本文選題：卟啉 + 基非�。� 參考：《吉林大學》2015年博士論文

【摘要】：隨著能源危機日趨嚴重,人們對直接甲醇燃料電池(Direct Methanol Fuel Cell,DMFC)和微生物燃料電池(Microbial Fuel Cell,MFC)進行了廣泛研究,而制約這兩種電池技術(shù)廣泛應(yīng)用的主要瓶頸之一是其陰極氧還原反應(yīng)的催化劑。目前,最常用的陰極催化劑是鉑基催化劑,但鉑基催化劑較為昂貴,且容易中毒。因此,開發(fā)廉價且高效的非貴金屬替代催化劑已成為燃料電池和微生物燃料電池研究和應(yīng)用的一個重要科學問題,具有重要的研究意義。自然界輔酶和輔基的催化中心結(jié)構(gòu)為氧還原反應(yīng)催化劑的開發(fā)提供了重要啟示。這些輔酶和輔基通常具有鐵卟啉或鈷卟啉配合中心,在生物體內(nèi)的氧氣運載和多種氧化還原反應(yīng)中發(fā)揮重要作用。受此啟發(fā),人們廣泛研究了非貴金屬大環(huán)配合物的氧還原催化性能,研究較多的非貴金屬包括鐵、鈷等,而配位大環(huán)則多是卟啉、酞菁及其衍生物。但此類離散的配合物在電解質(zhì)溶液中容易解離,不利于電池的長期穩(wěn)定運行。為進一步提高非貴金屬大環(huán)配合物催化劑在溶液中的穩(wěn)定性,人們構(gòu)建了嵌入多金屬中心的共價有機框架。共價有機框架(Covalent Organic Frameworks)是一類相對有序的共價有機聚合物(Covalent Organic Polymers),具有多孔的有序結(jié)構(gòu)和良好的穩(wěn)定性,因此,基于共價有機框架的多金屬中心催化材料已成為近期氧還原催化劑研究的熱點。本文基于空氣陰極直接甲醇燃料電池和微生物燃料電池等應(yīng)用背景,針對氧還原催化劑研究中的重要科學問題,利用師法自然的仿生思想,借鑒自然界輔酶和輔基的中心結(jié)構(gòu),制備了嵌入非貴金屬有機大環(huán)分子配合中心的二維和三維共價有機框架,對其進行了物理化學表征和電化學測試,并將部分材料應(yīng)用于微生物燃料電池。主要工作和研究結(jié)論如下:1.首次通過炔烴復(fù)分解反應(yīng)合成了一種共軛多孔的二維鈷卟啉基有機框架材料(Co PEF),并將廉價的碳黑作為電子導體與Co PEF進行混合,將混合物(Co PEF/C)作為氧還原催化劑。無論是在酸性還是堿性介質(zhì)中,Co PEF/C均表現(xiàn)出了良好的氧還原催化性能。相比于鈷卟啉單體,共軛的框架材料增強了氧還原的催化活性,具體表現(xiàn)為更高(更正)的初始電勢和更大的限制電流密度。這可能是由于Co PEF的多孔性和共軛性使活性位點更充分暴露,并利于更有效的電子與物質(zhì)傳遞。催化機理研究發(fā)現(xiàn)Co PEF/C催化下的氧還原反應(yīng)主要通過4電子催化途徑,產(chǎn)物接近于全部為水。此外,相對于鈷卟啉單體和商用催化劑Pt/C,Co PEF/C還兼具更加良好的穩(wěn)定性和甲醇耐受性。2.基于二維鈷卟啉基有機框架材料(Co PEF),開發(fā)了一種多孔、高比表面積的三維鈷卟啉基有機框架材料(Co POP),并將其應(yīng)用于氧還原催化。Co POP在酸性和堿性介質(zhì)中均顯示出了優(yōu)異的穩(wěn)定性,持續(xù)工作50000秒時催化電流基本沒有變化。該材料熱解后的穩(wěn)定性和比表面積雖有所下降,但氧還原催化活性卻有所提升。TEM,HRTEM,XPS和XRD等一系列表征發(fā)現(xiàn)熱解后的材料是包裹著鈷納米粒子的摻氮碳材料。電化學測試表明最優(yōu)的熱解溫度為800°C,所得的材料(Co POP-800)具有最高的催化活性,其催化性能和商用Pt/C相比,相近、甚至更優(yōu)。另外,Co POP-800/C催化的氧還原為4電子催化機理,將氧氣直接還原成水,且Co POP-800/C還具有非常優(yōu)異的甲醇耐受性和穩(wěn)定性。3.通過熱解一種新型多孔、高比表面積的鐵卟啉基高分子材料獲得了Fe-Nx/C催化劑,并將其應(yīng)用于單室微生物燃料電池的空氣陰極。在中性介質(zhì)中,Fe-Nx/C展現(xiàn)出良好的氧還原催化性能。這可能是因為鐵基納米粒子和摻氮的石墨碳層產(chǎn)生了協(xié)同催化作用。此外,相對于Pt/C陰極的微生物燃料電池,Fe-Nx/C陰極的微生物燃料電池展示出了更加優(yōu)異的性能,具體表現(xiàn)在更佳的電池電壓、最大功率密度和庫倫效率。這些研究表明Fe-Nx/C比Pt/C能更加適應(yīng)和耐受具有細菌的微生物燃料電池體系,進而具有更好的實用前景。
[Abstract]:As the energy crisis is getting worse, people have studied the direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC) and microbial fuel cell (Microbial Fuel Cell, MFC), and one of the main bottlenecks that restricts the wide application of these two battery technologies is the catalyst for the negative oxygen reduction reaction. Chemical agents are platinum based catalysts, but platinum based catalysts are more expensive and easy to be poisoned. Therefore, the development of cheap and efficient non noble metal substitutive catalysts has become an important scientific problem in the research and application of fuel cells and microbial fuel cells. The development of the reduction reaction catalyst provides important inspiration. These coenzymes and cofactors usually have iron porphyrin or cobalt porphyrin, which play an important role in oxygen delivery and redox reactions in organisms. Inspired by this, people have extensively studied the catalytic performance of oxygen reduction of non precious metal macrocyclic complexes, and more research has been made. Non precious metals include iron and cobalt, while large rings are mostly porphyrin, phthalocyanine and their derivatives. But such discrete complexes are easily dissociated in electrolyte solutions and are not conducive to the long-term stable operation of the batteries. In order to further improve the stability of the catalyst in the solution of non precious metal macrocyclic complexes, a multi metal center is built. Covalent organic frame. The covalent organic framework (Covalent Organic Frameworks) is a kind of relatively ordered covalent organic polymer (Covalent Organic Polymers), which has porous structure and good stability. Therefore, the