基于分子催化劑的染料敏化光陽(yáng)極的性能研究
發(fā)布時(shí)間：2018-12-26 06:40
【摘要】：隨著能源和環(huán)境等全球性問(wèn)題的日益突出,可再生能源對(duì)于解決這些問(wèn)題起到了至關(guān)重要的作用。由于太陽(yáng)能取之不盡用之不竭,將其轉(zhuǎn)化為環(huán)保的、友好的可再生能源已備受世界各國(guó)科學(xué)家們的關(guān)注。利用人工光合作用構(gòu)建光電化學(xué)電池,模擬自然界中的綠色植物的光合作用原理,實(shí)現(xiàn)把太陽(yáng)能轉(zhuǎn)化為穩(wěn)定、易儲(chǔ)存的化學(xué)能[1-7],這種科技的研究正走在科學(xué)領(lǐng)域的前沿,但由于光合作用的復(fù)雜性和對(duì)外界條件要求較高,氧化水是將水解離出4個(gè)電子和4個(gè)質(zhì)子的過(guò)程,這個(gè)半反應(yīng)也是持續(xù)發(fā)展人工光合作用的瓶頸。因此研究經(jīng)濟(jì)、高效、穩(wěn)定的水氧化催化劑是解決上述問(wèn)題的突破口。本文制備了高效廉價(jià)的且合成簡(jiǎn)單的水氧化催化劑Co_4O_4(O2CMe)4(4-vinylpy)4(Co_4O_4),模仿了PSII的釋氧復(fù)合物(OEC)的立方結(jié)構(gòu),以TiO_2為基底的釕配合物作為光敏劑,通過(guò)共價(jià)鍵吸附和電聚合雙重方法將鈷立方烷分子催化劑修飾到釕配合物染料敏化的光陽(yáng)極上,其光電性能測(cè)試實(shí)驗(yàn)證明,以pH 7.0的0.10 mol/L硫酸鈉溶液為電解質(zhì),染料敏化修飾光陽(yáng)極光電流密度能夠達(dá)到100μA/cm2且穩(wěn)定性好,法拉第效率達(dá)到76%。同位素效應(yīng)的測(cè)試中也表明染料敏化修飾光陽(yáng)極在光解水的過(guò)程中,光敏劑與催化劑之間的電子轉(zhuǎn)移為整個(gè)光解水過(guò)程中的速率控制步驟。此外,本文還合成了高效釕配合物催化劑,同樣運(yùn)用共價(jià)鍵吸附和電聚合雙重方法組成分子型染料敏化光解水分子器件,其光電流密度明顯提升。由于TiO_2基底在整個(gè)修飾光陽(yáng)極中也具有影響,研究發(fā)現(xiàn)在涂有TiO_2漿料的基底上再通過(guò)TiCl4水解修飾上TiO_2的光陽(yáng)極效果更好,更有利于光敏劑和催化劑的吸附。并選擇了最優(yōu)光強(qiáng)100 mW/cm2,同樣選擇在pH 7.0,0.10 mol/L的Na2SO4溶液為電解質(zhì),在這樣的條件下,分子型染料敏化光解水分子器件的光電流密度比鈷立方烷催化劑修飾光陽(yáng)極提升6倍以上,達(dá)600μA/cm2且穩(wěn)定,基于兩種不同的水氧化催化劑運(yùn)用相同的修飾方法來(lái)組裝染料敏化光陽(yáng)極對(duì)研究分子型光陽(yáng)極的發(fā)展具有啟發(fā)作用。
[Abstract]:With the increasingly prominent global problems such as energy and environment, renewable energy plays a vital role in solving these problems. As solar energy is inexhaustible, it has attracted the attention of scientists all over the world. Using artificial photosynthesis to construct photovoltaic cells, simulate the principle of photosynthesis of green plants in nature, and realize the conversion of solar energy into stable and easily stored chemical energy [1-7]. The research of this kind of technology is at the forefront of the scientific field, but because of the complexity of photosynthesis and the high demand for external conditions, oxidized water is the process of dissociating water from four electrons and four protons. This half-reaction is also the bottleneck of sustainable development of artificial photosynthesis. Therefore, the research of economic, efficient and stable water oxidation catalyst is the breakthrough to solve the above problems. In this paper, a simple water oxidation catalyst Co_4O_4 (O2CMe) 4 (4-vinylpy) 4 (Co_4O_4) was prepared, which mimics the cubic structure of PSII's oxygen-releasing complex (OEC). Ruthenium complex based on TiO_2 was used as Guang Min. Cobalt cubic alkane molecular catalyst was modified on the photoanode sensitized by ruthenium complex by covalent bond adsorption and electropolymerization. The photoelectric properties of the catalyst were tested. Using 0.10 mol/L sodium sulfate solution of pH 7.0 as electrolyte, the dye sensitized modified photo-positive auroral current density can reach 100 渭 A/cm2 and the stability is good. Faraday efficiency is 76%. The isotopic effect also shows that the electron transfer between Guang Min and catalyst is the rate control step in the whole process of photodegradation of water. In addition, the highly efficient ruthenium complex catalyst was synthesized, and the photocurrent density of the molecular dye sensitized photodissociation molecular device was also increased by using covalent bond adsorption and electropolymerization. As the TiO_2 substrate also has an effect on the whole modified photoanode, it is found that the photoanode effect of TiO_2 on the substrate coated with TiO_2 slurry is better than that on the substrate coated with TiCl4 hydrolysis, which is more favorable for the