将掺杂铁离子的聚苯胺(PANI)与碳纳米管(MWCNT)复合物在900℃加热,得到含铁的催化剂FeNC;然后将含钴盐的FeNC在不同温度下焙烧,得到复合催化剂FeCoNC.对催化剂的表观结构、比表面积、热稳定性、组成以及氧还原(ORR)电催化活性进行表征,研究了焙烧温度和氮含量等因素对其催化活性的影响.结果表明:随着焙烧温度的升高,催化剂的表面结构趋于均匀,焙烧温度为500℃的催化剂表面结构最为均匀平整,高于500℃时出现烧结;较高的氮含量能改善催化剂的ORR电活性.焙烧温度为500℃的催化剂对ORR的电催化活性最高,在酸性和碱性溶液中ORR的起始电位分别为0.63和-0.12 V(vs SCE),电流密度分别为11.67和9.83 mAmg1@-0.3 V(vs SCE),并具有较好的热稳定性和催化活性稳定性.分步加入Fe和Co,并在加Co后在500℃焙烧得到的催化剂对ORR具有优异的电催化活性.
MWCNTs doped polyaniline (PANI) were used as a precursor and the precursor added Fe salt was heated at 900℃ to obtain the Fe-containing catalyst FeNC.Cobalt salt was then added to the FeNC and the mixture was subjected to heat treatment at different temperatures to prepare the various composites FeCoNC.The structure,specific surface area,thermal stability and compositions of the catalysts FeCoNC were characterized by TEM,SEM,TGA and elemental analysis,respectively.The results show that the catalyst structure becomes uniform when the temperature is 500℃,and it appears sintering at the temperature higher than 500℃.The content of N increases first and then decreases with the increasing of temperature.The temperature has a little influence on the specific surface area of the catalysts.TGA suggests that the catalysts have good thermal stability in the air.ORR activity of the catalysts has been tested by CV and RDE techniques.Results show that the catalyst FeCoNC5 obtained by the heating treatment at 500℃ presents the highest electrocatalytic activity for ORR.The ORR current density at 2000r/min is 11.67 mA/mg@-0.3 V(vs SCE) in acidic solution and 9.83 mA/mg@-0.8 V(vs SCE) in alkaline solution,and the onset potential of ORR is 0.63 V(vs SCE) in acidic solution and-0.12 V(vs SCE) in alkaline solution.
参考文献
| [1] | H.Liu,C.Song,H.Zhang,J.J.Zhang,H.J.Wang,D.P.Wilkinson,A review of anode catalysis in the direct methanol fuel cell,J.Power Sources,155,95(2006) |
| [2] | A.Swrov,C.Kwak,Review of non-platinum anode catalysts for DMFC and PEMFC application,Appl.Catal.B:Environmental,90,313(2009) |
| [3] | S.C.Thomas,X.M.Ren,S.Gottesfeld,P.Zelenoy,Direct methanol fuel cells:progress in cell performance and cathode research,Electrochim.Acta,47,3741 (2002) |
| [4] | R.Jasinski,A new fuel cell cathode catalyst,Nature,201,1212(1964) |
| [5] | J.H.Zagal,F.Bedioui,J.P.Dodelet,N4-Macrocyclic metal complexes.New York:Springer,2006,p.45 |
| [6] | G.Lalande,R.Cote,G.Tamizhmani,Physical,chemical and electrochemical characterization of heat-treated tetracarboxylic cobalt phthalocyanine adsorbed on carbon black as electrocatalyst for oxygen reduction in polymer electrolyte fuel cells,Electrochim Acta,40:2635(1995) |
| [7] | G.Faubert,R.Cote,D.Guay,Iron catalysts prepared by high-temperature pyrolysis of tetraphenylporphyrins adsorbed on carbon black for oxygen reduction in polymer electrolyte fuel cells,Electrochim Acta,43:341(1998). |
| [8] | M.Lefevre,J P.Dodelet,O2 reduction in PEM fuel cells:Activity and active site structural information for catalysts obtained by the pyrolysis at high temperature of Fe precursors,J Phys Chem B,104:11238-11247(2000). |
| [9] | H.Niwa,K.Horiba,Y.Harada,X-ray absorption analysis of nitrogen contribution to oxygen reduction reaction in carbon alloy cathode catalysts for polymer electrolyte fuel cells,J Power Sources,187:93-97(2009). |
