JAPC  >> Vol. 6 No. 3 (August 2017)

    水滑石前体法制备CoAl2O4/石墨烯气凝胶作为双功能电催化
    CoAl2O4/Graphene Aerogel by Hydrotalcite Precursor Method as Bifunctional Electrocatalysts

  • 全文下载: PDF(1600KB) HTML   XML   PP.113-120   DOI: 10.12677/japc.2017.63014  
  • 下载量: 239  浏览量: 793  

作者:  

张 聪,孟 格:北京化工大学化工资源有效利用国家重点实验室,北京

关键词:
钴铝水滑石钴铝氧化物石墨烯气凝胶ORR/OER双功能催化剂CoAl-LDH CoAl2O4 Graphene Aerogels OER/ORR Bifunctional Electrocatalysts

摘要:

研究氧还原(ORR)和氧析出(OER)反应的双功能电催化剂,对于新能源电池的探索和应用有着重要意义。本文利用水滑石前驱体法水热合成了钴铝水滑石/石墨烯气凝胶(CoAl-LDH/GA),再经过高温煅烧过程,得到钴铝氧化物/石墨烯气凝胶(CoAl2O4/GA)。采用SEM、TEM以及XRD对材料的表面特征及微观结构进行了表征,并考察了该电极材料的电化学性能。结果表明,CoAl2O4/GA复合材料具有双功能电催化特性,在碱性电解质中其对OER和ORR都具有优异的催化活性。CoAl2O4/GA对ORR的催化活性可与商业Pt/C (20 wt%)相媲美,且循环稳定性远高于后者,同时其对OER的循环稳定性也优于商业Ir/C (20wt%)。

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are critical paired reac-tions for both energy conversion and storage. Recently, the research on electrocatalysts for OER/ ORR has been focused on the study of easy, cost-effective, and highly active composites as potential alternatives to the precious metal materials (such as Pt, Ru, Ir). In this work, cobalt-aluminum hydrotalcite/graphene aerogels (CoAl-LDH/GA) were fabricated via a facile hydrothermal process, using the electrostatic interaction of single cobalt aluminum hydrotalcite (CoAl-LDH) and graphene oxide (GO). After high temperature calcination process, the cobalt aluminum oxide/gra- phene aerogel composites (CoAl2O4/GA) were obtained. The surface properties, microstructure pore size, element content and crystalline phase of the prepared products had been characterized by means of SEM, TEM and XRD, respectively. Results showed that the best catalyst exhibited high activity, which was close to commercial Pt/C and Ir/C catalysts, while the cycle stability was much higher than the commercial one. Therefore, the CoAl2O4/GA composite material was a perfect bifunctional electrocatalyst materials.

文章引用:
张聪, 孟格. 水滑石前体法制备CoAl2O4/石墨烯气凝胶作为双功能电催化[J]. 物理化学进展, 2017, 6(3): 113-120. https://doi.org/10.12677/japc.2017.63014

