Advertisement

Ionic liquid-assisted synthesis of reduced graphene oxide–supported hollow spherical PtCu alloy and its enhanced electrocatalytic activity toward methanol oxidation

  • Wanyi Duan
  • Aoqi Li
  • Yujuan Chen
  • Kelei ZhuoEmail author
  • Jianming Liu
  • Jianji WangEmail author
Research Paper
  • 192 Downloads

Abstract

In this work, a facile one-pot solvothermal method is developed for fabricating hollow spherical PtCu alloy nanoparticles (with the size of 124 ± 16 nm) supported on reduced graphene oxide (PtCu/rGO), with the assistance of 1-decyl-3-methylimidazolium bromide ([C10MIm]Br) as the structure-directing agent and capping agent. The influence of various experimental parameters on the morphology and structure of prepared PtCu/rGO hybrids is researched. Compared with the commercial Pt/C (10 wt%) and Pt/rGO, the as-prepared PtCu/rGO hybrid exhibits a larger electrochemical active surface area, higher electrocatalytic activity, and better tolerance for methanol oxidation in acidic media. We believe that the hollow spherical PtCu alloy supported on rGO will have great potential applications for direct methanol fuel cells.

Graphical abstract

Hollow spherical PtCu alloy supported on rGO hybrid is successfully synthesized by a facile one-pot solvothermal method with the assistance of 1-decyl-3-methylimidazolium bromide. 1-Decyl-3-methylimidazolium bromide acts as both shape-controlled agent and capping agent for synthesizing PtCu/rGO. The as-prepared PtCu/rGO exhibits high electrocatalytic activity and good poisoning-resistant ability for methanol oxidation in acidic media.

Keywords

Hollow spherical nanoparticles Platinum-copper alloy Nanostructured catalysts 1-Decyl-3-methylimidazolium bromide Methanol oxidation Graphene 

Notes

Funding information

Financial support from the National Natural Science Foundation of China (Nos. 21573058, 21303044, 21173070) and the Program for Innovative Research Team in Science and Technology in University of Henan Province (15IRTSTHN 003, 17IRTSTHN 001) are gratefully acknowledged.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2018_4400_MOESM1_ESM.docx (8.2 mb)
ESM 1 (DOCX 8348 kb)

