钴/氮掺杂碳催化剂及其氧还原催化机理研究

姜孟秀; 张晶; 李月华; 张蓉

doi:10.13208/j.electrochem.170105

电化学 >

2017 , Vol. 23 >Issue 6: 627 - 637

DOI: https://doi.org/10.13208/j.electrochem.170105

研究论文

钴/氮掺杂碳催化剂及其氧还原催化机理研究

姜孟秀 ,
张晶 ,
李月华 ,
张蓉

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太原理工大学化学化工学院，山西太原 030024

收稿日期: 2017-01-05

修回日期: 2017-02-28

网络出版日期: 2017-03-06

基金资助

山西省自然科学基金项目(No. 2013011012-1）资助

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Cobalt-Based Nitrogen-Doped Carbon Non-Noble Metal Catalysts for Oxygen Reduction Reaction

JIANG Meng-xiu ,
ZHANG Jing ,
LI Yue-hua ,
ZHANG Rong

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College of Chemistry and Chemical Engineering，Taiyuan University of Technology，Taiyuan 030024，Shanxi，China

Received date: 2017-01-05

Revised date: 2017-02-28

Online published: 2017-03-06

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摘要

以尿素做氮源、醋酸钴做金属源，用湿法合并高温热处理法合成了钴/氮共掺杂碳的非贵金属氧还原催化剂Co-N/C-T. 采用循环伏安（CV）法和线性扫描法（LSV）探究了氮源和金属源用量以及热处理温度对氧还原反应电催化活性的影响，活性最好的催化剂Co_0.13-N_0.3/C-800的峰电位达到0.829 V（vs.RHE），接近商用Pt/C的活性，但比商用Pt/C有更好的耐甲醇性和稳定性. 同时，采用SEM，TEM，BET，XRD和XPS方法表征了催化剂结构和组分特征，并提出催化剂可能的电催化活性氧还原反应机理.

关键词： 钴/氮共掺杂碳催化剂; 氧还原; 电催化作用; 活性位; 热处理

本文引用格式

姜孟秀 , 张晶 , 李月华 , 张蓉 . 钴/氮掺杂碳催化剂及其氧还原催化机理研究[J]. 电化学, 2017 , 23(6) : 627 -637 . DOI: 10.13208/j.electrochem.170105

Abstract

Transition metal-nitrogen co-doped carbon catalysts have attracted significant attention because of their reasonable activity and remarkable selectivity toward oxygen reduction reaction (ORR) as cathodic reaction in fuel cells. However, the role of transition metal in the active sites of the catalysts still is uncertain. In this work, the Co_x-N_y/C-T catalysts were prepared with BP2000 as a carbon source, urea (Ur) as a nitrogen source and Co(OAc)₂•4H₂O as a metal precursor by a simple chemical method. Meanwhile, in order to optimize the ORR activity, the catalysts were synthesized with different amounts of Co and urea, and heat-treated at different temperatures from 600-1000 ℃. SEM, TEM, BET, XRD and XPS techniques were used to characterize the catalysts in terms of structures and compositions, as well as the catalytic active sites. CV and LSV were measured to compare the ORR activity and to obtain the electron transfer number. The peak potential for oxygen reduction was approximately 0.829 V (vs. RHE) on the optimum Co_0.13-N_0.3/C-800 catalyst in an alkaline electrolyte. The results indicated that Co-N-C was potentially catalytic active site and responsible for the ORR catalytic activity in an alkaline electrolyte. The overall electron transfer number for ORR catalyzed by the optimum Co-N/C catalyst was determined to be 3.7, suggesting that the ORR catalyzed by Co-N/C was a mixture of 2- and 4-electron transfer pathways, dominated by a 4-electron transfer process. Furthermore, the Co_x-N_y/C-T catalysts also exhibited excellent methanol tolerance and stability.

Key words： Cobalt-based nitrogen-doped carbon catalyst; electrocatalysis；oxygen reduction reaction; catalytic active site; heat-treatment

参考文献

[1] Calle-Vallejo F, Martínez J I, Rossmeisl J. Density functional studies of functionalized graphitic materials with late transition metals for Oxygen Reduction Reactions[J]. Physical Chemistry Chemical Physics, 2011, 13(34): 15639-15643.

[2] Chen R, Li H, Chu D, et al. Unraveling oxygen reduction reaction mechanisms on carbon-supported Fe-phthalocyanine and Co-phthalocyanine catalysts in alkaline solutions[J]. The Journal of Physical Chemistry C, 2009, 113(48): 20689-20697.

[3] Ikeda T, Boero M, Huang S F, et al. Carbon alloy catalysts: active sites for oxygen reduction reaction[J]. Journal of Physical Chemistry C, 2008, 112(38): 14706-14709.

[4] Lee D H, Lee W J, Lee W J, et al. Theory, synthesis, and oxygen reduction catalysis of Fe-porphyrin-like carbon nanotube[J]. Physical Review Letters, 2011, 106(17): 175502-175505.

