水溶性多吡啶铜水氧化催化剂

发布时间：2018-06-06 04:42

本文选题：铜 + 光催化　；参考：《陕西师范大学》2016年硕士论文

【摘要】：本文分别研究了水溶性的多吡啶铜配合物[Cu(F_3tpa)ClO_4]C]O_4(tpa= tris-(2-pyridylmethyl)amine)催化剂在光化学和电化学氧化水的性能。在光化学三组分的体系中,配合物Cu-F_3tpa作为光驱动的WOC, [Ru(bpy)_3](ClO_4)_2作为光敏剂,过硫酸钠作为电子牺牲体。在不同的催化条件下,TON数值最高达到(11.61±0.23),且TOF最高达到(1.58±0.03)×10~(-1) s~(-1)。在电催化氧化水的均相体系中,我们利用ITO电极作为工作电极,在1.8V vs NHE条件下电解2 h,配合物Cu-F_3tpa的TON数最高达到8.2,相对应的TOF值可以达到0.38 s~(-1)。在起峰电位表现出较低的过电势值,即610 mV。配合物Cu-F_3tpa的催化活性要比[Cu(TPA)(ClO_4)_2]好,因此可以推断F吸电子取代基团起到一定的效应,使得配合物Cu-F_3tpa的中心金属呈现一定的高价态,那样更有利于催化剂氧化水的进行。从测试结果来看,配合物Cu-F_3tpa具有在光电化学领域应用的潜力。我们在总结前人工作的基础上以F_3tpa为配体,以六水合高氯酸铜为金属盐,利用乙醚扩散法培养出晶体配合物[Cu(F_3tpa)ClO_4]ClO_4。本文主要研究内容及结果包括以下几个方面：1.本论文采用传统的培养晶体的方法,以乙腈为良溶剂,乙醚为不良溶剂,培养出晶型较好的[Cu(F_3tpa)ClO_4]ClO_4配合物晶体,利用X-射线单晶衍射仪检测,经过对其晶体结构的分析,所得的晶体结构是四角双锥形。2.配合物进行了核磁共振波谱仪测试,根据出峰位置可以得出该配体是我们所需要的配体；同时,对其合成的最终配合物[Cu(F_3tpa)ClO_4]ClO_4测试了高效液相色谱,可以确定最终合成出的配合物就是我们所需要的目标产物。3.对配合物Cu-F_3tpa进行光化学分析,采用的条件是：[Ru(bpy)_3](ClO_4)_2作为光敏剂,过硫酸钠作为电子受体,75 mM pH 85硼酸缓冲溶液,光源的波长范围是λ=470±10 nm。利用标准Clark电极对其配制的溶液测试光催化水氧化活性,结果表明该催化剂具有一定产氧能力。通过测试动态光散射(DLS)和丁达尔效应等,可以得出光催化三组分体系中没有纳米颗粒形成。4.对配合物Cu-F_3tpa进行电化学分析,采用的是三电极系统：以铂丝为对电极、银/氯化银电极(含有饱和氯化钾溶液)为参比电极和1 cm~2的ITO为工作电极,0.1 M硼酸缓冲溶液为电解质溶液。催化剂在起峰电位134 V vs NHE处产生较低的过电势值,相对于已报道过的有关电催化水氧化的铜配合物小。通过测试不同催化剂浓度、不同扫描速率以及不同pH的循环伏安图,对其数据进行处理,可以得出该催化剂具有电催化水氧化的活性,且催化后没有纳米颗粒生成,是均相溶剂体系。与此同时,对电解前后的工作电极的表面形态进行了电镜扫描(SEM)和能谱分析(EDS)测试,且对电催化水氧化后的体系进行DLS和丁达尔效应表征,以上结果都表明了配合物Cu-F_3tpa在电催化水氧化后没有发生分解,具有良好的稳定性。
[Abstract]:In this paper, the photochemical and electrochemical oxidation of water over water-soluble polypyridine copper complex [Cu(F_3tpa)ClO_4] C] O _ S _ 4 TPA = tris-tpa = 2-pyridylmethylamine has been studied. In the photochemical three-component system, the complex Cu-F_3tpa is used as photo-driven WOC, [Ru(bpy)_3] ClO4S _ 2 is used as Guang Min agent, and sodium persulfate is used as electron sacrificial. Under different catalytic conditions, the maximum value of ton was 11.61 卤0.23, and the maximum of TOF was 1.58 卤0.03 脳 10 ~ (-1) ~ (-1) ~ (-1) 路s ~ (-1) ~ (-1). In the homogeneous system of electrocatalytic oxidation of water, we use ITO electrode as working electrode, electrolysis at 1.8 V vs NHE for 2 h, the TON number of complex Cu-F_3tpa is up to 8.2, and the corresponding TOF value can reach 0.38 s-1 ~ (-1). The peak potential showed a lower over potential value, that is, 610 MV. The catalytic activity of the complex Cu-F_3tpa is better than [Cu(TPA)(ClO_4)_2], so it can be inferred that the electron-absorbing group of F plays a certain role, which makes the central metal of the complex Cu-F_3tpa present a certain high valence state, which is more favorable to the oxidation of water over the catalyst. From the test results, the complex Cu-F_3tpa has the potential to be applied in the field of photochemistry. The crystal complex [Cu(F_3tpa)ClO_4] CIO _ 4 was