multi metal center accelerating material based on covalent organic frame has become a hot spot in the recent study of oxygen reduction catalyst. Based on the application background of the air cathode direct methanol fuel cell and the microbial fuel cell, this paper aims at the important scientific problems in the study of the oxygen reduction catalyst. By using the natural bionic idea of the teacher's method and drawing on the central structure of the natural coenzyme and auxiliary base in nature, the two-dimensional and three-dimensional structure of the organic macrocyclic molecular coordination center of the non precious gold genus is prepared. The covalent organic framework was used for physical and chemical characterization and electrochemical testing, and some materials were applied to microbial fuel cells. The main work and research conclusions are as follows: 1. a conjugated porous two-dimensional cobalt porphyrin organic frame material (Co PEF) was synthesized by the complex decomposition reaction of alkynes for the first time, and the cheap carbon black was used as the electron. The conductor is mixed with Co PEF, and the mixture (Co PEF/C) is used as an oxygen reduction catalyst. Both in acid or alkaline medium, Co PEF/C shows good catalytic performance in oxygen reduction. The conjugate frame material increases the catalytic activity of oxygen reduction compared to the cobalt porphyrin monomer. This may be due to the porosity and conjugation of Co PEF, which makes the active sites more fully exposed and is beneficial to the more effective electron and material transfer. The catalytic mechanism studies found that the oxygen reduction reaction under the catalysis of Co PEF/C is mainly through 4 electron catalysis, the product is nearly all water. In addition, relative to the cobalt porphyrin monomer. The commercial catalyst Pt/C, Co PEF/C also have a better stability and methanol tolerance.2. based on the two-dimensional cobalt porphyrin based organic frame material (Co PEF). A three-dimensional cobalt porphyrin based organic frame material (Co POP) with porous, high specific surface area (Co POP) has been developed and applied to the oxygen reduction catalyst.Co POP in both acidic and alkaline media. The catalytic current was basically unchanged at 50000 sec. The stability and specific surface area of the material decreased, but the catalytic activity of oxygen reduction was improved by.TEM, HRTEM, XPS and XRD. It is shown that the optimum pyrolysis temperature is 800 C, and the obtained material (Co POP-800) has the highest catalytic activity. Its catalytic performance is similar to that of commercial Pt/C, and even better. In addition, the oxygen reduction of Co POP-800/C is reduced to 4 electron catalytic mechanism, the oxygen is reduced to water directly, and Co POP-800/C also has excellent methanol tolerance and stability. Qualitative.3. obtained a Fe-Nx/C catalyst by pyrolysis of a new porous, high specific surface area iron porphyrin based polymer, and applied it to the air cathode of a single chamber microbial fuel cell. In neutral medium, Fe-Nx/C showed good catalytic performance in oxygen reduction. This may be due to the carbon layer of iron based nanoparticles and nitrogen doped graphite. Synergistic catalysis is produced. In addition, microbiological fuel cells of the Fe-Nx/C cathode exhibit better performance than the Pt/C cathode for microbial fuel cells, which are shown in better battery voltage, maximum power density and Kulun efficiency. These studies show that Fe-Nx/C is more adaptable and tolerable to bacteria than Pt/C. The fuel cell system has better practical prospects.
【學位授予單位】：吉林大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：O643.36;TM911.4

