A simple electrochemical method for conversion of Pt wires to Pt concave icosahedra and nanocubes on carbon paper for electrocatalytic hydrogen evolution

电化学方法把铂丝转化到碳布上形成铂二十面体和纳米立方体并用于电催化产氢

Abstract

In the controlled synthesis of noble metal nanostructures using wet-chemical methods, normally, metal salts/complexes are used as precursors, and surfactants/ ligands are used to tune/stabilize the morphology of nanostructures. Here, we develop a facile electrochemical method to directly convert Pt wires to Pt concave icosahedra and nanocubes on carbon paper through the linear sweep voltammetry in a classic three-electrode electrochemical cell. The Pt wire, carbon paper and Ag/AgCl (3 mol L−1 KCl) are used as the counter, working and reference electrodes, respectively. Impressively, the formed Pt nanostructures exhibit better electrocatalytic activity towards the hydrogen evolution compared to the commercial Pt/C catalyst. This work provides a simple and effective way for direct conversion of Pt wires into well-defined Pt nanocrystals with clean surface. We believe it can also be used for preparation of other metal nanocrystals, such as Au and Pd, from their bulk materials, which could exhibit various promising applications.

摘要

湿化学法可控合成贵金属纳米结构通常需要金属盐或金属配合物作为前体, 并利用表面活性剂和配体来调节和稳定纳米结构的形 貌. 本文通过一种简单的电化学方法(线性扫描伏安法), 在三电极体系中直接把铂线转化到碳布表面形成铂二十面体和纳米立方体. 在三 电极体系中, 铂线、碳布和Ag/AgCl(3 mol L−1 KCl)分别作为对电极、工作电极和参比电极. 与商业Pt/C催化剂相比, 制备的铂二十面体和 纳米立方体展现出优越的电催化活性. 该方法简单、有效, 可拓展到其他贵金属纳米结构的合成和应用研究. 如通过这种电化学方法直接 将Au、Pd等块体材料转化成具有各种潜在应用的Au、Pd等纳米结构.

References

  1. 1

    Joo SH, Park JY, Tsung CK, et al. Thermally stable Pt/mesoporous silica core–shell nanocatalysts for high-temperature reactions. Nat Mater, 2009, 8: 126–131

    Article  Google Scholar 

  2. 2

    Li Y, Cox JT, Zhang B. Electrochemical responses and electrocatalysis at single Au nanoparticles. J Am Chem Soc, 2010, 132: 3047–3054

    Article  Google Scholar 

  3. 3

    Wang C, Daimon H, Lee Y, et al. Synthesis of monodisperse Pt nanocubes and their enhanced catalysis for oxygen reduction. J Am Chem Soc, 2007, 129: 6974–6975

    Article  Google Scholar 

  4. 4

    Xia Y, Yang X. Toward cost-effective and sustainable use of precious metals in heterogeneous catalysts. Acc Chem Res, 2017, 50: 450–454

    Article  Google Scholar 

  5. 5

    Xiao L, Zhuang L, Liu Y, et al. Activating Pd by morphology tailoring for oxygen reduction. J Am Chem Soc, 2009, 131: 602–608

    Article  Google Scholar 

  6. 6

    Xu C, Wang H, Shen P, et al. Highly ordered Pd nanowire arrays as effective electrocatalysts for ethanol oxidation in direct alcohol fuel cells. Adv Mater, 2007, 19: 4256–4259

    Article  Google Scholar 

  7. 7

    Zhu W, Michalsky R, Metin Ö, et al. Monodisperse Au nanoparticles for selective electrocatalytic reduction of CO2 to CO. J Am Chem Soc, 2013, 135: 16833–16836

    Article  Google Scholar 

  8. 8

    Huang X, Li S, Huang Y, et al. Synthesis of hexagonal close-packed gold nanostructures. Nat Commun, 2011, 2: 292

    Article  Google Scholar 

  9. 9

    Fan Z, Bosman M, Huang X, et al. Stabilization of 4H hexagonal phase in gold nanoribbons. Nat Commun, 2015, 6: 7684

    Article  Google Scholar 

  10. 10

    Fan Z, Huang X, Han Y, et al. Surface modification-induced phase transformation of hexagonal close-packed gold square sheets. Nat Commun, 2015, 6: 6571

