Ionics

pp 1–11 | Cite as

Electrodeposited Pt–Pd dendrite on carbon support as anode for direct formic acid fuel cells

Original Paper
  • 36 Downloads

Abstract

The activity of bimetallic catalyst is predominantly determined by its composition and its shape. In this work, Pt–Pd bimetallic catalysts were codeposited using cyclic voltammetry on a carbon black-coated carbon paper at two different potential ranges (0 to 1.3 V and − 0.2 to 1.3 V vs. SHE) and with two different Pt precursors (H2PtCl6 and K2PtCl4). SEM analysis revealed that the deposit obtained from both K2PtCl4 and H2PtCl6 precursor resembled the shape of a flower-like dendrite when the deposition potential window was in the range of 0 to 1.3 V. However, shifting the lower potential limit from 0 to − 0.2 V resulted in a leaf-like dendritic structure, irrespective of the Pt precursor used. Leaf-like dendritic structures showed enhanced formic acid oxidation activity with high mass activity and superior stability compared to flower-like structures. The superior performance of the leaf-like structure was clearly evident from fuel cell polarization studies carried out at 70 °C, which showed a maximum power density of 49 mW cm−2, whereas flower-like structures showed a power density of 20 mW cm−2.

Keywords

Bimetallic alloy Codeposition Cyclic voltammetric deposition Nanodendritic structure Direct formic acid fuel cells 

Notes

Acknowledgements

The authors would like to thank Indian Institute of Technology (IIT) Madras for the financial support. We acknowledge the Department of Science and Technology, DST-FIST, for providing the instrumentation facility to the Department of Chemical Engineering, IIT Madras.