【相似文獻】

相關(guān)期刊論文 前10條

1 王麗娟;在石墨及聚酞菁化合物電極上氧還原的電催化[J];催化學報;1988年01期

2 黃幼菊;李偉善;黃青丹;李偉;張慶龍;蔣臘生;;氫鉬青銅對鉑催化氧還原反應(yīng)的促進作用[J];高等學�；瘜W學報;2007年05期

3 李之樂;曾為民;馬玉錄;;聚苯胺載鉑鈀電極的制備及氧還原催化性能研究[J];華東理工大學學報(自然科學版);2013年04期

4 李萍;李升憲;胡曉宏;王會勤;;球磨方法對氧還原催化劑性能的影響[J];電池;2006年03期

5 位辰先,田建華,梁寶臣,劉邦衛(wèi);制備條件對卟啉鈷氧還原催化性能的影響[J];天津理工學院學報;2004年03期

6 孫曉然;李光躍;夏定國;張立美;李釩;;均苯四甲酰亞胺橋聯(lián)的聚酞菁亞鐵的氧還原反應(yīng)(英文)[J];物理化學學報;2013年07期

7 左小剛;;硫酸鹽還原菌對陰極氧還原反應(yīng)的影響[J];新疆有色金屬;2013年05期

8 張麗娟,夏定國,王振堯,袁嶸,吳自玉;鉑鉍金屬間化合物催化劑的氧還原與抗甲醇氧化性能[J];物理化學學報;2005年03期

9 李英霞;陳章霖;羅瑞賢;陳靄t，

本文編號：2035283