    Article  Google Scholar 

  11. 11

    Fan Z, Luo Z, Chen Y, et al. Synthesis of 4H/fcc-Au@M (M = Ir, Os, IrOs) core-shell nanoribbons for electrocatalytic oxygen evolution reaction. Small, 2016, 12: 3908–3913

    Article  Google Scholar 

  12. 12

    Fan Z, Luo Z, Huang X, et al. Synthesis of 4H/fcc noble multimetallic nanoribbons for electrocatalytic hydrogen evolution re-action. J Am Chem Soc, 2016, 138: 1414–1419

    Article  Google Scholar 

  13. 13

    Fan Z, Zhang H. Crystal phase-controlled synthesis, properties and applications of noble metal nanomaterials. Chem Soc Rev, 2016, 45: 63–82

    Article  Google Scholar 

  14. 14

    Tian N, Zhou ZY, Sun SG, et al. Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electrooxidation activity. Science, 2007, 316: 732–735

    Article  Google Scholar 

  15. 15

    Schrinner M, Ballauff M, Talmon Y, et al. Single nanocrystals of platinum prepared by partial dissolution of Au-Pt nanoalloys. Science, 2009, 323: 617–620

    Article  Google Scholar 

  16. 16

    Jin M, Zhang H, Xie Z, et al. Palladium concave nanocubes with high-index facets and their enhanced catalytic properties. Angew Chem Int Ed, 2011, 50: 7850–7854

    Article  Google Scholar 

  17. 17

    Wei L, Fan YJ, Tian N, et al. Electrochemically shape-controlled synthesis in deep eutectic solvents—a new route to prepare Pt nanocrystals enclosed by high-index facets with high catalytic activity. J Phys Chem C, 2012, 116: 2040–2044

    Article  Google Scholar 

  18. 18

    Yu T, Kim DY, Zhang H, et al. Platinum concave nanocubes with high-index facets and their enhanced activity for oxygen reduction reaction. Angew Chem Int Ed, 2011, 50: 2773–2777

    Article  Google Scholar 

  19. 19

    Xiao J, Liu S, Tian N, et al. Synthesis of convex hexoctahedral Pt micro/nanocrystals with high-index facets and electrochemistrymediated shape evolution. J Am Chem Soc, 2013, 135: 18754–18757

    Article  Google Scholar 

  20. 20

    Zhang Z, Liu Y, Chen B, et al. Submonolayered Ru deposited on ultrathin Pd nanosheets used for enhanced catalytic applications. Adv Mater, 2016, 28: 10282–10286

    Article  Google Scholar 

  21. 21

    Zhang Z, Luo Z, Chen B, et al. One-pot synthesis of highly anisotropic five-fold-twinned ptcu nanoframes used as a bifunctional electrocatalyst for oxygen reduction and methanol oxidation. Adv Mater, 2016, 28: 8712–8717

    Article  Google Scholar 

  22. 22

    Zhang L, Han L, Liu H, et al. Potential-cycling synthesis of single platinum atoms for efficient hydrogen evolution in neutral media. Angew Chem Int Ed, 2017, 56: 13694–13698

    Article  Google Scholar 

  23. 23

    Huang X, Zhao Z, Fan J, et al. Amine-assisted synthesis of concave polyhedral platinum nanocrystals having {411} high-index facets. J Am Chem Soc, 2011, 133: 4718–4721

    Article  Google Scholar 

  24. 24

    Kim D, Lee YW, Lee SB, et al. Convex polyhedral Au@Pd coreshell nanocrystals with high-index facets. Angew Chem Int Ed, 2012, 51: 159–163

    Article  Google Scholar 

  25. 25

    Lim B, Lu X, Jiang M, et al. Facile synthesis of highly faceted multioctahedral Pt nanocrystals through controlled overgrowth. Nano Lett, 2008, 8: 4043–4047

    Article  Google Scholar 

  26. 26

    Stamenkovic VR, Fowler B, Mun BS, et al. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science, 2007, 315: 493–497

    Article  Google Scholar 

  27. 27

    Zhang L, Zhang J, Kuang Q, et al. Cu2+-assisted synthesis of hexoctahedral Au–Pd alloy nanocrystals with high-index facets. J Am Chem Soc, 2011, 133: 17114–17117

