Citation: Li Danqin, Zhang Zhiqi, Zang Pengyuan, Ma Yanwen, Wu Qiang, Yang Lijun, Chen Qiang, Wang Xizhang, Hu Zheng. Alloyed Pt–Ru Nanoparticles Immobilized on Mesostructured Nitrogen-Doped Carbon Nanocages for Efficient Methanol Electrooxidation[J]. Acta Chimica Sinica, ;2016, 74(7): 587-592. doi: 10.6023/A16040196 shu

Alloyed Pt–Ru Nanoparticles Immobilized on Mesostructured Nitrogen-Doped Carbon Nanocages for Efficient Methanol Electrooxidation

Li Danqin ^a,b ,
Zhang Zhiqi ^a,b ,
Zang Pengyuan ^a,b ,
Ma Yanwen ^a,b ,
Wu Qiang ^a,b ,
Yang Lijun ^a,b ,
Chen Qiang ^a,b ,
Wang Xizhang ^a,b,*,, ,
Hu Zheng ^a,b

a.
Jiangsu Provincial Lab for Nanotechnology, Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
b.
High-Tech Research Institute of Nanjing University (Suzhou), Suzhou, Jiangsu 215123

Corresponding author: Wang Xizhang, wangxzh@nju.edu.cn
Received Date: 20 April 2016

Fund Project: Changzhou Technology Support Program CE20130032National Natural Science Foundation of China 51232003National Natural Science Foundation of China 21473089National Natural Science Foundation of China 21573107Suzhou Science and Technology Project ZXG2013025National Natural Science Foundation of China 51571110National Natural Science Foundation of China 21373108the National Basic Research Program of China (973 Program, 2013CB932902

Figures(4)

