【作者】 姑力米热·吐尔地（Gulmira Tuerdi）；

【导师】 阿布力孜·伊米提（Abliz Yimit）；

【作者基本信息】 新疆大学 ， 化学， 2018， 博士

【摘要】 随着国民经济的快速发展,各种污染物的生产量越来越多,其中有毒有害气体对人类生存空间的污染更为突出。因此,能够检测低浓度有毒有害环境污染物的化学传感器的开发显得尤为迫切。本文主要研究了基于卟啉及其金属配合物的化学传感器的研制;自由基卟啉及其衍生物的电子跃迁行为和气敏性;自由基卟啉与酸性气体的相互作用;基于自由基卟啉及其衍生物的光学和电化学传感器的研制,根据电化学传感器对被测气体的响应信号进一步判断卟啉及其衍生物的半导体类型。主要研究内容如下:（1）通过Alder和Lindsey等方法成功合成了四苯基卟啉（TPP）,四苯基卟啉锌（ZnTPP）、四苯基卟啉铜（CuTPP）和Meso-四（4-硝基苯基）卟啉（TNPP）。利用紫外-可见吸收光谱、傅里叶红外光谱、核磁共振（氢谱）等表征手段检测了它们光谱特征,以及通过X-射线光电子能谱（XPS）对CuTPP粉末中Cu离子的价态进行表征。结果显示,金属取代卟啉与自由基卟啉（TPP）相比,其Soret-峰向蓝移（ZnTPP和CuTPP的蓝移程度不一样）,而TNPP的Soret-峰向红移,这与硝基卟啉的吡咯环的电子跃迁有关。红外光谱中,卟啉环内N-H键的消失和金属-H键的出现表明金属卟啉的生成。TNPP中吸电子基团降低了卟啉分子外围电子云密度,导致了其氢原子向低磁场位移。CuTPP的XPS数据显示,在配合物中Cu离子的价态为2。（2）将TPP用匀胶机涂敷于玻璃光波导（OWG）表面,通过一定量H₂S气体处理,研制了气相质子化的TPP薄膜,并研发了NH₃气体传感器。结果表明,H₂S气体暴露后,因薄膜表面TPP单体质子化而形成J-型聚集体。质子化的TPP薄膜光波导传感元件作为NH₃受体,因为NH₃与质子化的TPP薄膜接触之后会导致质子化的TPP薄膜脱质子化,从而气相质子化的TPP薄膜表面的J-型聚集体变成游离单体。在这种情况下,H₂S气体可用于增加TPP薄膜中J-型聚集体的相对量并恢复传感器的响应。通过¹H NMR光谱,原子力显微镜（AFM）和紫外-可见吸收光谱（UV-vis）分析TPP薄膜的可逆表面形态。此外,在室温状态下,TPP电化学传感器对H₂S、NO₂等气体具有一定的响应。（3）将金属卟啉ZnTPP作为光波导传感器的敏感材料,在一定条件下铺成薄膜,检测了NO₂气体。利用AFM和扫描电镜（SEM）对传感元件的表面形貌进行表征。传感元件与NO₂气体作用前后的光谱变化通过UV-vis、FT-IR并X-射线衍射光谱（XRD）等表征方法来进行考察并对气敏机理进行了探讨。结果表明,Zn TPP与NO₂的气敏机理经过两步反应进行,反应的第一步反映在红外吸收光谱的变化上,而第二步则直接引起敏感元件的颜色变化。并且,通过ZnTPP作为敏感材料,研制电化学传感元件并检测其对NO₂气敏性,发现其检测限远远高于光波导方法检测的最低浓度。（4）将CuTPP在一定条件下固定在光波导表面铺成薄膜,并将CuTPP涂覆于陶瓷管表面研制了电化学气敏元件,检测了这两种敏感元件对各种气体的气敏性响应。通过AFM、SEM等方法对其表面形貌进行表征。CuTPP薄膜气敏特性与ZnTPP薄膜/K⁺-交换OWG气敏元件一致,但是其对NO₂气体的气敏性不如ZnTPP气敏元件好。同时,CuTPP气敏元件与NO₂气体作用前后的气敏机理进行探讨。结果表明,气敏机理与ZnTPP气敏元件和NO₂气体之间的气敏机理一致。（5）硫化氢（H₂S）和乙二胺等工业废气的检测对健康和安全至关重要。基于固定在Nafion膜（Nf）中并沉积在光波导载玻片上的TNPP的吸收光谱,开发了用于检测这些气体的光学传感器。对TNPP和Nf-TNPP复合材料改性的传感器的响应进行了比较。其中,Nf-TNPP对H₂S和乙二胺显示出显著的响应信号。研究了Nf-TNPP修饰传感器对H₂S和乙二胺的响应特性,并详细讨论了其响应机理。该传感器具有出色的重现性,可逆性和选择性;H₂S和乙二胺的检测限分别为7×10^-10（V/V₀）和1×10^-8（V/V₀）,是工业传感应用领域的一个很有前途的检测方法。此外,TNPP电化学传感器对各种气体的响应表明,其半导体类型与TPP电化学传感器一致。更多还原

