【摘要】：卟啉廣泛存在于自然界中,具有強(qiáng)的光敏性,超快的電子轉(zhuǎn)移性和高的光捕獲系數(shù),在生命體中起著非常重要的作用。它們?cè)谏w中與其它分子或器官?gòu)?fù)合組裝,發(fā)揮出獨(dú)特的生物催化活性。因此,研究卟啉分子的組裝,開(kāi)發(fā)新的卟啉類復(fù)合材料,提高卟啉分子催化活性,有助于我們?cè)谏飳W(xué)、化學(xué)、光電子學(xué)和醫(yī)藥學(xué)取得進(jìn)一步發(fā)展。針對(duì)這一研究目的,本論文以卟啉為基礎(chǔ)反應(yīng)物,結(jié)合二氧化鈦和石墨烯等優(yōu)良的納米材料,合成了一系列的卟啉類的復(fù)合材料,并將它們有效的用于氧還原反應(yīng)、光催化降解、電催化氧化和抑菌作用等。具體創(chuàng)新研究如下:(1)在燃料電池的實(shí)際應(yīng)用中,其陰極發(fā)生的氧還原反應(yīng)(ORR)起著非常重要的作用。于此,通過(guò)溶劑熱反應(yīng)的方法成功制備了類似花朵結(jié)構(gòu)的二氧化鈦/石墨烯修飾的氯化血紅素超結(jié)構(gòu)分子復(fù)合材料(TiO_2/Gr/Hem)。該化合物經(jīng)過(guò)高溫?zé)崽幚?對(duì)復(fù)合材料的電催化活性進(jìn)行了分析,結(jié)果表明經(jīng)過(guò)700 ℃熱處理的復(fù)合材料呈現(xiàn)出最高的ORR電催化活性。熱處理提高了吡啶N和吡咯N的百分含量以及增加了材料結(jié)構(gòu)缺陷、活性位點(diǎn)和幾何復(fù)雜性,因此熱處理溫度對(duì)催化劑的活性起著關(guān)鍵性的影響。相比較于TiO_2/Gr和Gr/Hem催化劑,TiO_2/Gr/Hem復(fù)合材料表現(xiàn)出更高的ORR催化活性。此外,復(fù)合材料中的鐵元素對(duì)ORR呈現(xiàn)出抑制效應(yīng),在堿性溶液中Ti-C-N材料相比較Ti-C-N-Fe材料具有更高的ORR催化活性。同時(shí),實(shí)驗(yàn)證明了 TiO_2/Gr/Hem復(fù)合材料在ORR電催化過(guò)程中具有更高的抗甲醇中毒能力和強(qiáng)的穩(wěn)定性。這些結(jié)果說(shuō)明了裂解溫度和化合物元素組成對(duì)于復(fù)合材料用作ORR電催化劑起著關(guān)鍵影響。(2)通過(guò)快速自組裝的方法制備了三維結(jié)構(gòu)的氯化血紅素-功能化的石墨烯水凝膠(Hem/GH)。制備得到的Hem/GH呈現(xiàn)出存儲(chǔ)模量為609-642 kPa的高機(jī)械強(qiáng)度和好的有機(jī)染料吸附能力(對(duì)羅丹明B的吸附量為341 mg g~(-1))。與單純的石墨烯水凝膠(GH)和商業(yè)用的P25相比,Hem/GH可以用作光敏劑對(duì)MB表現(xiàn)出更高的光催化降解活性。即便Hem/GH材料多次用來(lái)吸附和光催化降解MB,它仍舊保持較好的穩(wěn)定性和活性。同時(shí)發(fā)現(xiàn),當(dāng)光催化降解MB之后,其溶液的pH值從堿性的8.99轉(zhuǎn)變?yōu)樗嵝缘?.82,總有機(jī)碳含量只剩下10%。并通過(guò)液相色譜/時(shí)間飛行-質(zhì)譜(LC/TOF-MS)對(duì)光催化MB的降解產(chǎn)物進(jìn)行了分析。隨后通過(guò)捕獲劑的捕獲實(shí)驗(yàn)對(duì)MB的光催化降解機(jī)制進(jìn)行了研究,結(jié)果證實(shí)了 MB的降解主要受到超氧負(fù)離子自由基的影響。作為拓展應(yīng)用,以直接觀察的方法說(shuō)明了 Hem/GH材料還具有強(qiáng)的抑菌性能。Hem/GH材料擁有的高吸附性能、優(yōu)良的光催化降解活性和強(qiáng)的抑菌作用使它具有潛在的實(shí)際應(yīng)用價(jià)值。(3)材料的表面結(jié)構(gòu)對(duì)于構(gòu)建光電器件并用于催化和生物學(xué)方面具有重要的影響。在本工作中以二氧化鈦、原卟琳IX和氯化血紅素為反應(yīng)物,通過(guò)聚苯乙烯模板去除的方法制備得到了雙卟啉(TiO_2/PPIX/Hem)的蜂巢狀薄膜。相比較Ti02和TiO_2/PPIX,雙卟啉TiO_2/PPIX/Hem的蜂巢狀薄膜展示了更高的光電流響應(yīng),證實(shí)了雙卟啉復(fù)合材料具有更好的光電轉(zhuǎn)換效率和協(xié)同效應(yīng)。在可見(jiàn)光照射下,雙卟啉TiO_2/PPIX/Hem的蜂巢狀薄膜作為良好的光敏劑能夠有效的產(chǎn)生單線態(tài)氧(~1O_2),并以此來(lái)抑制細(xì)菌的生長(zhǎng)。此外,還制備了其它類型的雙卟啉(TiO_2/MnPPIX/Hem,TiO_2/CoPPIX/Hem,TiO_2/NiPPIX/Hem,TiO_2/CuPPIX/Hem和TiO_2/ZnPPIX/Hem)的蜂巢狀薄膜,并對(duì)它們產(chǎn)生單線態(tài)氧的情況進(jìn)行了對(duì)比分析,證實(shí)了雙卟啉的薄膜可明顯的提高復(fù)合材料的光電轉(zhuǎn)換性能。這種高性能的雙卟啉復(fù)合材料為人們開(kāi)發(fā)光電化學(xué)器件和生物醫(yī)藥等應(yīng)用方面提供了很好的參考意義。(4)通過(guò)自下向上的方法制備了卟啉基的二維(2D)金屬-有機(jī)骨架(MOF)納米圓盤(pán)�；诔珊苏{(diào)節(jié)劑4,4'-聯(lián)苯二甲酸(BPDC)和反應(yīng)溶劑的影響,產(chǎn)物Zn-TCPP納米圓盤(pán)的粒徑可以有效的調(diào)節(jié),同時(shí)提出了其粒徑大小的調(diào)控機(jī)理。通過(guò)進(jìn)一步表征和分析Zn-TCPP(BP)納米圓盤(pán)的形態(tài),明顯的觀察到了 Zn-TCPP(BP)的MOF結(jié)構(gòu)。這種Zn-TCPP(BP)納米圓盤(pán)對(duì)亞硝酸根離子表現(xiàn)出明顯的電催化活性和高靈敏檢測(cè)性,其靈敏度為158.1 μAmM~(-1) cm~(-2)。同時(shí)它還對(duì)亞硝酸根離子表現(xiàn)出優(yōu)良的選擇性,其最低檢測(cè)限為0.26 μM。卟啉分子在這種MOF結(jié)構(gòu)中以單分子形式存在,而納米圓盤(pán)本身又類似三明治結(jié)構(gòu),這些特點(diǎn)都有效的增加了Zn-TCPP(BP)納米圓盤(pán)的可接觸活性位點(diǎn),提高了對(duì)亞硝酸根離子的檢測(cè)靈敏度,降低了檢測(cè)限。
