本文關(guān)鍵詞： 燃料電池 氧還原反應(yīng) 過渡金屬 氮摻雜 碳基催化劑　出處：《安徽大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：燃料電池作為最具前景的能源轉(zhuǎn)換技術(shù)之一,具有能量轉(zhuǎn)化效率高、環(huán)境友好等優(yōu)點(diǎn),備受研究者的青睞。它是一種高效利用氫能的新能源,在電化學(xué)反應(yīng)中能直接將化學(xué)能轉(zhuǎn)換為電能的裝置。因此陰極氧還原反應(yīng)(Oxygen Reduction Reaction,ORR)在燃料電池中顯得十分重要,其中,貴金屬催化劑依然是當(dāng)前性能最好的陰極ORR催化劑。然而,由于這些貴金屬催化劑在自然界中儲(chǔ)存量及其稀少、價(jià)格非常昂貴以及遲滯的動(dòng)力學(xué)效應(yīng)等,嚴(yán)重限制了燃料電池商業(yè)化應(yīng)用。因此,開發(fā)和探索價(jià)格低廉、資源豐富、高效、耐用的非貴金屬ORR催化劑顯得十分重要,具有非凡的現(xiàn)實(shí)意義和應(yīng)用前景。在目前研究的陰極ORR催化劑中,非貴金屬碳基催化劑以其高效的催化活性和穩(wěn)定性及高超抗甲醇毒性等特點(diǎn),成為學(xué)術(shù)界廣泛研究的課題�；诜琴F金屬碳基催化劑的研究現(xiàn)狀及本課題組的工作基礎(chǔ),本論文選用碳納米管、瓊脂為主要的碳源,通過幾種不同的方法將雜原子摻入過渡金屬碳骨架中,成功制備了一系列高效的過渡金屬碳基ORR催化劑。主要工作內(nèi)容和成果包括以下幾個(gè)方面:1.以碳納米管、氨基磺酸鈷、二腈二胺為原料,采用簡(jiǎn)單的超聲分散、蒸發(fā)溶劑的方法制備前軀體復(fù)合物,并經(jīng)過高溫?zé)峤獬晒χ苽淞说⒘螂p摻雜鈷/碳催化劑。通過掃描電鏡、透射電鏡、X射線衍射、BET比表面積測(cè)試等對(duì)最終產(chǎn)物進(jìn)行表征,并分別在堿性和酸性溶液中測(cè)試最終產(chǎn)物的ORR性能。電化學(xué)測(cè)試結(jié)果表明,在堿性溶液中,典型催化劑表現(xiàn)出優(yōu)異的ORR性能,極限擴(kuò)散電流可達(dá)-5.43 mA cm-2,電子轉(zhuǎn)移數(shù)接近4,抗甲醇毒性和長(zhǎng)期穩(wěn)定性也非常好。此外,典型催化劑在酸性條件下的電催化性能也比較好。這種介孔納米管狀氮、硫雙摻雜鈷/碳催化劑在電催化氧還原領(lǐng)域有一定的應(yīng)用前景。2.以乙酰丙酮鐵和生物質(zhì)瓊脂為前軀體,通過簡(jiǎn)單的自我膨脹過程制備了一種新穎的泡沫狀的碳化鐵氮摻雜瓊脂材料(標(biāo)記為Fe/C-NA)。乙酰丙酮鐵可以均勻的分散在瓊脂中,避免了納米粒子的團(tuán)聚現(xiàn)象。這種方法制備的催化劑具有非常大的比表面積(1327.7 m2g-1),氮摻雜量可達(dá)到3.09%。其中典型催化劑泡沫狀的網(wǎng)絡(luò)結(jié)構(gòu)使其導(dǎo)電性提高,能夠促進(jìn)離子和電子的傳輸,有利于Fe-C活性位點(diǎn)形成。在堿性溶液中,我們制備的代表性催化劑表現(xiàn)出優(yōu)異的電催化氧還原性能,起始電位與商業(yè)Pt/C(20 wt%)相當(dāng),極限擴(kuò)散電可以達(dá)到-5.34mA cm-2,略低于商業(yè)Pt/C的5.47 mA cm-2;典型催化劑顯示出優(yōu)異的抗甲醇性能,同時(shí)穩(wěn)定性測(cè)試表明經(jīng)過5000次循環(huán)之后極限擴(kuò)散電流依然可以保持91.4%,ORR反應(yīng)幾乎全部按四電子過程進(jìn)行。典型催化劑在酸性溶液中同樣具有較好的氧還原催化性能、穩(wěn)定性和抗甲醇性能。3.以二茂鐵作為鐵源,通過水熱、高溫?zé)峤獾娜椒?成功制備一維竹節(jié)狀氮摻雜碳納米管負(fù)載鐵基納米粒子(FexCyNz/N-CNT)材料。通過調(diào)控二茂鐵和二氰二胺的比例及熱解溫度,得到代表性產(chǎn)物FexCyNz/N-CNT-1000材料。電化學(xué)測(cè)試結(jié)果表明,典型材料呈現(xiàn)優(yōu)異的電催化氧還原性能,在堿性介質(zhì)中,極限電流密度比商業(yè)Pt/C還要高0.54 mA cm-2、與商業(yè)Pt/C相比,表現(xiàn)出更加優(yōu)異的長(zhǎng)期穩(wěn)定性及抗甲醇性能,其氧還原過程接近4電子轉(zhuǎn)移過程。更有趣的是,通過吸波測(cè)試發(fā)現(xiàn),當(dāng)FexCyNz/N-CNT-1000的含量為12 wt%時(shí),代表性產(chǎn)物與石蠟的混合物表現(xiàn)出最佳的吸波性能。因此,我們制備的FexCyNz/N-CNT-1000產(chǎn)物是一種高效的氧還原催化劑和電磁波吸收劑。這種新型的雙功能納米材料體系,可以為合理設(shè)計(jì)目標(biāo)應(yīng)用的多功能材料開辟一條新路。
[Abstract]:Fuel cell energy conversion technology as one of the most promising, with high energy efficiency, environmental friendly, more widely. It is a kind of new energy efficient use of hydrogen, in electrochemical reaction can directly convert chemical energy into electrical energy device. Because the cathodic oxygen reduction reaction (Oxygen Reduction Reaction, ORR) is very important in the fuel cell, the noble metal catalyst is still the best performance of the ORR cathode catalyst. However, because of these noble metal catalysts in nature reserves and scarce, the price is very expensive and the dynamic hysteresis effect, seriously restrict the commercialization of fuel cell applications. Therefore, the development and exploration of abundant resources, low price, high efficiency, non noble metal ORR catalyst durability is very important, has extraordinary practical significance and application prospect in current research. ORR cathode catalyst, carbon based catalyst of non noble metal for its high catalytic activity and stability and excellent anti methanol toxicity and other characteristics, has become extensive academic research topic. The research status of non noble metal carbon based catalyst and the basis of the work of our research group based on the use of carbon nanotubes, agar as the main carbon the source, through several different methods of hetero atom doped with transition metal carbon skeleton, a series of efficient transition metal carbon based ORR catalysts were prepared successfully. The main contents and