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碳纳米粒子支撑的钯纳米催化剂在甲酸氧化中的电催化活性

  • 黄洁 ,
  • 周志有 ,
  • 宋洋 ,
  • 康雄武 ,
  • 刘珂 ,
  • 周万城 ,
  • 陈少伟
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  • 1. 加利福尼亚大学化学与生物化学系,美国 圣克鲁兹 95064; 2. 西北工业大学凝固技术国家重点实验室,陕西 西安710072

收稿日期: 2012-01-20

  修回日期: 2012-02-01

  网络出版日期: 2012-12-28

基金资助

This work was supported, in part, by the National Science Foundation (CHE–1012256 and DMR–0804049) and by the ACS-Petroleum Research Fund (49137–ND10). J. H. was supported, in part, by a research fellowship from the China Scholarship Council. TEM work was performed as a User Project at the National Center for Electron Microscopy, Lawrence Berkeley National Laboratory, which is supported by the US Department of Energy

Electrocatalytic Activity of Palladium Nanocatalysts Supported on Carbon Nanoparticles in Formic Acid Oxidation

  • Jie Huang ,
  • Zhiyou Zhou ,
  • Yang Song ,
  • Xiongwu Kang ,
  • Ke Liu ,
  • Wancheng Zhou ,
  • Shaowei Chen
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  • 1. Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, United States; 2. State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072, China

Received date: 2012-01-20

  Revised date: 2012-02-01

  Online published: 2012-12-28

Supported by

This work was supported, in part, by the National Science Foundation (CHE–1012256 and DMR–0804049) and by the ACS-Petroleum Research Fund (49137–ND10). J. H. was supported, in part, by a research fellowship from the China Scholarship Council. TEM work was performed as a User Project at the National Center for Electron Microscopy, Lawrence Berkeley National Laboratory, which is supported by the US Department of Energy

摘要

采用化学还原法制备了碳纳米粒子支撑的钯纳米结构(Pd-CNP). 透射电镜表征显示在Pd-CNP纳米复合物中,金属Pd呈菜花状结构,粒径约20~30 nm。它们由许多更小的Pd纳米粒子(3~8 nm)组成. 电化学研究表明,虽然Pd-CNP的电化学活性面积比商业Pd黑低40%(可能原因是部分Pd表面被一层碳纳米粒子覆盖),但其对甲酸氧化却表现出更好的电催化活性:质量比活性和面积比活性都比Pd黑高几倍. 催化活性增强的原因可能是碳纳米粒子支撑的Pd纳米结构具有特殊的层次化结构,可以形成更多的活性位,以及表面位更利于反应进行.

本文引用格式

黄洁 , 周志有 , 宋洋 , 康雄武 , 刘珂 , 周万城 , 陈少伟 . 碳纳米粒子支撑的钯纳米催化剂在甲酸氧化中的电催化活性[J]. 电化学, 2012 , 18(6) : 508 -514 . DOI: 10.61558/2993-074X.2619

Abstract

Palladium nanostructures were deposited onto carbon nanoparticle surface by a chemical reduction method. Transmission electron microscopic studies showed that whereas the resulting metal-carbon (Pd-CNP) nanocomposites exhibited a diameter of 20 to 30 nm, the metal components actually showed a cauliflower-like surface morphology that consisted of numerous smaller Pd nanoparticles (3 to 8 nm). Electrochemical studies showed that the effective surface area of the Pd-CNP nanoparticles was about 40% less than that of Pd black, possibly because the Pd nanoparticles were coated with a layer of carbon nanoparticles; yet, the Pd-CNP nanocomposites exhibited marked enhancement of the electrocatalytic activity in formic acid oxidation, as compared to that of Pd black. In fact, the mass- and surface-specific activities of the former were about three times higher than those of the latter. This improvement was likely a result of the enhanced accessibility of the Pd catalyst surface and the formation of abundant active sites of Pd on the carbon nanoparticle surface due to the hierarchical structure of the metal nanocatalysts.

