本文選題：直接甲醇燃料電池 + 功能化石墨烯�。� 參考：《新疆大學》2015年碩士論文

【摘要】：直接甲醇燃料電池(DMFC)具有結(jié)構(gòu)簡單和能量轉(zhuǎn)化效率高等特點,被認為是一種新型綠色的環(huán)保能源,越來越受到人們的關注。催化劑的活性和穩(wěn)定性是影響DMFC商業(yè)化的重要因素之一。因此,制備具有較高催化活性和穩(wěn)定性的催化劑成為DMFC的研究熱點,其中載體對催化劑的性能起著關鍵性的作用;石墨烯具有良好的物理和化學性能,在催化劑載體方面有潛在的應用前景。本文以功能化石墨烯為載體負載Pt,制備了直接甲醇燃料電池陽極催化劑,并研究了電催化活性及穩(wěn)定性。主要研究結(jié)果如下:1.采用高溫熱解聚苯胺修飾的氧化石墨烯(PANI-GO),通過改變氧化石墨烯與苯胺(GO/ANI)的質(zhì)量比,制備了一系列氮摻雜還原氧化石墨烯碳材料(N-RGO),以其負載Pt合成了Pt/N-RGO納米結(jié)構(gòu)電催化劑。采用透射電鏡(TEM)、X射線衍射譜(XRD)、拉曼光譜(Raman)及X射線光電子能譜(XPS)等技術對Pt/N-RGO的形貌及結(jié)構(gòu)進行表征。用循環(huán)伏安和計時電流等電化學技術研究了Pt/N-RGO電極催化劑對CO溶出反應和甲醇電氧化反應的催化性能。發(fā)現(xiàn)GO/ANI質(zhì)量比為1:1.3時所制備Pt/N-RGO(1:1.3)催化劑顯示出最好的抗CO中毒能力;催化甲醇氧化的電流密度達到160.8 A·g-1;與未摻雜氮樣品Pt/RGO相比,Pt/N-RGO(1:1.3)樣品顯示出更強的抗CO中毒能力和更高的甲醇電氧化催化活性及穩(wěn)定性。2.以苯胺(ANI)及聚苯胺(PANI)對還原氧化石墨烯(RGO)進行非共價修飾,并以其為載體負載Pt制備了Pt/ANI-RGO和Pt/PANI-RGO催化劑。結(jié)果顯示,ANI及PANI對RGO進行修飾能明顯減小Pt納米顆粒的尺寸和分布范圍;ANI及PANI的引入,提高了催化劑Pt的電化學活性面積,所制備的Pt/ANI-RGO和Pt/PANI-RGO催化劑對甲醇氧化的催化活性(125.6 A·g-1和86.4 A·g-1)要高于Pt/RGO催化劑(77.3 A·g-1),但ANI及PANI對RGO的修飾對RGO負載的Pt電催化劑的催化穩(wěn)定性沒有影響。3.采用聚乙烯吡咯烷酮(PVP)非共價修飾的RGO為載體,以其負載Pt得到Pt/PVP-RGO催化劑。結(jié)果顯示,Pt/PVP-RGO催化劑表面的Pt顆粒分布均勻、尺寸較小;相對于Pt/RGO催化劑而言,PVP的加入,對Pt/PVP-RGO催化劑甲醇氧化活性無顯著改善;但Pt/PVP-RGO催化劑的穩(wěn)定性(下降51%)明顯高于Pt/RGO催化劑(下降62%),PVP的存在對催化劑穩(wěn)定性的提高有一定的積極作用。4.利用甲基紫精(MV)非共價功能化RGO,并以其負載Pt制備了Pt/MV-RGO納米催化劑。結(jié)果表明,Pt/MV-RGO催化劑表面的Pt顆粒分布狀況和尺寸大小有明顯改善;Pt/MV-RGO催化劑的電化學活性面積為24.7 m2·g-1,是Pt/RGO的3倍;同時,Pt/MV-RGO催化劑催化甲醇氧化的電流密度為221.4 A·g-1,是Pt/RGO的2.6倍;在氧還原反應中Pt/MV-RGO催化劑亦有著較高的催化活性,Pt/MV-RGO催化劑的穩(wěn)定性也較好。
[Abstract]:Direct methanol fuel cell (DMFC), which has the characteristics of simple structure and high energy conversion efficiency, is considered as a new type of green environmental energy, which has attracted more and more attention. The activity and stability of the catalyst is one of the important factors affecting the commercialization of DMFC. Therefore, the preparation of catalysts with high catalytic activity and stability has become a research hotspot in DMFC, in which the support plays a key role in the performance of the catalyst, and graphene has good physical and chemical properties. It has potential application prospect in catalyst support. In this paper, the anode catalyst for direct methanol fuel cell was prepared with functionalized graphene as the carrier, and its electrocatalytic activity and stability were studied. The main results are as follows: 1. A series of nitrogen-doped reduced graphene oxide carbon materials (N-RGON) were prepared by changing the mass ratio of graphene oxide to aniline in the presence of high temperature Polyaniline modified graphene oxide (PANI-GON). A series of nitrogen-doped graphene oxide carbon materials (N-RGON) were prepared by supported Pt to synthesize Pt/N-RGO nanostructure electrocatalysts. The morphology and structure of Pt/N-RGO