    Article  Google Scholar 

  28. 28

    Li GR, Xu H, Lu XF, et al. Electrochemical synthesis of nanostructured materials for electrochemical energy conversion and storage. Nanoscale, 2013, 5: 4056–4069

    Article  Google Scholar 

  29. 29

    Wang D, Zhou WL, McCaughy BF, et al. Electrodeposition of metallic nanowire thin films using mesoporous silica templates. Adv Mater, 2003, 15: 130–133

    Article  Google Scholar 

  30. 30

    Lee W, Scholz R, Nielsch K, et al. A template-based electrochemical method for the synthesis of multisegmented metallic nanotubes. Angew Chem Int Ed, 2005, 44: 6050–6054

    Article  Google Scholar 

  31. 31

    Keilbach A, Moses J, Kohn R, et al. Electrodeposition of copper and silver nanowires in hierarchical mesoporous silica/anodic alumina nanostructures. Chem Mater, 2010, 22: 5430–5436

    Article  Google Scholar 

  32. 32

    Kanno Y, Suzuki T, Yamauchi Y, et al. Preparation of Au nanowire films by electrodeposition using mesoporous silica films as a template: vital effect of vertically oriented mesopores on a substrate. J Phys Chem C, 2012, 116: 24672–24680

    Article  Google Scholar 

  33. 33

    Tian N, Zhou ZY, Sun SG. Electrochemical preparation of Pd nanorods with high-index facets. Chem Commun, 2009, 293: 1502–1504

    Article  Google Scholar 

  34. 34

    Zhou ZY, Huang ZZ, Chen DJ, et al. High-Index faceted platinum nanocrystals supported on carbon black as highly efficient catalysts for ethanol electrooxidation. Angew Chem Int Ed, 2010, 49: 411–414

    Article  Google Scholar 

  35. 35

    Liu S, Tian N, Xie AY, et al. Electrochemically seed-mediated synthesis of sub-10 nm tetrahexahedral Pt nanocrystals supported on graphene with improved catalytic performance. J Am Chem Soc, 2016, 138: 5753–5756

    Article  Google Scholar 

  36. 36

    Yang Y, Jin H, Kim HY, et al. Ternary dendritic nanowires as highly active and stable multifunctional electrocatalysts. Nanoscale, 2016, 8: 15167–15172

    Article  Google Scholar 

  37. 37

    Wu J, Qi L, You H, et al. Icosahedral platinum alloy nanocrystals with enhanced electrocatalytic activities. J Am Chem Soc, 2012, 134: 11880–11883

    Article  Google Scholar 

  38. 38

    Zhou W, Wu J, Yang H. Highly uniform platinum icosahedra made by hot injection-assisted GRAILS method. Nano Lett, 2013, 13: 2870–2874

    Article  Google Scholar 

  39. 39

    Wang X, Choi SI, Roling LT, et al. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction. Nat Commun, 2015, 6: 7594

    Article  Google Scholar 

  40. 40

    He DS, He D, Wang J, et al. Ultrathin icosahedral Pt-enriched nanocage with excellent oxygen reduction reaction activity. J Am Chem Soc, 2016, 138: 1494–1497

    Article  Google Scholar 

  41. 41

    Wang H, Zhou S, Gilroy KD, et al. Icosahedral nanocrystals of noble metals: Synthesis and applications. Nano Today, 2017, 15: 121–144

    Article  Google Scholar 

  42. 42

    Tang Q, Zhang H, Meng Y, et al. Dissolution engineering of platinum alloy counter electrodes in dye-sensitized solar cells. Angew Chem Int Ed, 2015, 54: 11448–11452

    Article  Google Scholar 

  43. 43

    Lu CL, Prasad KS, Wu HL, et al. Au nanocube-directed fabrication of Au−Pd core−shell nanocrystals with tetrahexahedral, concave octahedral, and octahedral structures and their electrocatalytic activity. J Am Chem Soc, 2010, 132: 14546–14553

    Article  Google Scholar 

  44. 44

    Wang S, Yang G, Yang S. Pt-frame@Ni quasi core–shell concave octahedral PtNi3 bimetallic nanocrystals for electrocatalytic methanol oxidation and hydrogen evolution. J Phys Chem C, 2015, 119: 27938–27945