References

  1. Best RJ, Russell WW (1954) Nickel, copper and some of their alloys as catalysts for ethylene hydrogenation. J Am Chem Soc 76:838–842.  https://doi.org/10.1021/ja01632a060 CrossRefGoogle Scholar
  2. Bin D, Ren FF, Wang HW, Zhang K, Yang B, Zhai C, Zhu M, Yang P, du Y (2014) Facile synthesis of PVP-assisted PtRu/RGO nanocomposites with high electrocatalytic performance for methanol oxidation. RSC Adv 4:39612–39618.  https://doi.org/10.1039/C4RA07742C CrossRefGoogle Scholar
  3. Bock C, Paquet C, Couillard M, Botton GA, MacDougall BR (2004) Size-selected synthesis of PtRu nano-catalysts: reaction and size control mechanism. J Am Chem Soc 126:8028–8037.  https://doi.org/10.1021/ja0495819 CrossRefGoogle Scholar
  4. Cao X, Wang N, Han Y, Gao C, Xu Y, Li M, Shao Y (2015) PtAg bimetallic nanowires: facile synthesis and their use as excellent electrocatalysts toward low-cost fuel cells. Nano Energy 12:105–114.  https://doi.org/10.1016/j.nanoen.2014.12.020 CrossRefGoogle Scholar
  5. Chen ZW, Xu LB, Li WZ, Waje M, Yan Y (2006) Polyaniline nanofibre supported platinum nanoelectrocatalysts for direct methanol fuel cells. Nanotechnology 17:5254–5259.  https://doi.org/10.1088/0957-4484/17/20/035 CrossRefGoogle Scholar
  6. Chen DH, Zhao YC, Peng XL, Wang X, Hu W, Jing C, Tian S, Tian J (2015a) Star-like PtCu nanoparticles supported on graphene with superior activity for methanol electro-oxidation. Electrochim Acta 177:86–92.  https://doi.org/10.1016/j.electacta.2015.03.066 CrossRefGoogle Scholar
  7. Chen DJ, Zhang QL, Feng JX, Ju KJ, Wang AJ, Wei J, Feng JJ (2015b) One-pot wet-chemical co-reduction synthesis of bimetallic gold–platinum nanochains supported on reduced graphene oxide with enhanced electrocatalytic activity. J Power Sources 287:363–369.  https://doi.org/10.1016/j.jpowsour.2015.04.080 CrossRefGoogle Scholar
  8. Duan X, Lian J, Ma J, Kim T, Zheng W (2010) Shape-controlled synthesis of metal carbonate nanostructure via ionic liquid-assisted hydrothermal route: the case of manganese carbonate. Cryst Growth Des 10:4449–4455.  https://doi.org/10.1021/cg1006567 CrossRefGoogle Scholar
  9. Ferrari AC, Basko DM (2013) Raman spectroscopy as a versatile tool for studying the properties of graphene. Nat Nanotechnol 8:235–246.  https://doi.org/10.1038/NNANO.2013.46 CrossRefGoogle Scholar
  10. Firestone MA, Dzielawa JA, Zapol P, Curtiss LA, Seifert S, Dietz ML (2002) Lyotropic liquid-crystalline gel formation in a room-temperature ionic liquid. Langmuir 18:7258–7260.  https://doi.org/10.1021/la0259499 CrossRefGoogle Scholar
  11. Foo ML, Wang Y, Watauchi S, Zandbergen HW, He T, Cava RJ, Ong NP (2004) Charge ordering, commensurability and metallicity in the phase diagram of the layered NaxCoO2. Phys Rev Lett 92:247001.  https://doi.org/10.1103/PhysRevLett.92.247001 CrossRefGoogle Scholar
  12. Gao HL, He LL, Xiao YH, Zhang Y, Zhang S (2016) One-step synthesis of reduced graphene oxide-supported PtCo nanoalloys with enhanced electrocatalytic activity for methanol oxidation. Ionics 22:2175–2182.  https://doi.org/10.1007/s11581-016-1727-9 CrossRefGoogle Scholar
  13. Goodchild I, Collier L, Millar SL, Prokeš I, Lord JCD, Butts CP, Bowers J, Webster JRP, Heenan RK (2007) Structural studies of the phase, aggregation and surface behaviour of 1-alkyl-3-methylimidazolium halide + water mixtures. J Colloid Interface Sci 307:455–468.  https://doi.org/10.1016/j.jcis.2006.11.034 CrossRefGoogle Scholar
