本文選題：氧還原反應(yīng)　切入點(diǎn)：催化劑　出處：《中國科學(xué)院大學(xué)(中國科學(xué)院過程工程研究所)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：當(dāng)今社會(huì),由化石能源過度消耗引起的能源危機(jī)、環(huán)境污染問題日益突出,制約著社會(huì)的進(jìn)步、危害人們的身體健康。因此,開發(fā)新型綠色能源技術(shù)已是迫在眉睫。燃料電池可以通過正負(fù)極的氧化還原反應(yīng)將儲(chǔ)存在化學(xué)物質(zhì)中的化學(xué)能直接轉(zhuǎn)化為電能,產(chǎn)物只有水。這種能量轉(zhuǎn)換技術(shù)轉(zhuǎn)換效率高、綠色環(huán)保、構(gòu)造簡(jiǎn)單、穩(wěn)定性好、啟動(dòng)快,近些年掀起了研究熱潮,成為繼化石能源后又一重要的能源利用形式。然而,燃料電池內(nèi)部陰極的氧氣還原反應(yīng)(ORR)動(dòng)力學(xué)過程比陽極反應(yīng)慢,大大降低了電池的輸出電壓。為提高陰極反應(yīng)速率,常用的傳統(tǒng)催化劑為鉑(Pt)。但是鉑價(jià)格昂貴,穩(wěn)定性差,嚴(yán)重制約了燃料電池的大規(guī)模商業(yè)化發(fā)展。因此研發(fā)廉價(jià)、高效的燃料電池陰極ORR催化劑是推動(dòng)燃料電池發(fā)展產(chǎn)業(yè)的重要研究課題之一。本論文主要通過摻雜碳材料和復(fù)合多金屬氧酸鹽(多酸,POMs)兩種方法制備非Pt的非貴金屬和無金屬的ORR催化劑,并研究了材料在不同pH條件下催化氧還原的性能。取得以下研究成果:(1)通過對(duì)石墨炔進(jìn)行雜原子摻雜處理,研發(fā)了一種新型、無金屬、摻雜石墨炔的二維碳材料。對(duì)石墨炔進(jìn)行N、B、S、F單原子和NS、NB、NF雙原子的摻雜,制備了摻雜材料,并在堿性條件下分別對(duì)其進(jìn)行半電池和全電池性能測(cè)試,發(fā)現(xiàn)NF共摻的材料的半電池及全電池測(cè)試性能均優(yōu)于其它材料。并且材料在穩(wěn)定性、抗甲醇干擾性、抗CO中毒性能等方面都優(yōu)于Pt/C。密度泛函理論(DFT)計(jì)算從機(jī)理角度解釋了摻雜效應(yīng)。實(shí)驗(yàn)表明摻雜石墨炔是一種廉價(jià)、穩(wěn)定、高效的非金屬催化劑。(2)開發(fā)了一種自下而上設(shè)計(jì)合成催化劑的方法。以對(duì)二氰基苯為單體,在實(shí)驗(yàn)指導(dǎo)下自下而上的通過不同反應(yīng)溫度、不同反應(yīng)時(shí)長(zhǎng)及不同元素?fù)诫s處理等條件制備結(jié)構(gòu)可控的三維多孔碳材料(PTF),并進(jìn)行電化學(xué)測(cè)試以研究該材料在堿性條件下的催化ORR性能。發(fā)現(xiàn),隨著溫度升高,材料的導(dǎo)電性大幅度提升,催化效果顯著;N的形態(tài)對(duì)材料催化ORR影響顯著,石墨氮是活性最高的N形態(tài);不同元素影響氧還原反應(yīng)不同的反應(yīng)參數(shù):B有利于提高材料的選擇性,F有利于提高起始電位和電流密度。通過這種自下而上的制備方法為氧還原反應(yīng)機(jī)理的研究帶來便利。在此工作的基礎(chǔ)上還探索了通過引入Fe和I,制備適用于酸性介質(zhì)中的ORR催化劑。發(fā)現(xiàn)Fe和I的摻雜順序?qū)Σ牧闲阅苡绊懨黠@,先摻Fe后摻I的PTF-Fe-I性能最好。(3)首次制備一種多金屬氧酸鹽和碳材料復(fù)合的非貴金屬多酸基復(fù)合材料,并用于催化中性和堿性條件下的氧還原反應(yīng)。借助多酸和碳材料強(qiáng)相互作用力,簡(jiǎn)單一步法制備了復(fù)合材料。將該材料用于中性及堿性介質(zhì)中測(cè)試,發(fā)現(xiàn)材料出現(xiàn)4e-催化反應(yīng)區(qū),研究了多酸基催化劑催化ORR的反應(yīng)機(jī)理。該工作對(duì)于指導(dǎo)多酸在燃料電池中的應(yīng)用提供了借鑒意義。(4)開發(fā)了一種將含有不同3d金屬的多酸和不同的碳基底材料復(fù)合的簡(jiǎn)單方法。將制備的材料用于中性及堿性條件氧還原催化,研究了不同的3d金屬(Cu,Co,Ni)和不同的碳基底材料(Vulcan XC-72,石墨烯,有機(jī)碳材料)對(duì)材料性能的影響。探索制備高效多酸基復(fù)合催化劑的多酸活性位點(diǎn)和優(yōu)秀的碳材料的條件。
[Abstract]:In today's society, the excessive consumption of energy caused by fossil energy crisis, environmental pollution problems have become increasingly prominent, which restricts the progress of society, endanger people's health. Therefore, the development of new green energy technology is imminent. The fuel cell can be stored in chemicals in the chemical energy directly into electrical energy through the anode oxidation the reduction reaction product is only water. This energy conversion technology of high conversion efficiency, green environmental protection, simple structure, good stability, quick start, has been a hot research topic in recent years, becoming an important fossil energy use energy form. However, inside the fuel cell cathode oxygen reduction reaction (ORR) than the anodic reaction kinetics slowly, greatly reduces the output voltage of the battery. In order to improve the cathodic reaction rate, the traditional catalyst used for platinum platinum (Pt). But the price is expensive, poor stability, serious constraints The large-scale commercial development of the fuel cell. So the development of low-cost, efficient ORR fuel cell cathode catalyst is one of the important research topics to promote fuel cell industry development. This paper mainly by doping carbon materials and composite polyoxometalates (POM, POMs) two were prepared