    Article  Google Scholar 

  45. 45

    Zhang H, Jin M, Xia Y. Noble-metal nanocrystals with concave surfaces: synthesis and applications. Angew Chem Int Ed, 2012, 51: 7656–7673

    Article  Google Scholar 

  46. 46

    Lv H, Xi Z, Chen Z, et al. A new core/shell NiAu/Au nanoparticle catalyst with pt-like activity for hydrogen evolution reaction. J Am Chem Soc, 2015, 137: 5859–5862

    Article  Google Scholar 

  47. 47

    Zhang Z, Hui J, Liu ZC, et al. Glycine-mediated syntheses of Pt concave nanocubes with high-index {hk0} facets and their enhanced electrocatalytic activities. Langmuir, 2012, 28: 14845–14848

    Article  Google Scholar 

  48. 48

    Lim B, Jiang M, Camargo PHC, et al. Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction. Science, 2009, 324: 1302–1305

    Article  Google Scholar 

  49. 49

    Marković NM, Grgur BN, Ross PN. Temperature-dependent hydrogen electrochemistry on platinum low-index single-crystal surfaces in acid solutions. J Phys Chem B, 1997, 101: 5405–5413

    Article  Google Scholar 

  50. 50

    Bai S, Wang C, Deng M, et al. Surface polarization matters: enhancing the hydrogen-evolution reaction by shrinking Pt shells in Pt-Pd-graphene stack structures. Angew Chem Int Ed, 2014, 53: 12120–12124

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Ministry of Education under AcRF Tier 2 (ARC 19/15, No. MOE2014-T2-2-093; MOE2015-T2-2-057; MOE2016-T2-2-103; MOE2017-T2-1-162) and AcRF Tier 1 (2016-T1-001-147; 2016-T1-002-051; 2017-T1-001-150; 2017-T1-002-119), and Nanyang Technological University under Start- Up Grant (M4081296.070.500000) in Singapore. We would like to acknowledge the Facility for Analysis, Characterization, Testing and Simulation, Nanyang Technological University, Singapore, for use of their electron microscopy (and/or X-ray) facilities.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Hua Zhang.

Additional information

Zhimin Luo is currently a professor at Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications. He received his bachelor degree from Fujian Normal University in 2002 and completed his PhD in 2013 under the supervision of Prof. Lianhui Wang. He worked as a postdoctoral fellow in Prof. Hua Zhang’s group in the School of Materials Science and Engineering at Nanyang Technological University in Singapore from 2013 to 2018. His research interests include the synthesis and applications of advanced catalysts such as two-dimensional metal dichalcogenides and noble metal nanostructures.

Hua Zhang obtained his bachelor and master degrees at Nanjing University in 1992 and 1995, respectively, and completed his PhD with Prof. Zhongfan Liu at Peking University in 1998. As a Postdoctoral Fellow, he joined Prof. Frans C. De Schryver’s group at Katholieke Universiteit Leuven (Belgium) in 1999, and then moved to Prof. Chad A. Mirkin’s group at Northwestern University in 2001. After he worked at NanoInk Inc. (USA) and Institute of Bioengineering and Nanotechnology (Singapore), he joined Nanyang Technological University in July 2006. His current research interests focus on the the (crystal-)phase engineering of nanomaterials and controlled epitaxial growth of heterostructures, including the synthesis of ultrathin two-dimensional nanomaterials (e.g. metal nanosheets, graphene, metal dichalcogenides, metal-organic frameworks, covalent organic frameworks, etc.), novel metallic and semiconducting nanomaterials, novel amorphous nanomaterials and their hybrid composites, for various applications such as catalysis, clean energy, (opto-)electronic devices, nano- and biosensors, and water remediation.

Supporting Information

40843_2018_9315_MOESM1_ESM.pdf

A simple electrochemical method for conversion of Pt wires to Pt concave icosahedra and nanocubes on carbon paper for electrocatalytic hydrogen evolution

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Luo, Z., Tan, C., Lai, Z. et al. A simple electrochemical method for conversion of Pt wires to Pt concave icosahedra and nanocubes on carbon paper for electrocatalytic hydrogen evolution. Sci. China Mater. 62, 115–121 (2019). https://doi.org/10.1007/s40843-018-9315-5

Download citation

Keywords

  • noble metals
  • electrochemical conversion
  • concave nanostructures
  • electrocatalysis
  • hydrogen evolution