本文關(guān)鍵詞： 卟啉 自組裝 反應(yīng)/擴(kuò)散 協(xié)調(diào) 結(jié)構(gòu)多樣性　出處：《哈爾濱理工大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：納米材料的結(jié)構(gòu)決定其性能，因此制備具有不同結(jié)構(gòu)的材料對于材料性能的優(yōu)化及開發(fā)具有十分重要的意義，另一方面，多樣性和復(fù)雜性是材料結(jié)構(gòu)的一個內(nèi)在特征，這為材料結(jié)構(gòu)的可控制備增加了難度，因此有效調(diào)控材料結(jié)構(gòu)的方法及理論發(fā)展非常緩慢�？紤]到很多復(fù)雜結(jié)構(gòu)都是在遠(yuǎn)離熱力學(xué)平衡態(tài)的條件下生成，動力學(xué)因素對材料結(jié)構(gòu)具有重要的調(diào)控作用，因此本文以卟啉分子自組裝過程為例，以組裝分子的擴(kuò)散和組裝速率為調(diào)控手段，研究這兩個動力學(xué)因素對自組裝結(jié)構(gòu)的調(diào)控作用和規(guī)律，為制備卟啉自組裝光電材料提供相應(yīng)的理論依據(jù)。 通過調(diào)節(jié)溶液的pH值來調(diào)節(jié)四苯基卟啉（TPP）分子的組裝速率，分別在溶液pH1.5，6.5，12.0條件下進(jìn)行了卟啉分子組裝。在低pH條件下，TPP質(zhì)子化，靜電排斥作用使卟啉分子沿著分子平面滑移，形成head-to-tail的聚集形式。在高pH條件下，質(zhì)子化作用消失，分子間主要為π-π相互作用，此時分子堆疊方式為face-to-face。在pH接近中性時，π-π相互作用與靜電排斥作用之間的競爭，使得分子間的排列方式產(chǎn)生新的規(guī)則，導(dǎo)致了分子的非對稱性組裝，因而形成管狀結(jié)構(gòu)。因此，在不同pH條件下，靜電排斥力與π-π相互作用之間的競爭導(dǎo)致了分子聚集方式的差異，生成了不同結(jié)構(gòu)的組裝體。 接下來，通過改變醇水溶液中乙醇與水的體積比，來調(diào)控卟啉分子的擴(kuò)散速率，得到了帶狀、中空帶狀、中空管狀和實心柱狀結(jié)構(gòu)的組裝體。采用原位觀測法觀察了管狀結(jié)構(gòu)與柱狀結(jié)構(gòu)的生成過程，發(fā)現(xiàn)了不同醇水體系中TPP分子組裝行為的差異， TPP分子在溶液中分布和擴(kuò)散環(huán)境不同，會產(chǎn)生微觀濃度場，導(dǎo)致卟啉分子沿著不同的方向優(yōu)勢組裝，從而形成各種不同的結(jié)構(gòu)。因此，分子擴(kuò)散過程也是影響材料結(jié)構(gòu)的一個重要原因。
[Abstract]:The structure of nanomaterials determines their properties, so the preparation of materials with different structures is very important for the optimization and development of material properties, on the other hand. Diversity and complexity is an inherent feature of material structure, which makes it more difficult to control the preparation of material structure. Therefore, the development of effective methods and theories of material structure control is very slow. Considering that many complex structures are formed far from the thermodynamic equilibrium state, the kinetic factors play an important role in regulating the material structure. In this paper, the self-assembly process of porphyrin molecules is taken as an example, and the diffusion and assembly rate of the assembled molecules are taken as the means to study the regulation of these two kinetic factors on the self-assembly structure. It provides a theoretical basis for the preparation of porphyrin self-assembly optoelectronic materials. By adjusting the pH value of the solution, the assembly rate of TPP was adjusted at pH 1.5 ~ 6.5, respectively. Porphyrin molecules were assembled under the condition of 12.0.The porphyrin molecules slid along the molecular plane by electrostatic repulsion under the condition of low pH and protonation of TPP. The aggregation form of head-to-tail was formed. At high pH, the protonation disappeared and the intermolecular interaction was mainly 蟺-蟺. When pH is near neutral, the competition between 蟺-蟺 interaction and electrostatic repulsion results in new rules of molecular arrangement. Therefore, the competition between electrostatic repulsion force and 蟺-蟺 interaction leads to the difference of molecular aggregation mode under different pH conditions. Different structures of the assembly were formed. Next, the diffusion rate of porphyrin molecules was regulated by changing the volume ratio of ethanol to water in alcohol aqueous solution, resulting in banded and hollow banded porphyrin molecules. In situ observation method was used to observe the formation process of tubular and columnar structures, and the difference of assembly behavior of TPP molecules in different alcohol-water systems was found. Different distribution and diffusion environment of TPP molecules in solution will produce microcosmic concentration field, leading porphyrin molecules to be assembled in different directions, thus forming a variety of different structures. The molecular diffusion process is also an important factor affecting the structure of materials.
【學(xué)位授予單位】：哈爾濱理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：O626;TB383.1

【參考文獻(xiàn)】

相關(guān)期刊論文 前5條

1 王蘭芝,佘遠(yuǎn)斌,徐未未,張燕慧,紀(jì)紅兵;金屬卟啉類模擬酶催化劑研究[J];化學(xué)進(jìn)展;2005年04期

2 吳迪,吳健;卟啉的分子自組裝[J];化學(xué)世界;2004年10期

3 宋鈺珠，古昆，杜官本，，何森泉;卟啉化學(xué)簡介[J];云南化工;1996年01期

4 章詠華,馮連玉;鈷卟啉修飾電極為基底的葡萄糖酶電極[J];應(yīng)用化學(xué);1990年04期

5 楊建東;王都留;盧小泉;;卟啉微納米材料的制備及應(yīng)用研究進(jìn)展[J];應(yīng)用化學(xué);2012年10期

本文編號：1484264