Register
ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 2016,Vol.32>> Issue(6)>> 1473-1481     doi: 10.3866/PKU.WHXB201603112         中文摘要
New Methanol-Tolerant Oxygen Reduction Electrocatalyst——Nitrogen-Doped Hollow Carbon Microspheres@Platinum Nanoparticles Hybrids
TIAN Chun-Xia, YANG Jun-Shuai, LI Li, ZHANG Xiao-Hua, CHEN Jin-Hua
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. China
Full text: PDF (7489KB) HTML Export: BibTeX | EndNote (RIS)

A new methanol-tolerant oxygen reduction electrocatalyst, nitrogen-doped hollow carbon microspheres@platinum nanoparticles hybrids (HNCMS@Pt NPs), has been synthesized by a facile template route. In brief, Pt NPs were loaded on the surface of NH2-functionalized SiO2 microspheres (Pt NPs/SiO2). Then, the Pt NPs/SiO2 hybrids were wrapped by polydopamine (PDA) film. After direct carbonization of PDA-wrapped Pt NPs/SiO2 hybrids under a nitrogen atmosphere and further treatment in a hydrofluoric acid solution, Pt NPs embedded within nitrogen-doped hollow carbon microsphere (HNCMS) were obtained and labeled as HNCMS@Pt NPs. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, specific surface area analysis, and X-ray photoelectron spectroscopy were used to characterize the HNCMS@Pt NPs hybrids. The electrochemical properties of the HNCMS@Pt NPs hybrids for oxygen reduction reaction have also been investigated by cyclic voltammetry and linear sweep voltammetry. The results show that the Pt loading mass in the HNCMS@Pt NPs hybrids is up to 11.9% (w, mass fraction). Furthermore, the as-prepared HNCMS@Pt NPs catalyst exhibits good electrocatalytic activity, high stability, and excellent methanol-tolerance toward oxygen reduction reactions, implying potential applications in practical direct methanol fuel cells (DMFCs) as methanol-tolerant cathodic catalysts.



Keywords: Pt nanoparticle   Nitrogen-doping   Hollow carbon microsphere   Oxygen-reduction reaction   Methanol-tolerance  
Received: 2016-01-15 Accepted: 2016-03-11 Publication Date (Web): 2016-03-11
Corresponding Authors: CHEN Jin-Hua Email: chenjinhua@hnu.edu.cn

Fund: The project was supported by the Program for Changjiang Scholars and Innovative Research Team in University, China (IRT1238) and National Natural Science Foundation of China (21275041, J1210040, J1103312).

Cite this article: TIAN Chun-Xia, YANG Jun-Shuai, LI Li, ZHANG Xiao-Hua, CHEN Jin-Hua. New Methanol-Tolerant Oxygen Reduction Electrocatalyst——Nitrogen-Doped Hollow Carbon Microspheres@Platinum Nanoparticles Hybrids[J]. Acta Phys. -Chim. Sin., 2016,32 (6): 1473-1481.    doi: 10.3866/PKU.WHXB201603112