【Abstract】 The amount of pollutants are becoming more and more along with the development of national economy,among them,toxic or harmful gases are the main cause that accrue pollution in human living area.Therefore,it is indispensible to develop low-cost chemical sensors to accurately detect toxic substance with low concentration.This paper mainly concentrates on the development of chemical sensors based on porphyrin and it’s metal complexes;the electronic transition behavior and gas sensitivity of free-base porphyrins and it`s derivatives;interaction of free-base porphyrin with acidic gases;development of optical and electrochemical sensors based on free-base porphyrin and it`s derivatives;comparison of two gas detection methods at room temperature.The semiconductor-type of porphyrins and it`s derivatives were discussed by response signals of electrochemical sensors when exposed to analyte gases.The more details are as follows:（1）Tetraphenylporphyrin（TPP）,zinc tetraphenylporphyrin（ZnTPP）,copper tetraphenylporphyrin（CuTPP）and Meso-tetrakis（4-nitrophenyl）porphyrin（TNPP）were synthesized by Alder and Lindsey method.UV-vis spectra,Fourier infrared（FT-IR）spectroscopy,nuclear magnetic resonance（¹H NMR）were applied to study thier spectral charactersitics;besides X-ray phtoelectron spectroscopy（XPS）was utilized to characterize valence state of Cu ions in CuTPP powders The results indicated that,Soret-peak of metalloporphyrins were blue shifted camparing to that of free-base porphyrin（blue-shift degreee of ZnTPP and CuTPP was different）,while the Soret-peak of TNPP is red-shifted,xhich is related to the electronic transition of the-NO₂ and porphyrin ring.The disappearance of the N-H bond and appearance of the metal-H bond in the FT-IR spectrum indicated formation of the metal porphyrin.Due to electron-withdrawing groups in TNPP,the density of electron clouds at the periphery of the porphyrin molecule is reduced,resulting in the displacement of hydrogen atoms to low magnetic fields.The XPS data of CuTPP showed that the valence of Cu ions in the complex was 2.（2）A glass optical waveguide was coated with a gas-phase protonated TPP thin film to develop a sensor for the detection of NH₃ gas.The results showed that the TPP thin film agglomerate to H-based J-type aggregates after treatment of TPP sensing element with H₂S gas.The protonated TPP molecules in the OWG sensing element acted as NH₃ receptors because of the gas-phase protonated TPP film morphologically changed from J-type aggregates to free base monomers when it was deprotonated by exposure to NH₃.In this case,H₂S gas could be used to increase the relative amount of J-type aggregation in the TPP film and restore the sensor response.The reversible surface morphology of the TPP film was analyzed by ¹H NMR spectroscopy,atomic force microscopy（AFM）,and UV-vis spectroscopy.In addition,TPP electrochemical sensors revealed certain response to H₂S,NO₂ gases at room temperature.（3）ZnTPP was used as sensing material to fabricate optical waveguide thin film for the detection of NO₂ gas.The surface morphology of the ZnTPP film was analyzed by AFM and SEM microscopies.Spectral changes of the gas-sensitive element before and after exposure to NO₂ gas were investigated by FT-IR,UV-vis and XRD,then gas-sensing mechansim was discussed.Experimental data indicated that,the gas-sensing mechanism of ZnTPP undergoes two-step reactions;first step reflected in the change of FT-IR,the second step chages the color of gas-sensing element.Furthermore,ZnTPP as a sensitive material,the electrochemical sensing element was developed and its gas sensitivity to NO₂ was monitored.The result depicted,detection limit was found to be much higher than the lowest concentration detected by the optical waveguide method.（4）The CuTPP was fixed on the surface of the optical waveguide to form thin films,and an electrochemical gas sensor was fabricated by coating CuTPP on the surface of the ceramic tube,then gas-sensitivity of the two sensitive elements to various gases was monitored.AFM and SEM microscopies were used to charatereised the surface morphologies of the sensitive element.The gas-sensing properties of CuTPP were the same with thoes of the ZnTPP film/K⁺-exchanged optical waveguide gas sensor,but the gas sensitivity to NO₂ gas was poorer than that of the ZnTPP gas sensor.Meanwhile,the gas-sensing mechansim of CuTPP sensitive element to NO₂gas was simular with that discribed in Zn TPP.（5）The detection of hydrogen sulfide（H₂S）and ethanediamine（EDA）,toxic gases emitted from industrial processes,is important for health and safety.An optical sensor,based on the absorption spectrum of TNPP immobilized in a Nafion membrane（Nf）and deposited onto an optical waveguide glass slide,has been developed for the detection of these gases.Responses to analytes were compared for sensors modified with TNPP and Nf-TNPP composites.Among them,Nf-TNPP exhibited significant responses to H₂S and EDA.The analytical performance characteristics of the Nf-TNPP-modified sensor were investigated and the response mechanism was discussed in detail.The sensor exhibited excellent reproducibilities,reversibilities,and selectivities,with detection limits for H₂S and EDA of 70 ppt and10 ppb,respectively,and is a promising candidate for use in industrial sensing applications.In addition,the response of TNPP electrochemical sensors to various gases showed that semiconductor-type of the TNPP was simular with that of TPP.更多还原