  14. He LL, Song P, Feng JJ, Fang R, Yu DX, Chen JR, Wang AJ (2016) Porous dandelion-like gold@palladium core-shell nanocrystals in-situ growth on reduced graphene oxide with improved electrocatalytic properties. Electrochim Acta 200:204–213.  https://doi.org/10.1016/j.electacta.2016.03.098 CrossRefGoogle Scholar
  15. Huang HJ, Wang X (2012) Pd nanoparticles supported on low-defect graphene sheets: for use as high-performance electrocatalysts for formic acid and methanol oxidation. J Mater Chem 22:22533–22541.  https://doi.org/10.1039/C2JM33727D CrossRefGoogle Scholar
  16. Inoue T, Dong B, Zheng LQ (2007) Phase behavior of binary mixture of 1-dodecyl-3-methylimidazolium bromide and water revealed by differential scanning calorimetry and polarized optical microscopy. J Colloid Interface Sci 307:578–581.  https://doi.org/10.1016/j.jcis.2006.12.063 CrossRefGoogle Scholar
  17. Ju KJ, Liu L, Feng JJ, Zhang QL, Wei J, Wang AJ (2016) Bio-directed one-pot synthesis of Pt-Pd alloyed nanoflowers supported on reduced graphene oxide with enhanced catalytic activity for ethylene glycol oxidation. Electrochim Acta 188:696–703.  https://doi.org/10.1016/j.electacta.2015.11.126 CrossRefGoogle Scholar
  18. Kaper H, Smarsly BM (2006) Templating and phase behaviour of the long chain ionic liquid C16mimCl. Z Phys Chem 220:1455–1471.  https://doi.org/10.1524/zpch.2006.220.10.1455 CrossRefGoogle Scholar
  19. Li SS, Wang AJ, Hu YY, Fang KM, Chen JR, Feng JJ (2014) One-step, seedless wet-chemical synthesis of gold@palladium nanoflowers supported on reduced graphene oxide with enhanced electrocatalytic properties. J Mater Chem A 2:18177–18183.  https://doi.org/10.1039/c4ta04164j CrossRefGoogle Scholar
  20. Li AQ, Chen YJ, Duan WY, Wang C, Zhuo K (2017) Shape-controlled electrochemical synthesis of Au nanocrystals in reline: control conditions and electrocatalytic oxidation of ethylene glycol. RSC Adv 7:19694–19700.  https://doi.org/10.1039/C7RA01639E CrossRefGoogle Scholar
  21. Liu HS, Song CJ, Zhang L, Zhang J, Wang H, Wilkinson DP (2006) A review of anode catalysis in the direct methanol fuel cell. J Power Sources 155:95–110.  https://doi.org/10.1016/j.jpowsour.2006.01.030 CrossRefGoogle Scholar
  22. Liu X, Ma J, Peng P, Zheng W (2010) One-pot hydrothermal synthesis of ZnSe hollow nanospheres from an ionic liquid precursor. Langmuir 26:9968–9973.  https://doi.org/10.1021/la1000182 CrossRefGoogle Scholar
  23. Liu YJ, Huang YQ, Xie Y, Yang Z, Huang H, Zhou Q (2012) Preparation of highly dispersed CuPt nanoparticles on ionic-liquid-assisted graphene sheets for direct methanol fuel cell. Chem Eng J 197:80–87.  https://doi.org/10.1016/j.cej.2012.05.011 CrossRefGoogle Scholar
  24. Liu MM, Lu YZ, Chen W (2013) PdAg nanorings supported on graphene nanosheets: highly methanol-tolerant cathode electrocatalyst for alkaline fuel cells. Adv Funct Mater 23:1289–1296.  https://doi.org/10.1002/adfm.201202225 CrossRefGoogle Scholar
  25. Luo BM, Xu S, Yan XB, Xue Q (2013) PtNi alloy nanoparticles supported on polyelectrolyte functionalized graphene as effective electrocatalysts for methanol oxidation. J Electrochem Soc 160:262–268.  https://doi.org/10.1149/2.056303jes CrossRefGoogle Scholar
  26. Lv JJ, Feng JX, Li SS, Wang YY, Wang AJ, Zhang QL, Chen JR, Feng JJ (2014) Ionic liquid crystal-assisted synthesis of PtAg nanoflowers on reduced graphene oxide and their enhanced electrocatalytic activity toward oxygen reduction reaction. Electrochim Acta 133:407–413.  https://doi.org/10.1016/j.electacta.2014.04.077 CrossRefGoogle Scholar