(1) Wang, H.: Liang, J.: Zhu, L.: Peng, F.: Yu, H.: Yang, J. Fuel Cells 2010, 10 (1), 99. doi: 10.1002/fuce.200900112
(2) Li, L.: He, X. L.: Qin, T.: Dai, F. T.: Zhang, X. H.: Chen, J. H. Acta Phys. -Chim. Sin. 2015, 31 (5), 927. [李丽, 何小丽, 覃涛, 戴富涛, 张小华, 陈金华. 物理化学学报, 2015, 31 (5), 927.] doi: 10.3866/PKU.WHXB201503241
(3) Wang, C.: Kang, J. X.: Wang, L. L.: Chen, T.W.: Li, J.: Zhang, D. F.: Guo, L. Acta Phys. -Chim. Sin. 2014, 30 (4), 708. [王纯, 康建新, 王利利, 陈庭文, 李杰, 张东凤, 郭林. 物理化学学报, 2014, 30 (4), 708.] doi: 10.3866/PKU.WHXB201401222
(4) Cui, Z. M.: Chen, H.: Zhao, M. T.: Marshall, D.: Yu, Y. C.: Abruna, H.: DiSalvo, F. J. J. Am. Chem. Soc. 2014, 136 (29), 10206. doi: 10.1021/ja504573a
(5) Cui, Y.: Kuang, Y. J.: Zhang, X. H.: Liu, B.: Chen, J. H. Acta Phys. -Chim. Sin. 2013, 29 (5), 989. [崔颖, 匡尹杰, 张小华, 刘博, 陈金华. 物理化学学报, 2013, 29 (5), 989.] doi: 10.3866/PKU.WHXB201303121
(6) Zhou, Y.: Chu, Y. Q.: Liu, W. M.: Ma, C. A. Acta Phys. -Chim. Sin. 2013, 29 (2), 287. [周阳, 褚有群, 刘委明, 马淳安. 物理化学学报, 2013, 29 (2), 287.] doi: 10.3866/PKU.WHXB201211261
(7) Yang, W. X.: Liu, X. J.: Yue, X. Y.: Jia, J. B.: Guo, S. J. J. Am. Chem. Soc. 2015, 137 (4), 1436. doi: 10.1021/ja5129132
(8) Oh, J. G.: Lee, C. H.: Kim, H. Electrochem. Commun. 2007, 9
(10), 2629. doi: 10.1016/j.elecom.2007.08.019
(9) Lee, K.: Savadogo, O.: Ishihara, A.: Mitsushima, S.: Kamiya, N.: Ota, K. J. Electrochem. Soc. 2006, 153 (1), A20. doi: 10.1149/1.2128101
(10) Ozenler, S. S.: Kad?rgan, F. J. Power Sources 2006, 154 (2), 364. doi: 10.1016/j.jpowsour.2005.10.031
(11) Pylypenko, S.: Mukherjee, S.: Olson, T. S.: Atanassov, P. Electrochim. Acta 2008, 53 (27), 875. doi: 10.1016/j.electacta.2008.05.047
(12) Wen, Z. H.: Liu, J.: Li, J. H. Adv. Mater. 2008, 20 (4), 743. doi: 10.1002/adma.200701578
(13) Wu, Z. X.: Lv, Y.Y.: Xia, Y.Y.: Webley, P. A.: Zhao, D.Y. J. Am. Chem. Soc. 2012, 134 (4), 2236. doi: 10.1021/ja209753w
(14) Guo, X.: Li, L.: Zhang, X. H.: Chen, J. H. ChemElectroChem 2015, 2 (3), 404. doi: 10.1002/celc.v2.3
(15) Dai, Y. H.: Jiang, H.: Hu, Y. J.: Fu, Y.: Li, C. Z. Ind. Eng. Chem. Res. 2014, 53 (8), 3125. doi: 10.1021/ie403950t
(16) Zhang, C.: Xu, L.: Shan, N.: Sun, T.: Chen, J.: Yan, Y. ACS Catal. 2014, 4 (6), 1926. doi: 10.1021/cs500107t
(17) Galeano, C.: Meier, J. C.: Soorholtz, M.: Bongard, H.: Baldizzone, C.: Karl, J. J. ACS Catal. 2014, 4 (11), 3856. doi: 10.1021/cs5003492
(18) Huang, Y. Q.: Huang, H. L.: Gao, Q. Z.: Gan, C. F.: Liu, Y. J. Electrochim. Acta 2014, 149, 34. doi: 10.1016/j.electacta.2014.10.102
