cis to trans form after absorption of SO2. The physical dissolution of the SO2 capacity is the main cause of the CIS type azo phenyl ionic liquid. It is known from the rate constant of the photoisomerization that the photoisomerization process of the [P66614][azo-COO]-SO2 dilute solution is greatly suppressed relative to the dilute solution of the ionic liquid without absorption of SO2. In short, we expect the emergence and introduction of new concepts and strategies to bring new vitality to the CO2 capture of ionic liquids. We also expect to reap new discoveries in the process of solving scientific problems. Interdisciplinary thinking mode, because this often helps to get some original new discoveries. "
【學位授予單位】：浙江大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O645.1
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