[5] Lee K R, Lee K U, Lee J W, et al. Electrochemical oxygen reduction on nitrogen doped graphene sheets in acid media[J]. Electrochemistry Communications, 2010, 12(8): 1052-1056.

[6] Lefèvre M, Dodelet J P. Fe-based catalysts for the reduction of oxygen in polymer electrolyte membrane fuel cell conditions: determination of the amount of peroxide released during electroreduction and its influence on the stability of the catalysts[J]. Electrochimica Acta, 2003, 48(19): 2749-2760.

[7] Liu G, Li X, Ganesan P, et al. Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on N-doped ordered porous carbon[J]. Applied Catalysis B: Environmental, 2009, 93(1): 156-165.

[8] Li X G, Liu G, Popov B N. Activity and stability of non-precious metal catalysts for oxygen reduction in acid and alkaline electrolytes[J]. Journal of Power Sources, 2010, 195 (19): 6373-6378.

[9] Li X G, Popov B N, Kawahara T, et al. Non-precious metal catalysts synthesized from precursors of carbon, nitrogen, and transition metal for oxygen reduction in alkaline fuel cells[J]. Journal of Power Sources, 2011, 196 (4): 1717-1722.

[10] Ganesan S, Leonard N, Barton S C. Impact of transition metal on nitrogen retention and activity of iron-nitrogen-carbon oxygen reduction catalysts[J]. Physical Chemistry Chemical Physics, 2014, 16(10): 4576-4585.

[11] Kim D W, Li Q L, Saito N. The role of the central Fe atom in the N₄-macrocyclic structure for the enhancement of oxygen reduction reaction in a heteroatom nitrogen-carbon nanosphere[J]. Physical Chemistry Chemical Physics, 2014, 16(28): 14905-14911.

[12] Yan X H, Xu B Q. Mesoporous carbon material co-doped with nitrogen and iron (Fe-N-C): high-performance cathode catalyst for oxygen reduction reaction in alkaline electrolyte[J]. Journal of Materials Chemistey A, 2014, 2(23): 8617-8622.

[13] Srinivasu K, Ghosh S K. Transition metal decorated graphyne: an efficient catalyst for oxygen reduction reaction[J]. The Journal of Physical Chemistry C, 2013, 117(49): 26021-26028.

[14] Zhang H J, Li H L, Li X T, et al. Porolyzing cobalt diethylenetriamine chelate on carbon (CoDETA/C) as a family of non-precious metal oxygen reduction catalyst[J]. International Journal of Hydrogen Energy, 2014, 39(1): 267-276.

[15] Chen J Y, Cui X Q, Zheng W T. The role of trace Fe in Fe-N-doped amorphous carbon with excellent electrocatalytic performance for oxygen reduction reaction[J]. Catalysis Communications, 2015, 60: 37-41.

[16] Qian Y D, Du P, Wu P, et al. Chemical nature of catalytic active sites for the oxygen reduction reaction on nitrogen-doped carbon-supported non-noble metal catalysts[J]. The Journal of Physical Chemistry C, 2016, 120(18): 9884-9896.

[17] Bezerra C W B, Zhang L, Lee K, et al. A review of Fe–N/C and Co–N/C catalysts for the oxygen reduction reaction[J]. Electrochimica Acta, 2008, 53(15): 4937-4951.

[18] Thorum M S, Hankett J M, Gewirth A A. Poisoning the oxygen reduction reaction on carbon-supported Fe and Cu electrocatalysts: evidence for metal-centered activity[J]. Journal Physical Chemistry Letters, 2011, 2(4): 295-298.

[19] Lefèvre M, Dodelet J P, Bertrand P. Molecular oxygen reduction in PEM fuel cells: evidence for the simultaneous presence of two active sites in Fe-based catalysts[J]. The Journal of Physical Chemistry B, 2002, 106(34): 8705-8713.

[20] Bashyam R, Zelenay P. A class of non-precious metal composite catalysts for fuel cells[J]. Nature, 2006, 443(7107): 63-66.

[21] Lefèvre M, Proietti E, Jaouen F, etc. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells[J]. Science, 2009, 324(5923): 71-74.

[22] Mo Z Y, Liao S J, Zheng Y Y, et al. Preparation of nitrogen-doped carbon nanotube arrays and their catalysis towards cathodic oxygen reduction in acidic and alkaline media[J]. Carbon, 2012, 50(7): 2620-2627.

[23] Byon H R, Suntivich J, Crumlin E J, et al. Fe-N-modified multi-walled carbon nanotubes for oxygen reduction reaction in acid[J]. Physical Chemistry Chemical Physics, 2011, 13(48): 21437-21445.