(19) Zhang, X. H.: Zhong, J. D.: Yu, Y. M.: Zhang, Y. S.: Liu, B.: Chen, J. H. Acta Phys. -Chim. Sin. 2013, 29 (6), 1297. [张小华, 钟金娣, 于亚明, 张云松, 刘博, 陈金华. 物理化学学报, 2013, 29 (6), 1297.] doi: 10.3866/PKU.WHXB201304011
(20) Cheng, J. L.: Wang, Y.: Teng, C.: Shang, Y. J.: Ren, L. B.: Jiang, B.W. Chem. Eng. J. 2014, 242, 285. doi: 10.1016/j.cej.2013.12.089
(21) Li, Q.: Pan, H. Y.: Higgins, D.: Cao, R. G.: Zhang, G. Q.: Lv, H. F.: Wu, K. B.: Cho, J.: Wu, G. Small 2015, 11 (12), 1443. doi: 10.1002/smll.v11.12
(22) Lian, S. Y.: Ming, H.: Huang, H.: Kang, Z. H.: Liu, Y. Mater. Res. Bull. 2012, 11 (47), 3336. doi: 10.1016/j.marerresbull.2012.07.029
(23) Ficicilar, B.: Bayrakceken, A.: Eroglu, I. Int. J. Hydrog. Energy 2010, 35 (18), 9924. doi: 10.1016/j.ijhydene.2009.11.016
(24) Ding, B.: Yuan, C. Z.: Shen, L. F.: Xu, G. Y.: Nie, P.: Zhang, X. G. Chem. Eur. J. 2013, 19 (3), 1013. doi: 10.1002/chem.201202127
(25) Liang, C. D.: Li, Z. J.: Dai, S. Angew. Chem. Int. Ed. 2008, 47
(20), 3696. doi: 10.1002/anie.200702046
(26) Pachfule, P.: Dhavale, V. M.: Kandambeth, S.: Kurungot, S.: Banerjee, R. Chem. Eur. J. 2013, 19 (3), 974. doi: 10.1002/chem.201202940
(27) Wang, H. G.: Wu, Z.: Meng, F. L.: Ma, D. L.: Huang, X. L.: Wang, L. M.: Zhang, X. B. ChemSusChem 2013, 6 (1), 56. doi: 10.1002/cssc.201200680
(28) Guo, Y. X.: He, J. P.: Wang, T.: Xue, H. R.: Hu, Y. Y.: Li, G. X.: Tang, J.: Sun, X. J. Power Sources 2011, 196 (22), 9299. doi: 10.1016/j.jpowsour.2011.07.073
(29) Chang, K.W.: Lim, Z. Y.: Du, F. Y.: Yang, Y. L.: Chang, C. H.: Hu, C. C.: Lin, H. P. Diamond Relat. Mater. 2009, 18 (2), 448. doi: 10.1006/j.diamond.2008.10.003
(30) Li, S. S.: Lv, J. J.: Teng, L. N.: Wang, A. J.: Chen, J. R.: Feng, J. J. ACS Appl. Mater. Interfaces 2014, 6 (13), 10549. doi: 10.1021/am502148z
(31) Chaikittisilp, W.: Torad, N. L.: Li, C. L.: Imura, M.: Suzuki, N.: Ishihara, S.: Ariga, K.: Yamauchi, Y. Chem. Eur. J. 2014, 20
(15), 4217. doi: 10.1002/chem.201304404
(32) Lang, X. Y.: Han, G. F.: Xiao, B. B.: Gu, L.: Yang, Z. Z.: Wen, Z.: Zhu, Y. F.: Zhao, M.: Li, J. H.: Jiang, Q. Adv. Funct. Mater. 2015, 25 (2), 230. doi: 10.1002/adfm.v25.2

1. WANG Jun, LI Li, WEI Zi-Dong.Density Functional Theory Study of Oxygen Reduction Reaction on Different Types of N-Doped Graphene[J]. Acta Phys. -Chim. Sin., 2016,32(1): 321-328
2. HAYIERBIEK Kulisong, ZHAO Shu-Xian, YANG Yang, ZENG Han.Performance of Nitrogen-Doped Carbon Nanocomposite with Entrapped Enzyme-Based Fuel Cell[J]. Acta Phys. -Chim. Sin., 2015,31(9): 1715-1726
3. YANG Shuo, XU Gui-Yin, HAN Jin-Peng, BING Huan, DOU Hui, ZHANG Xiao-Gang.Nitrogen-Doped Porous Carbon Derived from Dopamine-Modified Polypyrrole and Its Electrochemical Capacitive Behavior[J]. Acta Phys. -Chim. Sin., 2015,31(4): 685-692