  27. Mani P, Srivastava R, Strasser P (2008) Dealloyed Pt–Cu core–shell nanoparticle electrocatalysts for use in PEM fuel cell cathodes. J Phys Chem C 112:2770–2778.  https://doi.org/10.1021/jp0776412 CrossRefGoogle Scholar
  28. Peng Y, Liu C, Pan C, Qiu L, Wang S, Yan F (2013) PPyNT-Im-PtAu alloy nanoparticle hybrids with tunable electroactivity and enhanced durability for methanol electrooxidation and oxygen reduction reaction. ACS Appl Mater Interfaces 5:2752–2760.  https://doi.org/10.1021/am4004478 CrossRefGoogle Scholar
  29. Peng XL, Zhao YC, Chen DH, Fan Y, Wang X, Wang W, Tian J (2014) One-pot synthesis of reduced graphene oxide supported PtCuy catalysts with enhanced electro-catalytic activity for the methanol oxidation reaction. Electrochim Acta 136:292–300.  https://doi.org/10.1016/j.electacta.2014.05.110 CrossRefGoogle Scholar
  30. Shin SI, Go A, Kim IY, Lee JM, Lee Y, Hwang SJ (2013) A beneficial role of exfoliated layered metal oxide nanosheets in optimizing the electrocatalytic activity and pore structure of Pt-reduced graphene oxide nanocomposites. Energy Environ Sci 6:608–617.  https://doi.org/10.1039/C2EE22739H CrossRefGoogle Scholar
  31. Singh B, Murad L, Laffir F, Dickinson C, Dempsey E (2011) Pt based nanocomposites (mono/bi/tri-metallic) decorated using different carbon supports for methanol electro-oxidation in acidic and basic media. Nanoscale 3:3334–3349.  https://doi.org/10.1039/c1nr10273g CrossRefGoogle Scholar
  32. Strasser P, Koh S, Anniyev T, Greeley J, More K, Yu C, Liu Z, Kaya S, Nordlund D, Ogasawara H, Toney MF, Nilsson A (2010) Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat Chem 2:454–460.  https://doi.org/10.1038/nchem.623 CrossRefGoogle Scholar
  33. Sun Y, Zheng W (2010) Ultrathin SmVO4 nanosheets: ionic liquid-assisted hydrothermal synthesis, characterization, formation mechanism and optical property. Dalton Trans 39:7098–7103.  https://doi.org/10.1039/c002626c CrossRefGoogle Scholar
  34. Sun LT, Wang HJ, Eid K, Alshehri SM, Malgras V, Yamauchi Y, Wang L (2016) One-step synthesis of dendritic bimetallic PtPd nanoparticles on reduced graphene oxide and its electrocatalytic properties. Electrochim Acta 188:845–851.  https://doi.org/10.1016/j.electacta.2015.12.068 CrossRefGoogle Scholar
  35. Tokuda H, Hayamizu K, Ishii K, Susan MABH, Watanabe M (2004) Physicochemical properties and structures of room temperature ionic liquids. 1. Variation of anionic species. J Phys Chem B 108:16593–16600.  https://doi.org/10.1021/jp047480r CrossRefGoogle Scholar
  36. Tokuda H, Hayamizu K, Ishii K, Susan MABH, Watanabe M (2005) Physicochemical properties and structures of room temperature ionic liquids. 2. Variation of alkyl chain length in imidazolium cation. J Phys Chem B 109:6103–6110.  https://doi.org/10.1021/jp044626d CrossRefGoogle Scholar
  37. Wang YS, Yang SY, Li SM, Tien HW, Hsiao ST, Liao WH, Liu CH, Chang KH, Ma CCM, Hu CC (2013) Three-dimensionally porous graphene–carbon nanotube composite-supported PtRu catalysts with an ultrahigh electrocatalytic activity for methanol oxidation. Electrochim Acta 87:261–269.  https://doi.org/10.1016/j.electacta.2012.09.013 CrossRefGoogle Scholar
  38. Wu J, Duan F, Zheng Y, Xie Y (2007) Synthesis of Bi2WO6 nanoplate-built hierarchical nest-like structures with visible-light-induced photocatalytic activity. J Phys Chem C 111:12866–12871.  https://doi.org/10.1021/jp073877u CrossRefGoogle Scholar
