本文選題：能源　切入點：燃料電池　出處：《吉林大學(xué)》2015年博士論文

【摘要】：能源是人類社會存在和發(fā)展必不可少的物質(zhì)基礎(chǔ)。隨著社會的發(fā)展，能源在日漸減少，同時引發(fā)各種環(huán)境問題，這必將會阻礙人類社會經(jīng)濟的發(fā)展。因此，圍繞著3E(Economy,Energy,Environment)尋找新的能源是非常有必要的。燃料電池有著能量密度高、低污染、方便充電、結(jié)構(gòu)簡單，在低溫下也能快速啟動，能量轉(zhuǎn)換過程不需要經(jīng)過卡諾循環(huán)，可以直接將化學(xué)能轉(zhuǎn)換為電能的裝置，這符合綠色能源的條件。目前，，Pt以及PtM/C催化劑廣泛應(yīng)用于燃料電池中的各種電催化反應(yīng)：醇 類燃料電池的陽極氧化；氫氣燃料電池中正極以及制備氫氣的析氫反應(yīng)(HER)以及燃料電池的陰極氧還原(ORR)等等。但是，世界上Pt儲量有限，價格昂貴，并且Pt催化劑在醇類燃料電池中對甲醇的氧化反應(yīng)(MOR)中的中間產(chǎn)物CO容易中毒；在燃料電池的陰極中，陽極為甲醇時容易產(chǎn)生“跨界反應(yīng)”，催化劑失活等特點，大規(guī)模地發(fā)展Pt型燃料電池非常困難。因此，探索制備新的非鉑電催化劑至關(guān)重要。如何提高催化劑的催化活性，開發(fā)新的非貴金屬催化劑已經(jīng)成為燃料電池發(fā)展的長期研究課題之一。本文主要圍繞燃料電池中的非鉑基催化劑的制備進行了研究。首先，在無有機模板條件下使用四乙基氫氧化銨(TEAOH)合成的Beta分子篩(Beta-TEA)作為晶種來誘導(dǎo)制備富鋁的Beta分子篩(Beta-SDS)，通過離子交換制備了Ni-Beta分子篩。通過研究表明Beta-SDS因為富鋁，離子交換能力大，可以引入更多的鎳離子(Ni2+)。通過循環(huán)伏安法和計時電流法，在堿性溶液中Ni-Beta-SDS電極對甲醇的氧化反應(yīng)(MOR)的電催化活性明顯高于用傳統(tǒng)的Ni-Beta-TEA。 其次，利用無模板水熱法制備具有大表面積的多級孔的urchin-like狀的鈷酸鎳(NiCo2O4)。通過循環(huán)伏安法和計時電流法，在堿性溶液中NiCo2O4對MOR的電催化活性明顯高于單一的金屬氧化物氧化鎳(NiO)和四氧化三鈷(Co3O4)。 再次，通過添加氟化銨(NH4F)改變形貌制備了nanosheet狀的二硫化鉬(MoS2)。在硫酸溶液中進行了析氫反應(yīng)(HER)的測試，研究結(jié)果表明nanosheet狀的MoS2由于其薄片從而使暴露出更多的活性位，比沒有添加NH4F制備的塊狀MoS2具有更好的電催化活性。 最后，在高溫退火氧化聚六亞基胍(PHMB)與氧化石墨烯(GO)的混合物，制備了氮摻雜的石墨烯(N-Graphene)，并在堿性溶液中對氧還原性能進行了測試。研究表明該催化材料在堿性溶液中的氧還原反應(yīng)以四電子為主。
[Abstract]:Energy is the essential material foundation for the existence and development of human society. With the development of society, energy is decreasing day by day, and at the same time, it will lead to various environmental problems, which will inevitably hinder the development of human society and economy. It's very necessary to find new energy around the 3EW economy. Fuel cells have high energy density, low pollution, easy charging, simple structure, fast start at low temperatures, and the energy conversion process doesn't have to go through the Carnot cycle. A device that converts chemical energy directly to electrical energy, which is in line with green energy conditions. At present, Pt and PtM/C catalysts are widely used in various electrocatalytic reactions in fuel cells: alcohols. Anodic oxidation of similar fuel cells; hydrogen evolution in hydrogen fuel cells and hydrogen evolution reactions to produce hydrogen; and cathodic oxygen reduction ORR for fuel cells, etc. However, the world's Pt reserves are limited and expensive. The intermediate product CO in methanol oxidation reaction of Pt catalyst in methanol fuel cell is easy to be poisoned, and in the cathode of fuel cell, the "cross boundary reaction" is easy to occur when the anode is methanol, and the catalyst is deactivated. It is very difficult to develop Pt fuel cells on a large scale. Therefore, it is very important to explore the preparation of new non-platinum electrocatalysts. The development of new non-precious metal catalysts has become one of the long-term research topics in the development of fuel cells. In the absence of organic templates, the Beta molecular sieve (Beta) synthesized by tetraethyl ammonium hydroxide (TEAOH) was used as seed to induce the preparation of aluminum-rich Beta molecular sieve, and the Ni-Beta molecular sieve was prepared by ion exchange. By cyclic voltammetry and chronoamperometric method, the electrocatalytic activity of Ni-Beta-SDS electrode for methanol oxidation in alkaline solution is obviously higher than that of traditional Ni-Beta-TEA. Secondly, nickel cobaltate (NiCo2O4) with large surface area and multilevel pores was prepared by template free hydrothermal method. By cyclic voltammetry and chronoamperometry, The electrocatalytic activity of NiCo2O4 to MOR in alkaline solution is obviously higher than that of nickel oxide (Nio) and cobalt trioxide (Co _ 3O _ 4). Thirdly, nanosheet like molybdenum disulfide (MoS _ 2) was prepared by adding ammonium fluoride (NH _ 4F). The hydrogen evolution reaction was carried out in sulfuric acid solution. The results showed that the nanosheet like MoS2 was exposed to more active sites because of its thin film. The bulk MoS2 prepared without adding NH4F has better electrocatalytic activity. Finally, the mixture of polyhexamethylguanidine (PHMB) and graphene oxide (GOO) was oxidized at high temperature. The nitrogen-doped graphene N-Graphene has been prepared and its oxygen reduction properties have been tested in alkaline solution. The results show that the oxygen reduction reaction of the catalyst in alkaline solution is mainly composed of four electrons.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：O643.36;TM911.4

【參考文獻】

相關(guān)期刊論文 前1條

1 Hanaa B HASSAN;;Electrodeposited Pt and Pt-Sn nanoparticles on Ti as anodes for direct methanol fuel cells[J];燃料化學(xué)學(xué)報;2009年03期

本文編號：1678756