4. LI Li-Xiang, ZHAO Hong-Wei, XU Wei-Wei, ZHANG Yan-Qiu, AN Bai-Gang, GENG Xin.Preparation and Electrocatalytic Performance of Iron Based Nitrogen Doped Carbon Nanotubes[J]. Acta Phys. -Chim. Sin., 2015,31(3): 498-504
5. YANG Mei-Ni, LIN Rui, FAN Ren-Jie, ZHAO Tian-Tian, ZENG Hao.Preparation and Application of Pt-Ni Catalysts Supported on Cobalt-Polypyrrole-Carbon for Fuel Cells[J]. Acta Phys. -Chim. Sin., 2015,31(11): 2131-2138
6. GAO Hai-Li, LI Xiao-Long, HE Wei, GUO Rui-Ting, CHAI Bo.One-Step Synthesis of Reduced Graphene Oxide Supported Pt Nanoparticles and Its Electrocatalytic Activity for Methanol Oxidation[J]. Acta Phys. -Chim. Sin., 2015,31(11): 2117-2123
7. PENG San, GUO Hui-Lin, KANG Xiao-Feng.Preparation of Nitrogen-Doped Graphene and Its Electrocatalytic Activity for Oxygen Reduction Reaction[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1778-1786
8. XU Ling-Ling, ZHANG Xiao-Hua, CHEN Jin-Hua.Synthesis and Electrochemical Supercapacitive Properties of Nitrogen-Doped Mesoporous Carbons[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1274-1280
9. FAN Ren-Jie, LIN Rui, HUANG Zhen, ZHAO Tian-Tian, MA Jian-Xin.Preparation and Characterization of Pt Catalysts Supported on Cobalt-Polypyrrole-Carbon for Fuel Cells[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1259-1266
10. WANG Li, MA Jun-Hong.Synthesis and Electrocatalytic Properties of Pt Nanoparticles on Nitrogen-Doped Reduced Graphene Oxide for Methanol Oxidation[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1267-1273
11. YIN Hai-Feng, ZHANG Hong, YUE Li.Near-Infrared Plasmon Study on N-Doped Hexagonal Graphene Nanostructures[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1049-1054
12. XU Li, PAN Guo-Shun, LIANG Xiao-Lu, LUO Gui-Hai, ZOU Chun-Li, LUO Hai-Mei.Electrocatalytic Activity of Fe-N/C-TsOH Catalyst for the Oxygen Reduction Reaction in Alkaline Media[J]. Acta Phys. -Chim. Sin., 2014,30(2): 318-324
13. ZHAO Tian-Tian, LIN Rui, ZHANG Lu, CAO Chui-Hui, MA Jian-Xin.Effects of Pt Content on the Catalytic Performance of Co@Pt/C Core-Shell Structured Electrocatalysts[J]. Acta Phys. -Chim. Sin., 2013,29(08): 1745-1752
14. DAI Xian-Feng, ZHEN Ming-Fu, XU Pan, SHI Jing-Jing, MA Cheng-Yu, QIAO Jin-Li.Electrochemical Behavior of Pyridine-Doped Carbon-Supported Co-Phthalocyanine (Py-CoPc/C) for Oxygen Reduction Reaction and Its Application to Fuel Cell[J]. Acta Phys. -Chim. Sin., 2013,29(08): 1753-1761
15. ZHANG Xiao-Hua, ZHONG Jin-Di, YU Ya-Ming, ZHANG Yun-Song, LIU Bo, CHEN Jin-Hua.Well-Dispersed Platinum Nanoparticles Supported on Nitrogen-Doped Hollow Carbon Microspheres for Oxygen-Reduction Reaction[J]. Acta Phys. -Chim. Sin., 2013,29(06): 1297-1304