prepared by ether diffusion method with F_3tpa as ligand and copper perchlorate hexahydrate as metal salt. The main contents and results of this paper include the following aspects: 1. In this paper, the crystal of [Cu(F_3tpa)ClO_4] ClO_4 complex with good crystal form was obtained by using acetonitrile as good solvent and ether as bad solvent. The crystal structure was analyzed by X-ray single crystal diffractometer. The crystal structure obtained is tetragonal bicone. 2. The complex was tested by NMR spectrometer, and the ligand was found to be the ligands we needed according to the peak location, and the [Cu(F_3tpa)ClO_4] ClO_4, the final complex, was used to test the ligands in high performance liquid chromatography (HPLC). It can be determined that the final synthesized complex is the target product. 3. The photochemical analysis of the complex Cu-F_3tpa was carried out under the following conditions: [Ru(bpy)_3] clo _ 4s _ 2 was used as Guang Min agent, sodium persulfate as electron receptor 75 mm pH 85 boric acid buffer solution, and the wavelength range of light source was 位 ~ (470 卤10) nm. The photocatalytic activity of water oxidation was tested by using standard Clark electrode. The results showed that the catalyst had a certain ability to produce oxygen. By measuring the dynamic light scattering (DLS) and the Dundar effect, it can be concluded that there are no nanoparticles forming .4in the photocatalytic three-component system. A three-electrode system was used for electrochemical analysis of the complex Cu-F_3tpa, in which platinum wire was used as the opposite electrode. Silver / silver chloride electrode (containing saturated potassium chloride solution) was used as reference electrode and 1 cm~2 ITO as working electrode and 0.1 M boric acid buffer solution as electrolyte solution. The catalyst produced a lower overpotential at the peak potential of 134 V vs NHE, which is smaller than that of the reported copper complexes for the electrocatalytic oxidation of water. By measuring the cyclic voltammogram of different catalyst concentration, different scanning rate and different pH, it can be concluded that the catalyst has the activity of electrocatalytic water oxidation, and no nanoparticles are formed after catalysis. It is a homogeneous solvent system. At the same time, the surface morphology of the working electrode before and after electrolysis was measured by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), and the electrocatalytic water oxidation system was characterized by DLS and Dindall effect. The above results show that the complex Cu-F_3tpa does not decompose after electrocatalytic water oxidation and has good stability.
【学位授予单位】：陕西师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O643.36

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