Direct methanol fuel cells (DMFC) have attracted extensive attention as ideal candidates for automotive and portable applications owing to the fascinating advantages such as high conversion efficiency, environmental friendliness, safety, wide sources of methanol, and simple cell structure. Electrocatalysts are one of crucial factors limiting the performance of DMFC. Nowadays, precious Pt-based catalyst, in spite of costliness and scarcity, is the most popular catalyst for methanol oxidation reaction (MOR) at anode due to the much better performances than those of the non-Pt catalysts. But there exists some shortcomings such as poor CO-tolerance and durability. Pt alloying with other metals, e.g. Ru, is an effective strategy to improve the catalytic performance. In addition, the support with a large specific surface area (SSA), high conductivity and suitable porous structure, such as sp² carbon, could lead to high dispersion, high utilization and stability of Pt-based nanoparticles, also favorable for MOR. Recently, by in situ MgO template method, we reported the unique 3D hierarchical carbon-based nanocages featured with ultrahigh SSA, micro-meso-macro-pore coexistence, good conductivity and easy doping, which exhibited excellent electrochemical performances. Herein, taking the advantages of nitrogen-dopant anchoring function and unique mesostructures of hierarchical N-doped carbon nanocages (hNCNC), we report the Pt-Ru electrocatalysts immobilized on hNCNC (Pt-Ru/hNCNC) prepared via modified microwave-assisted ethylene glycol (EG) reduction method. The so-constructed Pt-Ru/hNCNC catalysts with ca. 30 wt% loading and tunable atomic ratio of Pt to Ru have a highly homogeneous dispersion of metal nanoparticles with the average size of ca. 3 nm. The alloying Pt-Ru/hNCNC catalysts demonstrate good CO-tolerance, high MOR activity and durability, superior to those of the counterparts of Pt/hNCNC and commercial PtRu/C. The good electrochemical performance can be ascribed to the synergistic effects of the bifunctional effect due to introduction of Ru, small size and high dispersion of metal nanoparticles induced by the large SSA and nitrogen participation of hNCNC, and multi-scaled hierarchical pore structures beneficial to the mass transportation. These results proposed a potential strategy to develop the high-performance Pt-based MOR catalysts based on the novel mesostructured hNCNC.
- direct methanol fuel cell,
- electrocatalyst,
- mesostructured,
- nitrogen-doped carbon nanocages,
- Pt-Ru alloy nano-particles,
- methanol oxidation
1. [1]
  Chen, A.; Holt-Hindle, P. Chem. Rev. 2010, 110, 3767. doi: 10.1021/cr9003902
2. [2]
  Kakati, N.; Maiti, J.; Lee, S. H.; Jee, S. H.; Viswanathan, B.; Yoon, Y. S. Chem. Rev. 2014, 114, 12397. doi: 10.1021/cr400389f
3. [3]
  Gasteiger, H. A.; Markovic, N.; Ross, P. N.; Cairns, E. J. J. Phys. Chem. 1994, 98, 617. doi: 10.1021/j100053a042
4. [4]
  Liu, Z. L.; Guo, B.; Hong, L.; Lim, T. H. Electrochem. Commun. 2006, 8, 83. doi: 10.1016/j.elecom.2005.10.019
5. [5]
  Pereira, L. G. S.; dos Santos, F. R.; Pereira, M. E.; Paganin, V. A.; Ticianelli, E. A. Electrochim. Acta 2006, 51, 4061. doi: 10.1016/j.electacta.2005.11.025
6. [6]
  Sun, J.; Ma, H.; Jiang, H.; Dang, L.; Lu, Q.; Gao, F. J. Mater. Chem. 2015, 3, 15882. doi: 10.1039/C5TA01613D
7. [7]
  Mylswamy, S.; Wang, C. Y.; Liu, R. S.; Lee, J. F.; Tang, M. J.; Lee, J. J.; Weng, B. J. Chem. Phys. Lett. 2005, 412, 444. doi: 10.1016/j.cplett.2005.07.035
8. [8]
  Watanabe, M.; Motoo, S. J. Electroanal. Chem. Interfacial Electrochem. 1975, 60, 267. doi: 10.1016/S0022-0728(75)80261-0
9. [9]
  Yue, B.; Ma, Y. W.; Tao, H. S.; Yu, L. S.; Jian, G. Q.; Wang, X. Z.; Wang, X. S.; Lu, Y. N.; Hu, Z. J. Mater. Chem. 2008, 18, 1747. doi: 10.1039/b718283j
10. [10]
  Jiang, S.; Zhu, L.; Ma, Y.; Wang, X.; Liu, J.; Zhu, J.; Fan, Y.; Zou, Z.; Hu, Z. J. Power Sources 2010, 195, 7578. doi: 10.1016/j.jpowsour.2010.06.025