  39. Xia BY, Wu HB, Wang X, Lou XW(D) (2012) One-pot synthesis of cubic PtCu3 nanocages with enhanced electrocatalytic activity for the methanol oxidation reaction. J Am Chem Soc 134:13934–13937.  https://doi.org/10.1021/ja3051662 CrossRefGoogle Scholar
  40. Xu D, Liu ZP, Yang HZ, Liu Q, Zhang J, Fang J, Zou S, Sun K (2009) Solution-based evolution and enhanced methanol oxidation activity of monodisperse platinum-copper nanocubes. Angew Chem Int Ed 48:4217–4221.  https://doi.org/10.1002/anie.200900293 CrossRefGoogle Scholar
  41. Yang LX, Zhu YJ, Tong H, Liang ZH, Wang WW (2007) Hierarchical β-Ni(OH)2 and NiO carnations assembled from nanosheet building blocks. Cryst Growth Des 7:2716–2719.  https://doi.org/10.1021/cg060530s CrossRefGoogle Scholar
  42. Yang HZ, Dai L, Xu D, Fang J, Zou S (2010) Electrooxidation of methanol and formic acid on PtCu nanoparticles. Electrochim Acta 55:8000–8004.  https://doi.org/10.1016/j.electacta.2010.03.026 CrossRefGoogle Scholar
  43. Yang LM, Ding YB, Chen L, Luo S, Tang Y, Liu C (2017) Hierarchical reduced graphene oxide supported dealloyed platinum-copper nanoparticles for highly efficient methanol electrooxidation. Int J Hydrog Energy 42:6705–6712.  https://doi.org/10.1016/j.ijhydene.2017.01.133 CrossRefGoogle Scholar
  44. Yuan CX, Fan YR, Zhang T et al (2014) A new electrochemical sensor of nitro aromatic compound based on three-dimensional porous Pt–Pd nanoparticles supported by graphene–multiwalled carbon nanotube composite. Biosens Bioelectron 58:85–91.  https://doi.org/10.1016/j.bios.2014.01.041 CrossRefGoogle Scholar
  45. Zan XL, Fang Z, Wu J, Xiao F, Huo F, Duan H (2013) Freestanding graphene paper decorated with 2D-assembly of Au@Pt nanoparticles as flexible biosensors to monitor live cell secretion of nitric oxide. Biosens Bioelectron 49:71–78.  https://doi.org/10.1016/j.bios.2013.05.006 CrossRefGoogle Scholar
  46. Zhang J, Dong B, Zheng L, Li N, Li X (2008) Lyotropic liquid crystalline phases formed in ternary mixtures of 1-cetyl-3-methylimidazolium bromide/p-xylene/water: a SAXS, POM, and rheology study. J Colloid Interf Sci 321:159–165.  https://doi.org/10.1016/j.jcis.2008.01.020
  47. Zhang K, Wang HW, Wang CQ, Yang B, Ren F, Yang P, du Y (2015) Facile fabrication of PtCuAu nanoparticles modified reduced graphene oxide with high electrocatalytic activity toward formic acid oxidation. Colloid Surface A 467:211–215.  https://doi.org/10.1016/j.colsurfa.2014.11.059 CrossRefGoogle Scholar
  48. Zhao YC, Wang FY, Tian JN, Yang X, Zhan L (2010) Preparation of Pt/CeO2/HCSs anode electrocatalysts for direct methanol fuel cells. Electrochim Acta 55:8998–9003.  https://doi.org/10.1016/j.electacta.2010.08.021 CrossRefGoogle Scholar
  49. Zhu YW, Murali S, Cai WW, Li X, Suk JW, Potts JR, Ruoff RS (2010) Graphene and graphene oxide: synthesis, properties, and applications. Adv Mater 22:3906–3924.  https://doi.org/10.1002/adma.201001068 CrossRefGoogle Scholar
  50. Zou LL, Guo J, Liu JY, Zou Z, Akins DL, Yang H (2014) Highly alloyed PtRu black electrocatalysts for methanol oxidation prepared using magnesia nanoparticles as sacrificial templates. J Power Sources 248:356–362.  https://doi.org/10.1016/j.jpowsour.2013.09.086 CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical EngineeringHenan Normal UniversityXinxiangPeople’s Republic of China

Personalised recommendations