本文選題：氧還原反應　切入點：有機多孔聚合物　出處：《湘潭大學》2017年碩士論文　論文類型：學位論文

【摘要】：燃料電池是一種應用前景廣闊的新能源轉換裝置,具有結構簡單、低污染、能量密度高等優(yōu)點。目前燃料電池常用的陰極催化劑是Pt基催化劑,但Pt基催化劑成本高且易被甲醇和CO毒化而失活。N摻雜及N/P共摻雜碳材料因其優(yōu)異的氧還原反應(ORR)催化活性、低成本以及良好的抗甲醇和CO毒化能力,被認為是最有希望替代Pt的不含金屬(metal-free)的ORR催化劑之一。本論文以有機多孔聚合物聚(三聚氰胺-醛)為前驅體,經直接熱解制備了N摻雜碳(N/C)和N/P共摻雜碳(N-P/C)三種電催化劑,并系統(tǒng)研究了它們的ORR催化性能。論文主要工作內容包括以下兩方面:(1)PMDP和PMTP基氮摻雜多孔碳材料的制備及其ORR催化性能研究。本章先分別將2,6-二甲�；鶎谆椒雍�1,3,5-三甲酰基間苯三酚與三聚氰胺在DMSO中縮聚,合成出聚(三聚氰胺 2,6-二甲�；鶎谆椒�)(PMDP)和聚(三聚氰胺 1,3,5-三甲�；g苯三酚)(PMTP)兩種有機多孔聚合物。BET測試結果表明,PMDP和PMTP的比表面積、總孔容和孔徑分別為671和302 m2g~(-1)、2.10和2.16cm3g~(-1)以及13和20 nm。而后將兩種有機多孔聚合物直接熱解,制備出N摻雜碳N/C_(PMDP)和N/CPMTP兩種催化劑。BET測試結果表明,催化劑N/C_(PMDP)和N/CPMTP的比表面積和總孔容分別為833和464 m2g~(-1)以及1.57和2.31 cm3 g~(-1);XPS測試結果表明,催化劑N/C_(PMDP)和N/CPMTP的N含量分別為4.03和2.68 at.%。在堿性電解質中,催化劑N/C_(PMDP)和N/CPMTP催化ORR的起始電位、半波電位和極限電流密度分別為0.007和0.002 V(vs.Ag/AgCl)、-0.10和-0.11 V(vs.Ag/AgCl)以及6.98和5.86 mA cm-2,二者的ORR催化活性均優(yōu)于商業(yè)Pt/C催化劑。(2)PMHP基氮磷摻雜多孔碳材料的制備及其ORR催化性能研究。采用上章同樣的方法先合成有機多孔聚合物聚(三聚氰胺-六醛基環(huán)三磷腈)(PMHP),再經高溫熱解制備得到N/P共摻雜碳(N-P/C)催化劑。BET測試結果表明,N-P/C催化劑的比表面積和總孔容分別為658 m2g~(-1)和1.48 cm3 g~(-1);XPS測試結果表明,催化劑N-P/C的N、P含量分別為5.57和1.32 at.%。在堿性電解質中,催化劑N-P/C催化ORR的起始電位、半波電位和極限電流密度分別為0.017 V(vs.Ag/AgCl)、-0.10 V(vs.Ag/AgCl)和6.57 mA cm-2,其ORR催化活性略優(yōu)于商業(yè)Pt/C催化劑。
[Abstract]:Fuel cell is a promising new energy conversion device with the advantages of simple structure, low pollution and high energy density. However, Pt-based catalysts have high cost and can be easily poisoned by methanol and CO, and can be deactivated. N doped and N / P co-doped carbon materials have good catalytic activity, low cost and good resistance to methanol and CO poisoning due to their excellent oxygen reduction reaction. It is considered to be one of the most promising alternatives to Pt for metal-free (metal-free) ORR catalysts. In this paper, three kinds of N-doped carbon monoxide (N-doped) and N / P co-doped N-P- (C) catalysts were prepared by direct pyrolysis of organic porous polymer poly (melamine aldehyde). The main contents of this paper are as follows: preparation and ORR catalytic performance of ORR and PMTP based nitrogen-doped porous carbon materials. The condensation of phenol and triacylpyrogallol with melamine in DMSO. Two kinds of organic porous polymers, Poly (melamine, 6-dimethylphenol) and poly (melamine 1, 3 and 5-trimethylidene), were synthesized. The results of BET measurements showed that the specific surface areas of PMDP and PMTP were determined. The total pore volume and pore size were 671 and 302 m2g-1 (2.10 and 2.16 cm ~ 3g ~ (-1)) and 13 and 20 nm, respectively. Two kinds of organic porous polymers were pyrolyzed directly to prepare N-doped carbon (N / C) PMDP) and N / CPMTP catalysts. The specific surface area and total pore volume of the catalysts N / C / C / P were 833 and 464 m ~ (2) g ~ (-1), respectively) and 1.57 and 2.31 cm3 / g ~ (-1) respectively. The results showed that the N contents of the catalyst N / C ~ (C ~ +) PMDP) and N / C ~ (CPMTP) were 4.03 and 2.68 at.In alkaline electrolytes, the initial potentials of the catalyst N / C / P _ P _ P) and N / P ~ (CPMTP) catalyzed ORR were 4.03 and 2.68 at.In the alkaline electrolyte, the initial potential of the catalyst N / C / P _ (PMDP) and N / P _ (CPMTP) was 4.03 and 2.68 at.respectively. The half-wave potential and limit current density were 0.007 and 0.002 V / v 路AgCl-0.10 and -0.11 V / Agcm-2, respectively, and 6.98 and 5.86 mAcm-2, respectively. The catalytic activity of ORR was better than that of commercial Pt/C catalyst. The preparation and the catalytic performance of ORR were studied. In the previous chapter, the same method was used to synthesize the organic porous polymer (melamine-hexafluorotriphosphazene) PMHPN, and then the N / P co-doped carbon N / P / C catalyst. BET test results showed that the specific surface area and total surface area of the N / P / C catalyst were determined by pyrolysis at high temperature. The pore volume is 658 m ~ (2) g ~ (-1) and 1.48 cm3 / g ~ (-1), respectively. In alkaline electrolytes, the initial potential, half wave potential and limit current density of ORR catalyzed by N-P / C are 0.017 V / V / V / V / V / V ~ (-1) and (-0.10) V / A / cm ~ (-2), respectively. The catalytic activity of N-P / C catalyst is slightly better than that of commercial Pt/C catalyst, and the catalytic activity of N-P / C catalyst is slightly better than that of commercial Pt/C catalyst, and its catalytic activity is slightly better than that of commercial Pt/C catalyst, and its catalytic activity is slightly better than that of commercial Pt/C catalyst.
【學位授予單位】：湘潭大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36;TM911.4

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