16. LI Shang, WANG Jia-Tang, CHEN Rui-Xin, ZHAO Wei, QIAN Liu, PAN Mu.Catalytic Performance of Heat-Treated Fe-Melamine/C and Fe-g-C3N4/C Electrocatalysts for Oxygen Reduction Reaction[J]. Acta Phys. -Chim. Sin., 2013,29(04): 792-798
17. CHEN Chong, CHEN Xiang-Ying, XIE Dong-Hua.Synthesis of Nitrogen Doped Porous Carbons from Sodium Carboxymethyl Cellulose and the Capacitive Performance[J]. Acta Phys. -Chim. Sin., 2013,29(01): 102-110
18. LI Li-Xiang, TAO Jing, GENG Xin, AN Bai-Gang.Preparation and Supercapacitor Performance of Nitrogen-Doped Carbon Nanotubes from Polyaniline Modification[J]. Acta Phys. -Chim. Sin., 2013,29(01): 111-116
19. WANG Wan-Li, MA Zi-Feng.Synthesis and Characteristics of Pt/graphene by Co-Reduction Method for Oxygen Reduction Reactions[J]. Acta Phys. -Chim. Sin., 2012,28(12): 2879-2884
20. SU Peng, GUO Hui-Lin, PENG San, NING Sheng-Ke.Preparation of Nitrogen-Doped Graphene and Its Supercapacitive Properties[J]. Acta Phys. -Chim. Sin., 2012,28(11): 2745-2753
21. LI Qiang, ZHAO Hui, JIANG Rui, GUO Li-Fan.Synthesis and Electrochemical Properties of La1.6Sr0.4Ni1-xCuxO4 as Cathode Materials for Intermediate Temperature Solid Oxide Fuel Cells[J]. Acta Phys. -Chim. Sin., 2012,28(09): 2065-2070
22. YIN Shi-Bin, LUO Lin, JING Sheng-Yu, ZHU Qiang-Qiang, QIANG Ying-Huai.Effect of Intermittent Microwave Heating on the Performance of Catalysts for Oxygen Reduction Reaction[J]. Acta Phys. -Chim. Sin., 2012,28(01): 85-89
23. XU Li, QIAO Jin-Li, DING Lei, HU Long-Yu, LIU Ling-Ling, WANG Hai-Jiang.Electrocatalytic Activity of CoPy/C Catalyst for the Oxygen Reduction Reaction in Alkaline Electrolyte[J]. Acta Phys. -Chim. Sin., 2011,27(10): 2251-2254
24. ZHANG Min, LI Jing-Jian, PAN Mu, XU Dong-Sheng.Catalytic Performance of Pt Nanowire Arrays for Oxygen Reduction[J]. Acta Phys. -Chim. Sin., 2011,27(07): 1685-1688
25. WANG Xi-Zhao, ZHENG Jun-Sheng, FU Rong, MA Jian-Xin.Pulse-Microwave Assisted Chemical Reduction Synthesis of Pt/C Catalyst and Its Electrocatalytic Oxygen Reduction Activity[J]. Acta Phys. -Chim. Sin., 2011,27(01): 85-90
26. ZHAO Yan-Chun, ZHAN Lu, TIAN Jian-Niao, NIE Su-Lian, NING Zhen.N-Doped Amorphous Carbon Supported Pd Catalysts for Methanol Electrocatalytic Oxidation[J]. Acta Phys. -Chim. Sin., 2011,27(01): 91-96
27. JIANG Lei, HUANG Hui, WANG Chun-Tao, ZHANG Wen-Kui, GAN Yong-Ping, TAO Xin-Yong.Photoelectrochromic Properties of TiO2-xNx/NiO Bilayer Thin Films[J]. Acta Phys. -Chim. Sin., 2010,26(02): 299-303