[Abstract]:Porphyrins are ubiquitous in nature and play an important role in living organisms because of their strong photosensitivity, ultrafast electron transfer and high light capture coefficient. They are assembled with other molecules or organs in living organisms and play a unique biocatalytic activity. Therefore, the assembly of porphyrins and the development of new porphyrins are studied. To improve the catalytic activity of porphyrin molecules, we have made further progress in biology, chemistry, optoelectronics and medicine. For this purpose, we have synthesized a series of porphyrin composite materials based on porphyrin and combined with titanium dioxide and graphene and other excellent nano-materials. They are effective in oxygen reduction, photocatalytic degradation, electrocatalytic oxidation and bacteriostasis. Specific innovations are as follows: (1) In the practical application of fuel cells, the oxygen reduction reaction (ORR) on the cathode plays a very important role. Thus, titanium dioxide with flower-like structure was successfully prepared by solvothermal reaction. The graphene modified hemin superstructure molecular composite (TiO_2/Gr/Hem). The electrocatalytic activity of the composite was analyzed after high temperature heat treatment. The results showed that the composite exhibited the highest ORR electrocatalytic activity after heat treatment at 700 C. The percentage of pyridine N and pyrrole N was increased by heat treatment. Compared with the TiO_2/Gr and Gr/Hem catalysts, the TiO_2/Gr/Hem composite exhibits higher ORR catalytic activity. In addition, the iron element in the composite exhibits an inhibitory effect on the ORR and is found to be alkaline. Compared with Ti-C-N-Fe material, Ti-C-N-N-Fe material has higher ORR catalytic activity in solution. At the same time, the experiment proves that the TiO_2/Gr/Hem composite material has higher methanol poisoning resistance and strong stability in ORR electrocatalytic process. These results show that the cracking temperature and the composition of compound elements are important for the composite materials to be used as ORR electrocatalysts. (2) Three-dimensional heme chloride-functionalized graphene hydrogel (Hem/GH) was prepared by rapid self-assembly method. The prepared hem/GH exhibited high mechanical strength with storage modulus of 609-642 kPa and good adsorption capacity for organic dyes (adsorption capacity for rhodamine B was 341 mg g-1). Compared with pure stone, the hem/GH hydrogel exhibited high mechanical strength and good adsorption capacity for organic dyes. Compared with commercial P25, Hem/GH can be used as a photosensitizer to show higher photocatalytic degradation activity for MB. Even though Hem/GH material has been used to adsorb and photocatalytic degradation MB for many times, it still maintains good stability and activity. At the same time, it was found that the pH value of the