11. [11]
  Feng, H.; Ma, J.; Hu, Z. J. Mater. Chem. 2010, 20, 1702. doi: 10.1039/b915667d
12. [12]
  Joo, S. H.; Kwon, K.; You, D. J.; Pak, C.; Chang, H.; Kim, J. M. Electrochim. Acta 2009, 54, 5746. doi: 10.1016/j.electacta.2009.05.022
13. [13]
  Guerrero-Ruiz, A.; Badenes, P.; Rodriguez-Ramos, I. Appl. Catal. A: Gen. 1998, 173, 313. doi: 10.1016/S0926-860X(98)00187-2
14. [14]
  Kuang, Y.; Cui, Y.; Zhang, Y.; Yu, Y.; Zhang, X.; Chen, J. Chem. Eur. J. 2012, 18, 1522. doi: 10.1002/chem.v18.5
15. [15]
  Che, G.; Lakshmi, B. B.; Fisher, E. R.; Martin, C. R. Nature 1998, 393, 346. doi: 10.1038/30694
16. [16]
  Lin, M. L.; Huang, C. C.; Lo, M. Y.; Mou, C. Y. J. Phys. Chem. C 2008, 112, 867. doi: 10.1021/jp076748m
17. [17]
  Liu, Z.; Su, F.; Zhang, X.; Tay, S. W. ACS Appl. Mater. Interfaces 2011, 3, 3824. doi: 10.1021/am2010515
18. [18]
  Yu, J. S.; Kang, S.; Yoon, S. B.; Chai, G. J. Am. Chem. Soc. 2002, 124, 9382. doi: 10.1021/ja0203972
19. [19]
  Li, F.; Chan, K.-Y.; Yung, H.; Yang, C.; Ting, S. W. Phys. Chem. Chem. Phys. 2013, 15, 13570. doi: 10.1039/c3cp00153a
20. [20]
  Cong, H.-P.; Ren, X.-C.; Yu, S.-H. ChemCatChem 2012, 4, 1555. doi: 10.1002/cctc.v4.10
21. [21]
  Bin, D.; Ren, F.; Wang, H.; Zhang, K.; Yang, B.; Zhai, C.; Zhu, M.; Yang, P.; Du, Y. RSC Adv. 2014, 4, 39612. doi: 10.1039/C4RA07742C
22. [22]
  La-Torre-Riveros, L.; Guzman-Blas, R.; Méndez-Torres, A. E.; Prelas, M.; Tryk, D. A.; Cabrera, C. R. ACS Appl. Mater. Interfaces 2012, 4, 1134. doi: 10.1021/am2018628
23. [23]
  Jiang, S.; Ma, Y.; Jian, G.; Tao, H.; Wang, X.; Fan, Y.; Lu, Y.; Hu, Z.; Chen, Y. Adv. Mater. 2009, 21, 4953. doi: 10.1002/adma.v21:48
24. [24]
  Chen, S.; Bi, J.; Zhao, Y.; Yang, L.; Zhang, C.; Ma, Y.; Wu, Q.; Wang, X.; Hu, Z. Adv. Mater. 2012, 24, 5593. doi: 10.1002/adma.201202424
25. [25]
  Xie, K.; Qin, X.; Wang, X.; Wang, Y.; Tao, H.; Wu, Q.; Yang, L.; Hu, Z. Adv. Mater. 2012, 24, 347. doi: 10.1002/adma.201103872
26. [26]
  Jiang, Y.; Yang, L.; Sun, T.; Zhao, J.; Lyu, Z.; Zhuo, O.; Wang, X.; Wu, Q.; Ma, J.; Hu, Z. ACS Catal. 2015, 5, 6707. doi: 10.1021/acscatal.5b01835
27. [27]
  Lyu, Z.; Xu, D.; Yang, L.; Che, R.; Feng, R.; Zhao, J.; Li, Y.; Wu, Q.; Wang, X.; Hu, Z. Nano Energy 2015, 12, 657. doi: 10.1016/j.nanoen.2015.01.033
28. [28]
  Zhao, J.; Lai, H.; Lyu, Z.; Jiang, Y.; Xie, K.; Wang, X.; Wu, Q.; Yang, L.; Jin, Z.; Ma, Y.; Liu, J.; Hu, Z. Adv. Mater. 2015, 27, 3541. doi: 10.1002/adma.v27.23
29. [29]
  Lyu, Z.; Feng, R.; Zhao, J.; Fan, H.; Xu, D.; Wu, Q.; Yang, L.; Chen, Q.; Wang, X.; Hu, Z. Acta Chim. Sinica 2015, 73, 1013.
30. [30]
  Feng, R.; Wang, L.; Lyu, Z.; Wu, Q.; Yang, L.; Wang, X.; Hu, Z. Acta Chim. Sinica 2014, 72, 653. doi: 10.6023/A14030227
31. [31]
  Prabhuram, J.; Zhao, T. S.; Liang, Z. X.; Chen, R. Electrochim. Acta 2007, 52, 2649. doi: 10.1016/j.electacta.2006.09.027
32. [32]
  Roth, C.; Benker, N.; Theissmann, R.; Nichols, R. J.; Schiffrin, D. J. Langmuir 2008, 24, 2191. doi: 10.1021/la7015929
33. [33]
  Bock, C.; Paquet, C.; Couillard, M.; Botton, G. A.; MacDougall, B. R. J. Am. Chem. Soc. 2004, 126, 8028. doi: 10.1021/ja0495819
34. [34]
  Giorgi, L.; Pozio, A.; Bracchini, C.; Giorgi, R.; Turtù, S. J. Appl. Electrochem. 2001, 31, 325. doi: 10.1023/A:1017595920726
35. [35]
  Wang, Z.-C.; Ma, Z.-M.; Li, H.-L. Appl. Surf. Sci. 2008, 254, 6521. doi: 10.1016/j.apsusc.2008.04.017
36. [36]
  Liu, S.-H.; Yu, W.-Y.; Chen, C.-H.; Lo, A.-Y.; Hwang, B.-J.; Chien, S.-H.; Liu, S.-B. Chem. Mater. 2008, 20, 1622. doi: 10.1021/cm702777j
1. [1]
  Yongmei Liu , Lisen Sun , Zhen Huang , Tao Tu . Curriculum-Based Ideological and Political Design for the Experiment of Methanol Oxidation to Formaldehyde Catalyzed by Electrolytic Silver. University Chemistry, 2024, 39(2): 67-71. doi: 10.3866/PKU.DXHX202308020
2. [2]