28. CAO Yong, JIAO Qing-Ze, ZHAO Yun.Synthesis of N-doped and Undoped Carbon Nanotubes on Fe/MgO Catalysts[J]. Acta Phys. -Chim. Sin., 2009,25(11): 2380-2384
29. YU Zhi-Yong; ZHANG Wei; MA Ming; CUI Xiao-Li.Visible Light Photoelectrochemical Response of Nitrogen-Doped TiO2 Thin Films Prepared by Anodic Oxidation of Titanium Nitride Films[J]. Acta Phys. -Chim. Sin., 2009,25(01): 35-40
30. BULGAN G.; ZONG Rui-Long; LIANG Shu-Hui; YAO Wen-Qing; ZHU Yong-Fa.CO Cataluminescence Property of Platinum Supported Composite Oxide Catalysts[J]. Acta Phys. -Chim. Sin., 2008,24(09): 1547-1552
31. ZHANG Xiao-Di; LI Wei-Shan; HUANG You-Ju; PENG Hai-Yan.Promotion of Oxygen Reduction Reaction on Vitreous Carbon Electrode by DTAB[J]. Acta Phys. -Chim. Sin., 2008,24(04): 691-694
32. LIANG Yun-Xiao; SHUI Miao; LI Rong-Sheng.Structures and Stabilities of Boron/Nitrogen-Doped Fullerene C20[J]. Acta Phys. -Chim. Sin., 2007,23(10): 1647-1651
33. TIAN Juan;ZHENG Dan;ZHANG Xi-Gui;ZHANG Bao-Hong;XIA Bao-Jia;YANG Hui.Preparation of Pt Nanoparticle Modified Porous Silicon Electrode and Its Electrocatalytic Performance[J]. Acta Phys. -Chim. Sin., 2007,23(01): 68-72
34. HUANG Jian-Shu;ZHANG Xiao-Gang.Microwave Synthesis of Pt-Au/MWCNTs Electrocatalyst and Its Catalytic Properties for Oxygen Reduction[J]. Acta Phys. -Chim. Sin., 2006,22(12): 1551-1554
35. ZHAO Feng-Ming;MA Chun-An;CHU You-Qun;XU Ying-Hua.Oxygen Reduction on Ni-MnO2 Electrode in Alkaline Solution[J]. Acta Phys. -Chim. Sin., 2006,22(06): 716-720
36. Zhu Su-Bing;Sun Si-Xiu;Wei-Wei;Xu Jun-Jian;Li Yan.The Preparation of Nitrogen-doped Carbon Nanotubes from Pyridine[J]. Acta Phys. -Chim. Sin., 2004,20(11): 1320-1323
37. Chu You-Qun;Ma Chun-An;Zhu Ying-Hong.Electrocatalytic Reduction of Oxygen on Carbon Nanotubes Electrode[J]. Acta Phys. -Chim. Sin., 2004,20(03): 331-335
38. Chen Wei;Sun Shi-Gang;Si Di;Chen Sheng-Pei.Electrocatalytic Properties of Agglomerates of Pt Nanoparticles in Methanol Oxidation[J]. Acta Phys. -Chim. Sin., 2003,19(05): 441-444
39. Li Xu-Guang;Han Fei;Xing Wei;Tang Ya-Wen;Lu Tian-Hong.Influence of Methanol on the Kinetics of Oxygen Reduction on Pt/C and CoPcTc/C[J]. Acta Phys. -Chim. Sin., 2003,19(04): 380-384
40. ZHU Hong, LUO Ming-Chuan, CAI Ye-Zheng, SUN Zhao-Nan.Core-Shell Structured Electrocatalysts for the Cathodic Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells[J]. Acta Phys. -Chim. Sin., 0,(): 0-0
Copyright © 2006-2016 Editorial office of Acta Physico-Chimica Sinica
Address: College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P.R.China
Service Tel: +8610-62751724 Fax: +8610-62756388 Email:whxb@pku.edu.cn
^ Top