本文選題：銅 + 光催化��； 參考：《陜西師范大學(xué)》2016年碩士論文

【摘要】：本文分別研究了水溶性的多吡啶銅配合物[Cu(F_3tpa)ClO_4]C]O_4(tpa= tris-(2-pyridylmethyl)amine)催化劑在光化學(xué)和電化學(xué)氧化水的性能。在光化學(xué)三組分的體系中,配合物Cu-F_3tpa作為光驅(qū)動(dòng)的WOC, [Ru(bpy)_3](ClO_4)_2作為光敏劑,過(guò)硫酸鈉作為電子犧牲體。在不同的催化條件下,TON數(shù)值最高達(dá)到(11.61±0.23),且TOF最高達(dá)到(1.58±0.03)×10~(-1) s~(-1)。在電催化氧化水的均相體系中,我們利用ITO電極作為工作電極,在1.8V vs NHE條件下電解2 h,配合物Cu-F_3tpa的TON數(shù)最高達(dá)到8.2,相對(duì)應(yīng)的TOF值可以達(dá)到0.38 s~(-1)。在起峰電位表現(xiàn)出較低的過(guò)電勢(shì)值,即610 mV。配合物Cu-F_3tpa的催化活性要比[Cu(TPA)(ClO_4)_2]好,因此可以推斷F吸電子取代基團(tuán)起到一定的效應(yīng),使得配合物Cu-F_3tpa的中心金屬呈現(xiàn)一定的高價(jià)態(tài),那樣更有利于催化劑氧化水的進(jìn)行。從測(cè)試結(jié)果來(lái)看,配合物Cu-F_3tpa具有在光電化學(xué)領(lǐng)域應(yīng)用的潛力。我們?cè)诳偨Y(jié)前人工作的基礎(chǔ)上以F_3tpa為配體,以六水合高氯酸銅為金屬鹽,利用乙醚擴(kuò)散法培養(yǎng)出晶體配合物[Cu(F_3tpa)ClO_4]ClO_4。本文主要研究?jī)?nèi)容及結(jié)果包括以下幾個(gè)方面：1.本論文采用傳統(tǒng)的培養(yǎng)晶體的方法,以乙腈為良溶劑,乙醚為不良溶劑,培養(yǎng)出晶型較好的[Cu(F_3tpa)ClO_4]ClO_4配合物晶體,利用X-射線單晶衍射儀檢測(cè),經(jīng)過(guò)對(duì)其晶體結(jié)構(gòu)的分析,所得的晶體結(jié)構(gòu)是四角雙錐形。2.配合物進(jìn)行了核磁共振波譜儀測(cè)試,根據(jù)出峰位置可以得出該配體是我們所需要的配體；同時(shí),對(duì)其合成的最終配合物[Cu(F_3tpa)ClO_4]ClO_4測(cè)試了高效液相色譜,可以確定最終合成出的配合物就是我們所需要的目標(biāo)產(chǎn)物。3.對(duì)配合物Cu-F_3tpa進(jìn)行光化學(xué)分析,采用的條件是：[Ru(bpy)_3](ClO_4)_2作為光敏劑,過(guò)硫酸鈉作為電子受體,75 mM pH 85硼酸緩沖溶液,光源的波長(zhǎng)范圍是λ=470±10 nm。利用標(biāo)準(zhǔn)Clark電極對(duì)其配制的溶液測(cè)試光催化水氧化活性,結(jié)果表明該催化劑具有一定產(chǎn)氧能力。通過(guò)測(cè)試動(dòng)態(tài)光散射(DLS)和丁達(dá)爾效應(yīng)等,可以得出光催化三組分體系中沒(méi)有納米顆粒形成。4.對(duì)配合物Cu-F_3tpa進(jìn)行電化學(xué)分析,采用的是三電極系統(tǒng)：以鉑絲為對(duì)電極、銀/氯化銀電極(含有飽和氯化鉀溶液)為參比電極和1 cm~2的ITO為工作電極,0.1 M硼酸緩沖溶液為電解質(zhì)溶液。催化劑在起峰電位134 V vs NHE處產(chǎn)生較低的過(guò)電勢(shì)值,相對(duì)于已報(bào)道過(guò)的有關(guān)電催化水氧化的銅配合物小。通過(guò)測(cè)試不同催化劑濃度、不同掃描速率以及不同pH的循環(huán)伏安圖,對(duì)其數(shù)據(jù)進(jìn)行處理,可以得出該催化劑具有電催化水氧化的活性,且催化后沒(méi)有納米顆粒生成,是均相溶劑體系。與此同時(shí),對(duì)電解前后的工作電極的表面形態(tài)進(jìn)行了電鏡掃描(SEM)和能譜分析(EDS)測(cè)試,且對(duì)電催化水氧化后的體系進(jìn)行DLS和丁達(dá)爾效應(yīng)表征,以上結(jié)果都表明了配合物Cu-F_3tpa在電催化水氧化后沒(méi)有發(fā)生分解,具有良好的穩(wěn)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 鹵0.23, and the maximum of TOF was 1.58 鹵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 鹵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.
【學(xué)位授予單位】：陜西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O643.36

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