参考文献

[1] Zhuang, Z.B., Stephen, A.G., Zheng, J., Glen, R.J., Stavros, C., Dionisios, G.V. and Yan, Y.S. (2016) Nickel Supported on Nitrogen-Doped Carbon Nanotubes as Hydrogen Oxidation Reaction Catalyst in Alkaline Electrolyte. Nature Communication, 7, Article No. 10141.
https://doi.org/10.1038/ncomms10141
[2] Lu, Z.Y., Yang, Q., Zhu, W., Zhu, W., Chang, Z., Liu, J.F., Sun, X.M., David, G.E. and Duan, X. (2012) Hierarchical Co3O4@Ni-Co-O Super-Capacitor Electrodes with Ultrahigh Specific Capacitance per Area. Nano Research, 5, 369- 378.
https://doi.org/10.1007/s12274-012-0217-2
[3] Yang, Q., Lu, Z.Y., Li, T., Sun, X.M. and Liu, J.F. (2014) Hierarchical Construction of Core-Shell Metal Oxide Nanoarrays with Ultrahigh Areal Capacitance. Nano Energy, 7, 170-178.
[4] Meng, G., Yang, Q., Wu, X.C., Wan, P.B., Li, Y.P., Lei, X.D., Sun, X.M. and Liu, J.F. (2016) Hierarchical Mesoporous NiO Nanoarrays with Ultrahigh Capacitance for Aqueous Hybrid Supercapacitor. Nano Energy, 30, 831-839.
[5] Xu, Y.T., Xiao, X.F., Ye, Z.M., Zhao, S.L., Shen, R.G., He, C.T., Zhang, J.P., Li, Y.D. and Chen, X.M. (2017) A Cage-Confinement Pyrolysis Route to Ultrasmall Tungsten Carbide Nanoparticles for Efficient Hydrogen Evolution. Journal of the American Chemical Society, 139, 5285.
https://doi.org/10.1021/jacs.7b00165
[6] Shui, J., Du, F., Xue, C., Li, Q. and Dai, L. (2014) Vertically Aligned N-Doped Coral-like Carbon Fiber Arrays as Efficient Air Electrodes for High-Performance Nonaqueous Li-O2 Batteries. Acs Nano, 8, 3015-3022.
https://doi.org/10.1021/nn500327p
[7] Kim, D.W., Li, O.L. and Saito, N. (2015) Enhancement of ORR Catalytic Activity by Multiple Heteroatom-Doped Carbon Materials. Physical Chemistry Chemical Physics, 17, 407-413.
https://doi.org/10.1039/C4CP03868A
[8] Davari, E., Johnson, A.D., Mittal, A., Xiong, M. and Ivey, D.G. (2016) Manga-nese-Cobalt Mixed Oxide Film as a Bifunctional Catalyst for Rechargeable Zinc-Air Batteries. Electrochimica Acta, 211, 735-743.
[9] 赖渊, 周德璧, 胡剑文, 崔莉莉. 碱性燃料电池Co-N/C复合催化剂的电化学性能[J]. 化学学报, 2008, 66(9): 1015-1020.
[10] Song, F. and Hu, X. (2014) Exfoliation of Layered Double Hydroxides for Enhanced Oxygen Evolution Catalysis. Nature Communications, 5, 4477.
https://doi.org/10.1038/ncomms5477
[11] Wu, H., Li, H., Zhao, X., Liu, Q., Wang, J., Xiao, J., et al. (2016) Highly Doped and Exposed Cu(I)-N Active Sites within Graphene towards Efficient Oxygen Reduction for Zinc-Air Batteries. Energy & Environmental Science.
https://doi.org/10.1039/C6EE01867J
[12] Deng, D., Yu, L., Chen, X., Wang, G., Jin, L., Pan, X., et al. (2013) Iron Encapsulated within Pod-Like Carbon Nanotubes for Oxygen Reduction Reaction. Angewandte Chemie, 52, 371-375.
https://doi.org/10.1002/anie.201204958
[13] Gupta, S., Tryk, D., Bae, I., Aldred, W. and Yeager, E. (1989) Heat-Treated Polyacrylonitrile-Based Catalysts for Oxygen Electroreduction. Journal of Applied Electrochemistry, 19, 19-27.
https://doi.org/10.1007/BF01039385
[14] Jasinski, R. (1964) A New Fuel Cell Cathode Catalyst. Nature, 201, 1212-1213.
https://doi.org/10.1038/2011212a0
[15] Lefèvre, M., Proietti, E., Jaouen, F. and Dodelet, J.P. (2009) Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells. Science, 324, 71-74.