[24] Niwa H, Horiba K, Harada Y, et al. X-ray absorption analysis of nitrogen contribution to oxygen reduction reaction in carbon alloy cathode catalysts for polymer electrolyte fuel cells[J]. Journal of Power Sources, 2009, 187(1): 93-97.

[25] Liu G, Li X G, Ganesan P, et al. Studies of oxygen reduction reaction active sites and stability of nitrogen-modified carbon composite catalysts for PEM fuel cells[J]. Electrochimica Acta, 2010, 55(8): 2853-2858.

[26] Gomathi A, Reshma S, Rao C N R. A simple urea-based route to ternary metal oxynitride nanoparticles[J]. Journal of Solid State Chemistry, 2009, 182(1): 72-76.

[27] Zhao C Y(赵灿云), Huang L(黄林), You Y(尤勇), et al. Recycling MF Solid Waste into Mesoporous Nitrogen-Doped Carbon with Iron Carbide Complex in Graphitic Layers as an Efficient Catalyst for Oxygen Reduction Reaction[J]. Journal of Electrochemistry(电化学), 2016, 22(2): 176-184.

[28] Chen C(陈驰), Zhou Z Y(周志有), Zhang X S(张新胜), et al. Synthesis of Fe, N-doped Graphene/Carbon Black Composite with High Catalytic Activity for Oxygen Reduction Reaction[J]. Journal of Electrochemistry(电化学), 2016, 22(1): 25-31.

[29] Liu Z Y, Zhang G X, Lu Z Y, et al. One-step scalable preparation of N-doped nanoporous carbon as a high-performance electrocatalyst for the oxygen reduction reaction[J]. Nano Research, 2013, 6(4):293-301.

[30] Oda K, Yoshio T, Oda K. Preparation of Co-C films by radio-frequency sputtering [J]. Journal of Materials Science Letters, 1990, 9(11): 1319-1321.

[31] Luigi O, Alessandro H A, Monteverde V, et al. Activity of CoeN multi walled carbon nanotubes electrocatalysts for oxygen reduction reaction in acid conditions[J]. Journal of Power Sources, 2015, 278: 296-307.

[32] Rao C V, Cabrera C R, Ishikawa Y. In search of the active site in nitrogen-doped carbon nanotube electrodes for the oxygen reduction reaction[J]. The Journal of Physical Chemistry Letters, 2010, 1(18): 2622-2627.

[33] Kónya Z, Kiss J, OszkóA, et al. XPS characterisation of catalysts during production of multiwalled carbon nanotubes [J]. Physical Chemistry Chemical Physics, 2001, 3: 155-158.

[34] Pels J R, Kapteijn F, Moulijn J A, et al. Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis[J]. Carbon, 1995, 33(11): 1641-1653.

[35] Xu F, Minniti M, Barone P, etc. Nitrogen doping of single walled carbon nanotubes by low energy ion implantation[J]. Carbon, 2008, 46(11): 1489-1496.

[36] Morozan A, Jegou P, Jousselme B, et al. Electrochemical performance of annealed cobalt–benzotriazole/CNTs catalysts towards the oxygen reduction reaction[J]. Physical Chemistry Chemical Physics, 2011,13(48): 21600-21607.

[37] Yuasa M, Yamaguchi A, Itsuki H, et al. Modifying carbon particles with polypyrrole for adsorption of cobalt ions as electrocatatytic site for oxygen reduction[J]. Materials Chemistry, 2005, 17(17): 4278-4281.

[38] Soin N, Roy S S, Karlsson L, et al. Sputter deposition of highly dispersed platinum nanoparticles on carbon nanotube arrays for fuel cell electrode material[J]. Diamond and Related Materials, 2010, 19(5): 595-598.

[39] Su F B, Tian Z Q, Poh C K, et al. Pt nanoparticles supported on nitrogen-doped porous carbon nanospheres as an electrocatalyst for fuel cells†[J]. Materials Chemistry, 2010, 22(3): 832-839.

[40] Yang S B, Feng X L, Wang X C, et al. Graphene-based carbon nitride nanosheets as efficient metal-free electrocatalysts for oxygen reduction reactions[J]. Angewandte Chemie(International Edition), 2011, 50(23): 5339-5343.

[41] Byon H R, Suntivich J, Shao-Horn Y. Graphene-based non-noble-metal catalysts for oxygen reduction reaction in acid[J]. Chemistry of Materials, 2011, 23(15): 3421-3428.

[42] Wen Z H, Wang X C, Mao S, et al. Crumpled nitrogen-doped graphene nanosheets with ultrahigh pore volume for high-performance supercapacitor[J]. Advanced Materials, 2012, 24(41): 5610−5616.

[43] Zhang R, Ma J H, Wang W Y, et al. Zeolite-encapsulated M(Co, Fe, Mn)(SALEN) complexes modified glassy carbon electrodes and their application in oxygen reduction[J]. Journal of Electroanalytical Chemistry, 2010, 643(1-2): 31-38.

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