参考文献

[1] Liu H S, Song C J, Zhang L, et al. A review of anode catalysis in the direct methanol fuel cell[J]. Journal of Power Sources, 2006, 155(2): 95-110.
[2] Yu X W, Pickup P G. Recent advances in direct formic acid fuel cells (DFAFC)[J]. Journal of Power Sources, 2008, 182(1): 124-132.
[3] Rhee Y W, Ha S Y, Masel R I. Crossover of formic acid through Nafion? membranes[J]. Journal of Power Sources, 2003, 117(1-2): 35-38.
[4] Sun S G, Clavilier J, Bewick A. The mechanism of electrocatalytic oxidation of formic acid on Pt (100) and Pt (111) in sulphuric acid solution: an emirs study[J]. Journal of Electroanalytical Chemistry, 1988, 240(1-2): 147-159.
[5] Osawa M, Komatsu K, Samjeske G, et al. The role of bridge-bonded adsorbed formate in the electrocatalytic oxidation of formic acid on platinum[J]. Angewandte Chemie-International Edition, 2011, 50(5): 1159-1163.
[6] Zhou W P, Lewera A, Larsen R, et al. Size effects in electronic and catalytic properties of unsupported palladium nanoparticles in electrooxidation of formic acid[J]. Journal of Physical Chemistry B, 2006, 110(27): 13393-13398.
[7] Zhou W J, Lee J Y. Particle size effects in Pd-catalyzed electrooxidation of formic acid[J]. Journal of Physical Chemistry C, 2008, 112(10): 3789-3793.
[8] Vidal-Iglesias F J, Solla-Gullon J, Herrero E, et al. Pd adatom decorated (100) preferentially oriented Pt nanoparticles for formic acid electrooxidation[J]. Angewandte Chemie-International Edition, 2010, 49(39): 6998-7001.
[9] Meng H, Wang C, Shen P K, et al. Palladium thorn clusters as catalysts for electrooxidation of formic acid[J]. Energy & Environmental Science, 2011, 4(4): 1522-1526.
[10] Zhou Z Y, Kang X W, Song Y, et al. Butylphenyl-functionalized palladium nanoparticles as effective catalysts for the electrooxidation of formic acid[J]. Chemical Communications, 2011, 47(21): 6075-6077.
[11] Zhou Z Y, Ren J, Kang X W, et al. Butylphenyl-functionalized Pt nanoparticles as CO-resistant electrocatalysts for formic acid oxidation[J]. Physical Chemistry Chemical Physics, 2012, 14(4): 1412-1417.
[12] Zheng H T, Li Y L, Chen S X, et al. Effect of support on the activity of Pd electrocatalyst for ethanol oxidation[J]. Journal of Power Sources, 2006, 163(1): 371-375.
[13] Tian L, Ghosh D, Chen W, et al. Nanosized carbon particles from natural gas soot[J]. Chemistry of Materials, 2009, 21(13): 2803-2809.
[14] Tian L, Song Y, Chang X J, et al. Hydrothermally enhanced photoluminescence of carbon nanoparticles[J]. Scripta Materialia, 2010, 62(11): 883-886.
[15] Song Y, Kang X W, Zuckerman N B, et al. Ferrocene-functionalized carbon nanoparticles[J]. Nanoscale, 2011, 3(5): 1984-1989.
[16] Nihoul G, Abdelmoula K, Metois J J. High-resolution images of a reconstructed surface structure on (111) gold platelets - Interpretation and comparison with theoretical models[J]. Ultramicroscopy, 1984, 12(4): 353-366.
[17] Golan Y, Margulis L, Hodes G, et al. Electrodeposited quantum dots. 2. High-resolution electron microscopy of epitaxial CdSe nanocrystals on (111) gold[J]. Surface Science, 1994, 311(1-2): L633-L640.
[18] Schlotterbeck U, Aymonier C, Thomann R, et al. Shape-selective synthesis of palladium nanoparticles stabilized by highly branched amphiphilic polymers[J]. Advanced Functional Materials, 2004, 14(10): 999-1004.
[19] Hoshi N, Kagaya K, Hori Y. Voltammograms of the single-crystal electrodes of palladium in aqueous sulfuric acid electrolyte: Pd(S)-[n(111) ? (111)] and Pd(S)-[n(100) ? (111)][J]. Journal of Electroanalytical Chemistry, 2000, 485(1): 55-60.
[20] Duncan H, Lasia A. Separation of hydrogen adsorption and absorption on Pd thin films[J]. Electrochimica Acta, 2008, 53(23): 6845-6850.
[21] Liang H P, Lawrence N S, Jones T G J, et al. Nanoscale tunable proton/hydrogen sensing: Evidence for surface-adsorbed hydrogen atom on architectured palladium nanoparticles[J]. Journal of the American Chemical Society, 2007, 129 (19): 6068-6069.
[22] Rand D A J, Woods R. The nature of adsorbed oxygen on rhodium, palladium and gold electrodes[J]. Journal of Electroanalytical Chemistry, 1971, 31(1): 29-38.
[23] Fang L L, Tao Q A, Li M F, et al. Determination of the real surface area of palladium electrode[J]. Chinese Journal of Chemical Physics, 2010, 23(5): 543-548.
[24] Chen M, Wang Z B, Zhou K, et al. Synthesis of Pd/C catalyst by modified polyol process for formic acid electrooxidation[J]. Fuel Cells, 2010, 10(6): 1171-1175.
[25] Cheng N C, Lv H F, Wang W, et al. An ambient aqueous synthesis for highly dispersed and active Pd/C catalyst for formic acid electro-oxidation[J]. Journal of Power Sources, 2010, 195(21): 7246-7249.
[26] Huang X Q, Tang S H, Mu X L, et al. Freestanding palladium nanosheets with plasmonic and catalytic properties[J]. Nature Nanotechnology, 2011, 6(1): 28-32.
[27] Baranova E A, Miles N, Mercier P H J, et al. Formic acid electro-oxidation on carbon supported PdxPt1-x (0 ≤ x ≤ 1) nanoparticles synthesized via modified polyol method[J]. Electrochimica Acta, 2010, 55(27): 8182-8188.
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