by non Pt and non noble metal no metal ORR catalyst, and to study the catalytic properties of materials under different pH conditions of oxygen reduction. The research results are as follows: (1) the graphdiyne of heteroatom doping treatment, developed a new, no metal, two dimensional carbon materials doped Shi Moque. N, B of graphdiyne, S F, single atoms and NS, NB, NF atoms doped, doped materials were prepared, and under alkaline conditions of the half cell and battery performance testing, found that half cell NF Co doped materials and the battery test performance is superior to other materials. And the material in the stability, anti methanol interference, anti CO poisoning performance are better than the Pt/C. density functional theory (DFT) calculation explains the doping effect mechanism from the point of view. The results showed that the graphite alkyne is a cheap, stable, non metal catalyst with high efficiency. (2) developed a bottom-up design synthesis catalyst. To two cyanobenzene as monomer in the experiment under the guidance of bottom-up by different reaction temperature, porous carbon materials with different reaction time and different doping processing conditions for preparing controllable structure (PTF), and to study the electrochemical catalytic performance of the ORR material under alkaline conditions. With the increase of temperature, conductivity, greatly enhance the material, the catalytic effect is significant; effects of N on morphology of ORR catalytic material significantly, graphite nitrogen is the highest activity of N form; different elements influence oxygen reduction reaction The same reaction parameters: B can improve the material selectivity of F can improve the initial potential and current density. For the convenience of the oxygen reduction reaction mechanism through a bottom-up preparation method. On the basis of the above work is explored through the introduction of Fe and I, is suitable for the preparation of ORR catalysts in acidic medium found. Effects of Fe and I doping on the properties of the material was first order, the performance of PTF-Fe-I doped I doped Fe (3) for the first time. The best preparation for polyoxometalates and carbon composite non noble metal polyoxometalate based composite materials, and used to catalyze the neutral and alkaline conditions of oxygen reduction reaction. With the help of multi acid and strong interaction of carbon materials, composite materials were prepared in a simple step method. The materials used for testing of neutral and alkaline medium, found the material 4e- catalytic reaction zone, the reaction mechanism catalyzed by ORR acid based catalysts. Provide a reference for guiding the application of the work of Polyoxometalates in the fuel cell. (4) a simple method of multi acid and different carbon substrate composite materials developed a 3D containing different metals. The prepared materials for neutral and alkaline conditions of oxygen reduction catalyst, was studied with 3D metal (Cu, Co, Ni) and different carbon substrates (Vulcan XC-72, graphene, carbon material) on the properties of materials. Explore acid active site preparation, POMS composite catalyst and excellent carbon material conditions.

【學(xué)位授予單位】：中國科學(xué)院大學(xué)(中國科學(xué)院過程工程研究所)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;TM911.4

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