were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy (Raman) and X-ray photoelectron spectroscopy (XPS). The catalytic properties of Pt/N-RGO electrode catalysts for CO dissolution and methanol electrooxidation were studied by cyclic voltammetry and chronoamperometry. When the mass ratio of GO/ANI is 1: 1.3, the catalyst prepared by Pt- / N-RGO1: 1.3) shows the best ability to resist CO poisoning. The current density of catalytic methanol oxidation reached 160.8 Ag-1.The Pt- / N-RGO1: 1.3) samples showed stronger resistance to CO poisoning and higher catalytic activity and stability of methanol electrooxidation than unadulterated nitrogen samples (Pt/RGO / RGO1: 1.3). Pt/ANI-RGO and Pt/PANI-RGO catalysts were prepared by noncovalent modification with aniline (ANI) and Polyaniline (Polyaniline), and supported on Pt. The results show that the modification of RGO by RGO and PANI can obviously reduce the size and distribution of Pt nanoparticles and increase the electrochemical active area of Pt. The catalytic activity of the prepared Pt/ANI-RGO and Pt/PANI-RGO catalysts for methanol oxidation was 125.6 Ag-1 and 86.4 Ag-1), which was higher than that of Pt/RGO catalyst 77.3 Ag-1G ~ (-1), but the modification of RGO by ANI and PANI had no effect on the catalytic stability of RGO supported Pt electrocatalyst. The non-covalent modified polyvinylpyrrolidone (PVP) RGO was used as the support and supported on Pt to obtain the Pt/PVP-RGO catalyst. The results showed that the Pt particles on the surface of PtP / PVP-RGO catalyst were uniformly distributed and the size of Pt particles was smaller than that of Pt/RGO catalyst, and the methanol oxidation activity of Pt/PVP-RGO catalyst was not significantly improved compared with the addition of PtPVP-RGO catalyst. However, the stability of Pt/PVP-RGO catalyst was significantly higher than that of Pt/RGO catalyst. Pt/MV-RGO nanocatalysts were prepared by non-covalent functionalization of methyl violet spermatine (MV) and supported on Pt. The results show that the distribution and size of Pt particles on the surface of Pt- / MV-RGO catalyst are obviously improved, the electrochemical activity area of Pt- MV-RGO catalyst is 24.7 m2 g ~ (-1), which is 3 times of that of Pt/RGO, and the current density of methanol oxidation is 221.4 Ag-1, 2.6 times of that of Pt/RGO, while the current density of Pt- / MV-RGO catalyst is 221.4 Ag-1. In the oxygen reduction reaction, Pt/MV-RGO catalyst also has higher catalytic activity. The stability of Pt- MV-RGO catalyst is better than that of Pt- MV-RGO catalyst.
【學位授予單位】：新疆大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：O643.36;TM911.4

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相關期刊論文 前1條

1 宋樹芹,梁振興,周衛(wèi)江,孫公權,辛勤;DMFC的阻甲醇滲透研究進展[J];電池;2004年04期

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本文編號：1876515