气敏材料是气体（化学）传感器的核心部位，直接影响传感器的稳定性、选择性、灵敏度和响应时间等各种性能。卟啉与金属卟啉配合物具有优良的气敏性能，目前国内外卟啉与金属卟啉传感器已应用于VOCs的检测。该文介绍了卟啉及其结构、合成方法、卟啉和金属卟啉配合物的合成及影响因素；卟啉和金属卟啉在传感器中的应用和对挥发性有机气体的检测原理。

Gas sensitive material is the core part of gas (chemical) sensor; it would directly affects the sensors stability, selectivity, sensitivity and its response time. Porphyrins and metalloporphyrins have excellent gas sensing properties, at present, porphyrins and metalloporphyrins sensors have been applied to detected the VOCs, both in China and abroad.In this paper,has been Introduced the porphyrins and its structure, synthesis method, synthesis of porphyrins and metalloporphyrins complexes and the influencing factors;metalloporphyrins application in sensors and the detection principle of VOCs.

以5-对氨基苯基-10,15,20-三苯基卟啉为起始物,经过金属插入反应以及与丙烯腈/丙烯酸共聚物侧链的反应,获得了高聚物负载卟啉铁和卟啉钴,结构经UV-Vis、IR光谱测定得到证实.将此高聚物负载金属卟啉用于光催化体系,进行有机染料亚甲基蓝水溶液的光催化降解.实验发现,利用自然光,经6h照射后,亚甲基蓝水溶液脱色率可达64.6%,表明高聚物负载卟啉催化剂有良好催化降解性能.

Two polymer-supported metalloporphyrins, including porphinatoiron and porphinatocobalt, were synthesized through metal insertion reaction on 5-(p-aminophenyl)-10,15,20-triphenylporphyrin and subsequent reaction with random copolymer of acrylic nitrile and acrylic acid. The structures of obtained compounds were confirmed by UV-Vis and IR characterization. The polymer-supported metalloporphyrins were investigated as the photocatalyst for the degradation of methylene blue. It was found that the decolorization efficiency was up as 64.6% after 6h illumination with natural sunlight, indicating the high photocatalytic activity of the polymer-supported metalloporphyrins.

合成了一系列石墨烯-金属四苯基卟啉(GR-MTPP)的复合材料,并将该复合材料作为电催化剂应用于氧气还原反应中。通过金属离子与四苯基卟啉发生配位反应得到金属四苯基卟啉(FeTPP、CoTPP、NiTPP、CuTPP、ZnTPP、MnTPP),进一步通过π-π堆积作用合成了一系列新型的石墨烯-金属卟啉复合材料,并将其修饰到玻碳电极上,研究其催化氧气还原的反应。结果表明,该复合材料在DMF与水的混合溶剂中分散性能良好;石墨烯与金属卟啉的协同作用使其催化氧气还原性能更优;该类复合材料尤其是GR-FeTPP与GR-CoTPP在中性溶液中(pH=7.0)显示出良好的对氧气还原的电催化性能。GR-FeTPP催化氧气还原的电位在-0.24 V处,响应电流为85μA;GR-CoTPP催化氧气还原的电位在-0.19 V,响应电流为44μA。表明石墨烯-金属卟啉复合材料是氧气传感器良好的电催化剂。

A series of graphene-metal-tetraphenylporphyrin(GR-MTPP) nanocomposite materials were prepared and applied in the oxygen reduction reaction as efficient electrocatalysts. MTPPs (FeTPP,CoTPP,NiTPP,CuTPP,ZnTPP and MnTPP) were synthesized via a coordination reaction between metal ions and TPP. Graphene -metal -tetraphenylporphyrin nanocomposition materials were successfully prepared by the π -π stacking interaction and applied in the electrocatalytic oxygen reduction reaction. The results showed that GR-MTPPs exhibited enhanced electrocatalytic activity toward oxygen reduction due to the synergistic effect between the graphene and MTTP. The large electro-active surface area and fast charge transfered of graphene facilitated the electrocatalytic oxygen reduction of MTPP. The GR-FeTPP showed the peak potential at -0.24 V with the current response of 85 μA for the eletrocatalytic reduction of oxygen. The GR-CoTPP showed the peak potential at -0.19 V with the current response of

通过区域选择性合成,得到了单取代的β-硝基四苯基卟啉金属配合物,经脱金属和还原得到β-氨基四苯基卟啉,再以活化过的中性氧化铝为催化剂,经加成脱水,合成了一种新的不对称单取代β-甲酰基二茂铁席夫碱四苯基卟啉.所合成化合物的结构经IR、1H NMR、MS、UV-Vis证实.

When a substituent group is incorporated onto theβ-pyrrolic position of a meso-substituted porphyrin, the planar of porphine core will be twisted out of the shape due to the steric hindrance. When ferrocene, which has a particular structure with a redox group, is introduced to the porphin core, the obtained compound would be expected to be a new kind of functional materials. Here the synthesis of a novel porphyrin mono-substituted with an formyl-ferrocene Schiff-base at theβ-pyrrolic position is reported. All of the compounds are characterized by elemental analysis, IR, UV-Vis, 1H NMR and MS.

结合笔者的工作,总结了近几年四氮杂卟啉及其金属配合物、聚合物和超分子体系研究的主要新进展和新成果.给出了对某些中文术语的科学界定,以及当前关于四氮杂卟啉化合物研究的主要特点和发展趋势.

Combined with the series of works made by the authors, the recent progresses in the research of porphyrazines and their complexes were reviewed. The latest advances about monomers, polymers and supramolecules of porphyrazines were specially discussed. Promising applications and new orientations in the future research were also presented.