https://doi.org/10.1126/science.1170051
[16] Yin, H., Tang, H., Wang, D., Gao, Y. and Tang, Z. (2012) Facile Synthesis of Surfactant-Free Au Cluster/Graphene Hybrids for High-Performance Oxygen Reduction Reaction. Acs Nano, 6, 8288-8297.
https://doi.org/10.1021/nn302984x
[17] Proietti, E., Jaouen, F., Lefèvre, M., Larouche, N., Tian, J., Herranz, J., et al. (2011) Iron-Based Cathode Catalyst with Enhanced Power Density in Polymer Electrolyte Membrane Fuel Cells. Nature Communications, 2, 416.
https://doi.org/10.1038/ncomms1427
[18] Wang, H., Bo, X., Luhana, C. and Guo, L. (2012) Nitrogen Doped Large Mesoporous Carbon for Oxygen Reduction Electrocatalyst Using DNA as Carbon and Nitrogen Precursor. Electrochemistry Communications, 21, 5-8.
[19] Zhang, C., Hao, R., Liao, H. and Hou, Y. (2013) Synthesis of Amino-Functionalized Graphene as Metal-Free Catalyst and Exploration of the Roles of Various Nitrogen States in Oxygen Reduction Reaction. Nano Energy, 2, 88-97.
[20] Wu, G., More, K.L., Johnston, C.M. and Zelenay, P. (2011) High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt. Science, 332, 443-447.
https://doi.org/10.1126/science.1200832
[21] Shui, J.L., Karan, N.K., Balasubramanian, M., Li, S.Y. and Liu, D.J. (2012) Fe/N/C Composite in Li-O2 Battery: Studies of Catalytic Structure and Activity toward Oxygen Evolution Reaction. Journal of the American Chemical Society, 134, 16654-16661.
https://doi.org/10.1021/ja3042993
[22] Wang, J., Song, Y., Li, Z., Liu, Q., Zhou, J., Jing, X., et al. (2010) In Situ Ni/Al Layered Double Hydroxide and Its Electrochemical Capacitance Performance. Energy & Fuels, 24, 6463-6467.
https://doi.org/10.1021/ef101150b
[23] 孙金陆, 甄卫军, 李进. LDHs材料的结构、性质及其应用研究进展[J]. 化工进展, 2013, 32(3): 610-616.
[24] 聂宏骞, 侯万国. 层状双金属氢氧化物的剥离方法及其应用[J]. 物理化学学报, 2011, 27(8): 1783-1796.
[25] Hima, H.I., Xiang, X., Zhang, L., Li, F. and Evans, D.G. (2008) Influence of Cobalt Content on Structure and Composition of Calcined Co-Al Layered Double Hydroxides and Catalytic Property for the Carbon Nanotubes Formation. Chinese Journal of Inorganic Chemistry, 24, 886-891.
[26] Ping, J., Wang, Y., Lu, Q., Chen, B., Chen, J., Huang, Y., et al. (2016) Self-Assembly of Single-Layer CoAl-Layered Double Hydroxide Nanosheets on 3D Graphene Network Used as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction. Advanced Materials, 28, 7640.
https://doi.org/10.1002/adma.201601019
[27] Itaya, K. and Bard, A.J. (1985) Clay-Modified Electrodes Preparation and Electrochemical Characterization of Pillared Clay-Modified Electrodes and Membranes. Journal of Physical Chemistry, 89, 5565-5568.
https://doi.org/10.1021/j100271a051
[28] Geim, A.K. and Novoselov, K.S. (2007) The Rise of Graphene. Nature Materials, 6, 183.
https://doi.org/10.1038/nmat1849
[29] Stoller, M.D., Park, S., Zhu, Y., An, J. and Ruoff, R.S. (2008) Graphene-Based Ultracapacitors. Nano Letters, 8, 3498.
https://doi.org/10.1021/nl802558y
[30] Lu, P., Xue, D., Yang, H. and Liu, Y. (2013) Supercapacitor and Nanoscale Research towards Electrochemical Energy Storage. International Journal of Smart & Nano Materials, 4, 2-26.
https://doi.org/10.1080/19475411.2011.652218
[31] 杨旭宇, 王贤保, 李静, 杨佳, 万丽, 王敬超. 氧化石墨烯的可控还原及结构表征[J]. 高等学校化学学报, 2012, 33(9): 1902-1907.