solution changed from 8.99 to 8.99 after photocatalytic degradation of MB. The degradation products of photocatalytic MB were analyzed by liquid chromatography/time-of-flight mass spectrometry (LC/TOF-MS). The photocatalytic degradation mechanism of MB was studied by trapping experiment. The results showed that the degradation of MB was mainly affected by superoxide anion radical. Hem/GH materials have high adsorption capacity, excellent photocatalytic degradation activity and strong bacteriostasis, which make it have potential practical application value. (3) Surface structure of hem/GH materials for the construction of optoelectronic devices and for catalysis and biology. In this work, the honeycomb-like films of bisporphyrin (TiO_2/PPIX/Hem) were prepared by polystyrene template removal method using titanium dioxide, protoporphyrin IX and Hemin as reactants. Compared with Ti02 and TiO_2/PPIX, the honeycomb-like films of bisporphyrin TiO_2/PPIX/Hem exhibited higher photocurrent response. The results show that the biporphyrin composite has better photoelectric conversion efficiency and synergistic effect. Under visible light irradiation, the biporphyrin titanium dioxide/PPIX/Hem honeycomb film as a good photosensitizer can effectively produce singlet oxygen (~1O_2) and inhibit the growth of bacteria. In addition, other types of biporphyrin (TiO_2/MnPPIX/Hem) were prepared. The honeycomb-like films of TiO_2/CoPPIX/Hem, TiO_2/NiPPIX/Hem, TiO_2/CuPPIX/Hem and TiO_2/ZnPPIX/Hem have been compared and analyzed. The results show that the photoelectric conversion properties of the composites can be improved obviously by the biporphyrin films. (4) Porphyrin-based two-dimensional (2D) metal-organic frameworks (MOF) Nanodiscs were fabricated by bottom-up method. Based on the influence of nucleation regulator 4,4'-biphthalic acid (BPDC) and reaction solvent, the particle size of the product Zn-TCPP Nanodiscs can be effectively adjusted, and the effect of the reaction solvent on the size of the product Zn-TCPP Nanodiscs can also be observed. By further characterization and analysis of the morphology of Zn-TCPP (BP) nanodiscs, the MOF structure of Zn-TCPP (BP) was observed. The Zn-TCPP (BP) Nanodiscs exhibited obvious electrocatalytic activity and high sensitivity for the detection of nitrite ions with a sensitivity of 158.1 mu AmM~(-1) cm~(-2). It also exhibits excellent selectivity to nitrite ions with a minimum detection limit of 0.26 mu M. Porphyrin molecules exist as single molecules in this MOF structure, while the nanodisk itself is similar to the sandwich structure. These characteristics effectively increase the contactable active sites of Zn-TCPP (BP) nanodisk and enhance the nitrite ionization. The detection sensitivity is reduced and the detection limit is reduced.
【學(xué)位授予單位】：東南大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB33;O643.36

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