聚合物基杂原子掺杂碳材料的制备及其氧还原性能研究

发布时间：2018-03-10 05:36

本文选题：氧还原反应　切入点：有机多孔聚合物　出处：《湘潭大学》2017年硕士论文　论文类型：学位论文

【摘要】：燃料电池是一种应用前景广阔的新能源转换装置,具有结构简单、低污染、能量密度高等优点。目前燃料电池常用的阴极催化剂是Pt基催化剂,但Pt基催化剂成本高且易被甲醇和CO毒化而失活。N掺杂及N/P共掺杂碳材料因其优异的氧还原反应(ORR)催化活性、低成本以及良好的抗甲醇和CO毒化能力,被认为是最有希望替代Pt的不含金属(metal-free)的ORR催化剂之一。本论文以有机多孔聚合物聚(三聚氰胺-醛)为前驱体,经直接热解制备了N掺杂碳(N/C)和N/P共掺杂碳(N-P/C)三种电催化剂,并系统研究了它们的ORR催化性能。论文主要工作内容包括以下两方面:(1)PMDP和PMTP基氮掺杂多孔碳材料的制备及其ORR催化性能研究。本章先分别将2,6-二甲酰基对甲基苯酚和1,3,5-三甲酰基间苯三酚与三聚氰胺在DMSO中缩聚,合成出聚(三聚氰胺 2,6-二甲酰基对甲基苯酚)(PMDP)和聚(三聚氰胺 1,3,5-三甲酰基间苯三酚)(PMTP)两种有机多孔聚合物。BET测试结果表明,PMDP和PMTP的比表面积、总孔容和孔径分别为671和302 m2g~(-1)、2.10和2.16cm3g~(-1)以及13和20 nm。而后将两种有机多孔聚合物直接热解,制备出N掺杂碳N/C_(PMDP)和N/CPMTP两种催化剂。BET测试结果表明,催化剂N/C_(PMDP)和N/CPMTP的比表面积和总孔容分别为833和464 m2g~(-1)以及1.57和2.31 cm3 g~(-1);XPS测试结果表明,催化剂N/C_(PMDP)和N/CPMTP的N含量分别为4.03和2.68 at.%。在碱性电解质中,催化剂N/C_(PMDP)和N/CPMTP催化ORR的起始电位、半波电位和极限电流密度分别为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催化活性均优于商业Pt/C催化剂。(2)PMHP基氮磷掺杂多孔碳材料的制备及其ORR催化性能研究。采用上章同样的方法先合成有机多孔聚合物聚(三聚氰胺-六醛基环三磷腈)(PMHP),再经高温热解制备得到N/P共掺杂碳(N-P/C)催化剂。BET测试结果表明,N-P/C催化剂的比表面积和总孔容分别为658 m2g~(-1)和1.48 cm3 g~(-1);XPS测试结果表明,催化剂N-P/C的N、P含量分别为5.57和1.32 at.%。在碱性电解质中,催化剂N-P/C催化ORR的起始电位、半波电位和极限电流密度分别为0.017 V(vs.Ag/AgCl)、-0.10 V(vs.Ag/AgCl)和6.57 mA cm-2,其ORR催化活性略优于商业Pt/C催化剂。
[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.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;TM911.4

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