  Haodong JIN , Qingqing LIU , Chaoyang SHI , Danyang WEI , Jie YU , Xuhui XU , Mingli XU . NiCu/ZnO heterostructure photothermal electrocatalyst for efficient hydrogen evolution reaction. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1068-1082. doi: 10.11862/CJIC.20250048
3. [3]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
4. [4]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
5. [5]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
6. [6]
  Hailang JIA , Hongcheng LI , Pengcheng JI , Yang TENG , Mingyun GUAN . Preparation and performance of N-doped carbon nanotubes composite Co₃O₄ as oxygen reduction reaction electrocatalysts. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 693-700. doi: 10.11862/CJIC.20230402
7. [7]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Cu基和Pt基甲醇水蒸气重整制氢催化剂研究进展. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-. doi: 10.1016/j.actphy.2025.100049
8. [8]
  Jinyi Sun , Lin Ma , Yanjie Xi , Jing Wang . Preparation and Electrocatalytic Nitrogen Reduction Performance Study of Vanadium Nitride@Nitrogen-Doped Carbon Composite Nanomaterials: A Recommended Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(4): 184-191. doi: 10.3866/PKU.DXHX202310094
9. [9]
  Fangxuan Liu , Ziyan Liu , Guowei Zhou , Tingting Gao , Wenyu Liu , Bin Sun . Hollow structured photocatalysts. Acta Physico-Chimica Sinica, 2025, 41(7): 100071-. doi: 10.1016/j.actphy.2025.100071
10. [10]
  Kaihui Huang , Dejun Chen , Xin Zhang , Rongchen Shen , Peng Zhang , Difa Xu , Xin Li . Constructing Covalent Triazine Frameworks/N-Doped Carbon-Coated Cu₂O S-Scheme Heterojunctions for Boosting Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(12): 2407020-. doi: 10.3866/PKU.WHXB202407020
11. [11]
  Fengqiao Bi , Jun Wang , Dongmei Yang . Specialized Experimental Design for Chemistry Majors in the Context of “Dual Carbon”: Taking the Assembly and Performance Evaluation of Zinc-Air Fuel Batteries as an Example. University Chemistry, 2024, 39(4): 198-205. doi: 10.3866/PKU.DXHX202311069
12. [12]
  Feng Han , Fuxian Wan , Ying Li , Congcong Zhang , Yuanhong Zhang , Chengxia Miao . Comprehensive Organic Chemistry Experiment: Phosphotungstic Acid-Catalyzed Direct Conversion of Triphenylmethanol for the Synthesis of Oxime Ethers. University Chemistry, 2025, 40(3): 342-348. doi: 10.12461/PKU.DXHX202405181
13. [13]
  Yongwei ZHANG , Chuang ZHU , Wenbin WU , Yongyong MA , Heng YANG . Efficient hydrogen evolution reaction activity induced by ZnSe@nitrogen doped porous carbon heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 650-660. doi: 10.11862/CJIC.20240386
14. [14]
  Tian TIAN , Meng ZHOU , Jiale WEI , Yize LIU , Yifan MO , Yuhan YE , Wenzhi JIA , Bin HE . Ru-doped Co₃O₄/reduced graphene oxide: Preparation and electrocatalytic oxygen evolution property. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 385-394. doi: 10.11862/CJIC.20240298
15. [15]
  Dan Li , Hui Xin , Xiaofeng Yi . Comprehensive Experimental Design on Ni-based Catalyst for Biofuel Production. University Chemistry, 2024, 39(8): 204-211. doi: 10.3866/PKU.DXHX202312046
16. [16]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
17. [17]
  Xuejie Wang , Guoqing Cui , Congkai Wang , Yang Yang , Guiyuan Jiang , Chunming Xu . 碳基催化剂催化有机液体氢载体脱氢研究进展. Acta Physico-Chimica Sinica, 2025, 41(5): 100044-. doi: 10.1016/j.actphy.2024.100044
18. [18]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
19. [19]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
20. [20]
  Mingjie Lei , Wenting Hu , Kexin Lin , Xiujuan Sun , Haoshen Zhang , Ye Qian , Tongyue Kang , Xiulin Wu , Hailong Liao , Yuan Pan , Yuwei Zhang , Diye Wei , Ping Gao . Co/Mn/Mo掺杂加速NiSe₂重构以提高其电催化尿素氧化性能. Acta Physico-Chimica Sinica, 2025, 41(8): 100083-. doi: 10.1016/j.actphy.2025.100083

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(880)
HTML views(124)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142