results are as follows: 1. with carbon nanotubes, cobalt sulfamate, two nitrile two amine as raw materials by a simple ultrasonic dispersion method, solvent evaporation preparation of the precursor compound, and after high-temperature pyrolysis successfully prepared nitrogen, sulfur doped cobalt / carbon catalyst. By scanning electron microscopy, transmission electron microscopy, X ray diffraction, BET surface area measurement and so on The final products were characterized respectively, and test the ORR performance of the final product in alkaline and acidic solution. The electrochemical test results show that in alkaline solution, typical catalysts exhibit excellent ORR performance, the limiting diffusion current up to -5.43 mA cm-2, the electron transfer number close to 4, anti methanol toxicity and long-term stability is also very good. In addition electrocatalytic performance of typical catalyst, under acidic conditions are relatively good. This kind of mesoporous nano tubular nitrogen, sulfur doped cobalt / carbon reduction catalyst in electrocatalytic oxygen has certain application prospect of.2. in iron acetylacetonate and raw material agar as the precursor by simple self expansion process of preparation of iron carbide nitrogen a foamed material doped agar of the novel (labeled Fe/C-NA). Iron acetylacetonate can be uniformly dispersed in the agar and avoid the agglomeration of nanoparticles. The preparation method. The agent has a very large surface area (1327.7 m2g-1), nitrogen doping amount can reach 3.09%. in which the network structure of a typical catalyst foam to improve the conductivity, can promote the transport of ions and electrons, is conducive to the formation of the active site of Fe-C. In alkaline solution, we prepared a representative catalyst showed power excellent catalytic oxygen reduction performance, initial potential and commercial Pt/C (20 wt%), the limiting diffusion electricity can reach -5.34mA cm-2, slightly lower than the commercial Pt/C mA 5.47 cm-2; typical catalysts show excellent anti methanol performance at the same time, the stability test shows that after 5000 cycles, the limiting diffusion current can still maintain 91.4%, ORR almost all of the four electron reaction process. Typical catalysts both have better electrocatalytic performance for oxygen reduction in acid solution, stability and anti methanol performance of.3. with two ferrocene as iron source, through Water heat, three step pyrolysis, the successful preparation of one-dimensional doped nitrogen doped carbon nanotubes supported Fe nanoparticles (FexCyNz/N-CNT) materials. Through the regulation of two ferrocene and two cyano two amine proportion and pyrolysis temperature, get the representative product of FexCyNz/N-CNT-1000 materials. The electrochemical test results show that the typical material exhibits excellent electrocatalytic oxygen reduction the performance in alkaline medium, the limiting current density is 0.54 higher than that of the commercial Pt/C mA cm-2, compared with the commercial Pt/C, showed more excellent long-term stability and anti methanol performance, the oxygen reduction process nearly 4 electron transfer process. More interestingly, by absorbing test found that when the content of FexCyNz/N-CNT-1000 is 12 wt%, a mixture of representative products and paraffin showed the best absorbing performance. Therefore, we made FexCyNz/N-CNT-1000 product prepared is an efficient catalyst for oxygen reduction and electricity Magnetic absorber. This new dual function nanomaterial system can open up a new way for the rational design of multi-functional materials applied to the target.

【學(xué)位授予單位】：安徽大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;TM911.4

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