| [10] | K.Lee,L.Zhang,H.Lui,Oxygen reduction reaction (ORR) catalyzed by carbon-supported cobalt polypyrrole (Co-PPy/C) electrocatalysts,Electrochim Acta,54:4704-4711 (2009). |
| [11] | V.Nallathambi,J W.Lee,S P.Kumaraguru,Development of high performance carbon composite catalyst for oxygen reduction reaction in PEM proton exchange membrane fuel cells,J Power Sources,183:34-42(2008). |
| [12] | C W B.Bezerra,L.Zhang,K.Lee,Novel carbon-supported Fe-N electrocatalysts synthesized through heat treatment of iron tripyridyl triazine complexes for the PEM fuel cell oxygen reduction reaction,Electrochim Acta,53:7703-7710(2008). |
| [13] | W B.Cicero,L.Zhang,K C.Lee A review of Fe-N/C and Co-N/C catalysts for the oxygen reduction reaction,Electrochim Acta,53:4937-4951(2008). |
| [14] | G.Wu,K.L.More,C.M.Johnston,P.Zelenay,High-performance electrocatalysts for oxygen reduction derived from polyaniline,iron,and cobalt,Science,322,443(2011) |
| [15] | M.Ladouceur,G.Lalande,D.Guay,J.P.Dodelet,L.Dignard-Bailey,M.L.Trudeau,R.Schulz,Pyrolyzed cobalt phthalocyanine as electrocatalyst for oxygen reduction,J.Electrochem.Soc.,140,1974(1993) |
| [16] | G.Q.Sun,J.T.Wang,R.F.Savinell,Iron(Ⅲ) tetramethoxyphenylporphyrin(FeTMPP) as methanol tolerant electrocatalyst for oxygen reduction in directmethanol fuel cells,J.Appl.Electrochem.,28,1087(1998) |
| [17] | A.L.Bouwkamp-Wijnoltz,W.Visscher,J.A.R.Van Veen,The selectivity of oxygen reduction by pyrolysed iron porphyrin supported on carbon,Electrochem.Acta,43,3141(1998) |
| [18] | H.R.Byon,J.Suntivich,E.J.Crumlin,S.Yang,Fe-N-modified multi-walled carbon nanotubes for oxygen reduction reaction in acid,Phys.Chem.Chem.Phys.,48,21437(2011) |
| [19] | G.Liu,X.G.Li,Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on N-doped ordered porous carbon,Appl.Catal.B:Enviromental,93,156(2009) |
| [20] | LI Sang,ZHOU Yanfang,QIU Peng.Chin.Sci.Bull.,54,881(2009)(李赏,周彦方,邱鹏,Co基非贵金属催化剂的制备及其氧还原电催化性能,科学通报,54,881(2009)) |
| [21] | A.Morozan,P.Jegou,B.Jousselme,S.Palacin,Electrochemial performance of annealed cobalt-benzotriazole/CNTS catalysts towards the oxygen reduction reaction,Phys.Chem.Chem.Phys.,48,21600(2011) |
| [22] | L.Deng,M.Zhou,C.Liu,L.Liu,C.Liu,S.Dong,Development of high performance of Co/Fe/N/CNT nanocatalyst for oxygen reduction in microbial fuel cells,Talanta,1-2,444(2010) |
| [23] | G.Wu,M.Nelson,S.Ma,H.Meng,G.F.Cui,P.K,Shen,Synthesis of nitrogen-doped onion-like carbon and its use in carbon-based CoFe binary non-precious-metal catalysts for oxygen-reduction,Carbon,12,3972(2011) |
| [24] | Li Y Z,Fan Y N,Chen Y.The preparation of molybdenum oxynitride by hydrazine reduction of MoO3 at moderate temperature and its application in the selective hydrogenation of long-chain linear alkadienes.Catalysis Lett,2002,82(1-2):111-116 |
| [25] | YANG wei,CHEN shengzhou,ZOU Hanbo,LIN Weiming,Chemical industry and engineering progress.11,29(2010)(杨伟,陈胜洲,邹汉波,林维明,氮掺杂非贵金属氧还原催化剂研究进展,化工进展,11,29(2010)) |
| [26] | S.Gottesfeld,I.D.Raistrick,S.Srinivasan,J.Electrochem.Soc.,134,1455(1987) |
| [27] | R.Lide,DCRC Handbook of Chemistry and Physics.CRC Press,Boca Raton,2001 |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%