adsorption of Guang Min and catalyst. The optimal light intensity of 100 mW/cm2, was also selected as the electrolyte in the Na2SO4 solution of pH 7.0 mol/L 0.10 mol/L. The photocurrent density of the molecular dye sensitized photodissociation molecular device is more than 6 times higher than that of the cobalt cubic alkane catalyst modified photoanode, reaching 600 渭 A/cm2 and stable. Using the same modification method to assemble dye sensitized photoanode based on two different kinds of water oxidation catalysts has enlightening effect on the development of molecular photoanode.
【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36
[Abstract]:With the increasingly prominent global problems such as energy and environment, renewable energy plays a vital role in solving these problems. As solar energy is inexhaustible, it has attracted the attention of scientists all over the world. Using artificial photosynthesis to construct photovoltaic cells, simulate the principle of photosynthesis of green plants in nature, and realize the conversion of solar energy into stable and easily stored chemical energy [1-7]. The research of this kind of technology is at the forefront of the scientific field, but because of the complexity of photosynthesis and the high demand for external conditions, oxidized water is the process of dissociating water from four electrons and four protons. This half-reaction is also the bottleneck of sustainable development of artificial photosynthesis. Therefore, the research of economic, efficient and stable water oxidation catalyst is the breakthrough to solve the above problems. In this paper, a simple water oxidation catalyst Co_4O_4 (O2CMe) 4 (4-vinylpy) 4 (Co_4O_4) was prepared, which mimics the cubic structure of PSII's oxygen-releasing complex (OEC). Ruthenium complex based on TiO_2 was used as Guang Min. Cobalt cubic alkane molecular catalyst was modified on the photoanode sensitized by ruthenium complex by covalent bond adsorption and electropolymerization. The photoelectric properties of the catalyst were tested. Using 0.10 mol/L sodium sulfate solution of pH 7.0 as electrolyte, the dye sensitized modified photo-positive auroral current density can reach 100 渭 A/cm2 and the stability is good. Faraday efficiency is 76%. The isotopic effect also shows that the electron transfer between Guang Min and catalyst is the rate control step in the whole process of photodegradation of water. In addition, the highly efficient ruthenium complex catalyst was synthesized, and the photocurrent density of the molecular dye sensitized photodissociation molecular device was also increased by using covalent bond adsorption and electropolymerization. As the TiO_2 substrate also has an effect on the whole modified photoanode, it is found that the photoanode effect of TiO_2 on the substrate coated with TiO_2 slurry is better than that on the substrate coated with TiCl4 hydrolysis, which is more favorable for the adsorption of Guang Min and catalyst. The optimal light intensity of 100 mW/cm2, was also selected as the electrolyte in the Na2SO4 solution of pH 7.0 mol/L 0.10 mol/L. The photocurrent density of the molecular dye sensitized photodissociation molecular device is more than 6 times higher than that of the cobalt cubic alkane catalyst modified photoanode, reaching 600 渭 A/cm2 and stable. Using the same modification method to assemble dye sensitized photoanode based on two different kinds of water oxidation catalysts has enlightening effect on the development of molecular photoanode.
【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36
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