卟啉基复合材料的制备及光、电催化方面的研究
发布时间：2018-08-20 17:34
【摘要】：卟啉广泛存在于自然界中,具有强的光敏性,超快的电子转移性和高的光捕获系数,在生命体中起着非常重要的作用。它们在生命体中与其它分子或器官复合组装,发挥出独特的生物催化活性。因此,研究卟啉分子的组装,开发新的卟啉类复合材料,提高卟啉分子催化活性,有助于我们在生物学、化学、光电子学和医药学取得进一步发展。针对这一研究目的,本论文以卟啉为基础反应物,结合二氧化钛和石墨烯等优良的纳米材料,合成了一系列的卟啉类的复合材料,并将它们有效的用于氧还原反应、光催化降解、电催化氧化和抑菌作用等。具体创新研究如下:(1)在燃料电池的实际应用中,其阴极发生的氧还原反应(ORR)起着非常重要的作用。于此,通过溶剂热反应的方法成功制备了类似花朵结构的二氧化钛/石墨烯修饰的氯化血红素超结构分子复合材料(TiO_2/Gr/Hem)。该化合物经过高温热处理,对复合材料的电催化活性进行了分析,结果表明经过700 ℃热处理的复合材料呈现出最高的ORR电催化活性。热处理提高了吡啶N和吡咯N的百分含量以及增加了材料结构缺陷、活性位点和几何复杂性,因此热处理温度对催化剂的活性起着关键性的影响。相比较于TiO_2/Gr和Gr/Hem催化剂,TiO_2/Gr/Hem复合材料表现出更高的ORR催化活性。此外,复合材料中的铁元素对ORR呈现出抑制效应,在碱性溶液中Ti-C-N材料相比较Ti-C-N-Fe材料具有更高的ORR催化活性。同时,实验证明了 TiO_2/Gr/Hem复合材料在ORR电催化过程中具有更高的抗甲醇中毒能力和强的稳定性。这些结果说明了裂解温度和化合物元素组成对于复合材料用作ORR电催化剂起着关键影响。(2)通过快速自组装的方法制备了三维结构的氯化血红素-功能化的石墨烯水凝胶(Hem/GH)。制备得到的Hem/GH呈现出存储模量为609-642 kPa的高机械强度和好的有机染料吸附能力(对罗丹明B的吸附量为341 mg g~(-1))。与单纯的石墨烯水凝胶(GH)和商业用的P25相比,Hem/GH可以用作光敏剂对MB表现出更高的光催化降解活性。即便Hem/GH材料多次用来吸附和光催化降解MB,它仍旧保持较好的稳定性和活性。同时发现,当光催化降解MB之后,其溶液的pH值从碱性的8.99转变为酸性的3.82,总有机碳含量只剩下10%。并通过液相色谱/时间飞行-质谱(LC/TOF-MS)对光催化MB的降解产物进行了分析。随后通过捕获剂的捕获实验对MB的光催化降解机制进行了研究,结果证实了 MB的降解主要受到超氧负离子自由基的影响。作为拓展应用,以直接观察的方法说明了 Hem/GH材料还具有强的抑菌性能。Hem/GH材料拥有的高吸附性能、优良的光催化降解活性和强的抑菌作用使它具有潜在的实际应用价值。(3)材料的表面结构对于构建光电器件并用于催化和生物学方面具有重要的影响。在本工作中以二氧化钛、原卟琳IX和氯化血红素为反应物,通过聚苯乙烯模板去除的方法制备得到了双卟啉(TiO_2/PPIX/Hem)的蜂巢状薄膜。相比较Ti02和TiO_2/PPIX,双卟啉TiO_2/PPIX/Hem的蜂巢状薄膜展示了更高的光电流响应,证实了双卟啉复合材料具有更好的光电转换效率和协同效应。在可见光照射下,双卟啉TiO_2/PPIX/Hem的蜂巢状薄膜作为良好的光敏剂能够有效的产生单线态氧(~1O_2),并以此来抑制细菌的生长。此外,还制备了其它类型的双卟啉(TiO_2/MnPPIX/Hem,TiO_2/CoPPIX/Hem,TiO_2/NiPPIX/Hem,TiO_2/CuPPIX/Hem和TiO_2/ZnPPIX/Hem)的蜂巢状薄膜,并对它们产生单线态氧的情况进行了对比分析,证实了双卟啉的薄膜可明显的提高复合材料的光电转换性能。这种高性能的双卟啉复合材料为人们开发光电化学器件和生物医药等应用方面提供了很好的参考意义。(4)通过自下向上的方法制备了卟啉基的二维(2D)金属-有机骨架(MOF)纳米圆盘。基于成核调节剂4,4'-联苯二甲酸(BPDC)和反应溶剂的影响,产物Zn-TCPP纳米圆盘的粒径可以有效的调节,同时提出了其粒径大小的调控机理。通过进一步表征和分析Zn-TCPP(BP)纳米圆盘的形态,明显的观察到了 Zn-TCPP(BP)的MOF结构。这种Zn-TCPP(BP)纳米圆盘对亚硝酸根离子表现出明显的电催化活性和高灵敏检测性,其灵敏度为158.1 μAmM~(-1) cm~(-2)。同时它还对亚硝酸根离子表现出优良的选择性,其最低检测限为0.26 μM。卟啉分子在这种MOF结构中以单分子形式存在,而纳米圆盘本身又类似三明治结构,这些特点都有效的增加了Zn-TCPP(BP)纳米圆盘的可接触活性位点,提高了对亚硝酸根离子的检测灵敏度,降低了检测限。
[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.
【学位授予单位】：东南大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB33;O643.36
[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.
【学位授予单位】：东南大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB33;O643.36
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