References

  1. 1.
    Soloveichik GL (2014) Liquid fuel cells. Beilstein J Nanotechnol 5:1399–1418.  https://doi.org/10.3762/bjnano.5.153 CrossRefGoogle Scholar
  2. 2.
    Rees NV, Compton RG (2011) Sustainable energy: a review of formic acid electrochemical fuel cells. J Solid State Electrochem 15:2095–2100.  https://doi.org/10.1007/s10008-011-1398-4 CrossRefGoogle Scholar
  3. 3.
    Zhu Y, Ha SY, Masel RI (2004) High power density direct formic acid fuel cells. J Power Sources 130:8–14.  https://doi.org/10.1016/j.jpowsour.2003.11.051 CrossRefGoogle Scholar
  4. 4.
    Rice C, Ha S, Masel RI, Waszczuk P, Wieckowski a, Barnard T (2002) Direct formic acid fuel cells. J Power Sources 111:83–89.  https://doi.org/10.1016/S0378-7753(02)00271-9 CrossRefGoogle Scholar
  5. 5.
    Singh AK, Xu Q (2013) Synergistic catalysis over bimetallic alloy nanoparticles. ChemCatChem 5:652–676.  https://doi.org/10.1002/cctc.201200591 CrossRefGoogle Scholar
  6. 6.
    Yu X, Pickup PG (2008) Recent advances in direct formic acid fuel cells (DFAFC). J Power Sources 182:124–132.  https://doi.org/10.1016/j.jpowsour.2008.03.075 CrossRefGoogle Scholar
  7. 7.
    Kundu A, Jang JH, Gil JH, Jung CR, Lee HR, Kim S, Ku B, Oh YS (2007) Micro-fuel cells—current development and applications. J Power Sources 170:67–78.  https://doi.org/10.1016/j.jpowsour.2007.03.066 CrossRefGoogle Scholar
  8. 8.
    Jiang K, Zhang H-X, Zou S, Cai W-B (2014) Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications. Phys Chem Chem Phys 16:20360–20376.  https://doi.org/10.1039/c4cp03151b CrossRefGoogle Scholar
  9. 9.
    Ma C, Jin Y, Shi M, Chu Y, Xu Y, Jia W, Yuan Q, Chen J, Pan H, Dai Q (2014) Highly active Pd/WO3-CNTs catalysts for formic acid electrooxidation and study of the kinetics. Ionics 20:1419–1426.  https://doi.org/10.1007/s11581-014-1100-9 CrossRefGoogle Scholar
  10. 10.
    Yang M, Zhu X, Tang Y, Wu P, Lu T (2015) Highly dispersed ultrafine palladium nanoparticles on three-dimensional mesoporous carbon for formic acid electro-oxidation. Ionics 21:2609–2614.  https://doi.org/10.1007/s11581-015-1445-8 CrossRefGoogle Scholar
  11. 11.
    Ren M, Kang Y, He W, Zou Z, Xue X, Akins DL, Yang H, Feng S (2011) Origin of performance degradation of palladium-based direct formic acid fuel cells. Appl Catal B Environ 104:49–53.  https://doi.org/10.1016/j.apcatb.2011.02.029 CrossRefGoogle Scholar
  12. 12.
    Łukaszewski M, Czerwin A (2006) Dissolution of noble metals and their alloys studied by electrochemical quartz crystal microbalance. J Electroanal Chem 589:38–45.  https://doi.org/10.1016/j.jelechem.2006.01.007 CrossRefGoogle Scholar
  13. 13.
    Du C, Chen M, Wang W, Yin G (2011) Nanoporous PdNi alloy nanowires as highly active catalysts for the electro-oxidation of formic acid. ACS Appl Mater Interfaces 3:105–109.  https://doi.org/10.1021/am100803d CrossRefGoogle Scholar
  14. 14.
    Choi JH, Jeong KJ, Dong Y, Han J, Lim TH, Lee JS, Sung YE (2006) Electro-oxidation of methanol and formic acid on PtRu and PtAu for direct liquid fuel cells. J Power Sources 163:71–75.  https://doi.org/10.1016/j.jpowsour.2006.02.072 CrossRefGoogle Scholar
  15. 15.
    Demirci UB (2007) Theoretical means for searching bimetallic alloys as anode electrocatalysts for direct liquid-feed fuel cells. J Power Sources 173:11–18.  https://doi.org/10.1016/j.jpowsour.2007.04.069 CrossRefGoogle Scholar
  16. 16.
    Chen W, Kim J, Sun S, Chen S (2007) Composition effects of FePt alloy nanoparticles on the electro-oxidation of formic acid. Langmuir 23:11303–11310.  https://doi.org/10.1021/la7016648 CrossRefGoogle Scholar
  17. 17.
    Kim Y, Kim HJ, Kim YS, Choi SM, Seo MH, Kim WB (2012) Shape- and composition-sensitive activity of Pt and PtAu catalysts for formic acid electrooxidation. J Phys Chem C 116:18093–18100.  https://doi.org/10.1021/jp3054795 CrossRefGoogle Scholar
  18. 18.
    Wang R, Liao S, Ji S (2008) High performance Pd-based catalysts for oxidation of formic acid. J Power Sources 180:205–208.  https://doi.org/10.1016/j.jpowsour.2008.02.027 CrossRefGoogle Scholar
  19. 19.
    Ghosh S, Raj CR (2015) Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of formic acid: towards tuning the reaction pathway. J Chem Sci 127:949–957.  https://doi.org/10.1007/s12039-015-0854-6 CrossRefGoogle Scholar
  20. 20.
    Obradović MD, Gojković SL (2014) Pd black decorated by Pt sub-monolayers as an electrocatalyst for the HCOOH oxidation. J Solid State Electrochem 18:2599–2607.  https://doi.org/10.1007/s10008-014-2509-9 CrossRefGoogle Scholar
  21. 21.
    Zhang HX, Wang C, Wang JY, Zhai JJ, Bin CW (2010) Carbon-supported Pd-Pt nanoalloy with low Pt content and superior catalysis for formic acid electro-oxidation. J Phys Chem C 114:6446–6451.  https://doi.org/10.1021/jp100835b CrossRefGoogle Scholar
  22. 22.
    Porter NS, Wu H, Quan Z, Fang J (2013) Shape-control and electrocatalytic activity-enhancement of Pt-based bimetallic nanocrystals. Acc Chem Res 46:1867–1877CrossRefGoogle Scholar
  23. 23.
    Nguyen VL, Ohtaki M, Matsubara T, Cao MT, Nogami M (2012) New experimental evidences of Pt-Pd bimetallic nanoparticles with core-shell configuration and highly fine-ordered nanostructures by high-resolution electron transmission microscopy. J Phys Chem C 116:12265–12274CrossRefGoogle Scholar
  24. 24.
    Chu Y-Y, Wang Z-B, Jiang Z-Z, Gu D-M, Yin G-P (2012) Facile synthesis of hollow spherical sandwich PtPd/C catalyst by electrostatic self-assembly in polyol solution for methanol electrooxidation. J Power Sources 203:17–25.  https://doi.org/10.1016/j.jpowsour.2011.11.025 CrossRefGoogle Scholar
  25. 25.
    Wang H, Xu C, Cheng F, Zhang M, Wang S, Jiang SP (2008) Pd/Pt core–shell nanowire arrays as highly effective electrocatalysts for methanol electrooxidation in direct methanol fuel cells. Electrochem Commun 10:1575–1578.  https://doi.org/10.1016/j.elecom.2008.08.011 CrossRefGoogle Scholar
  26. 26.
    Yuan Q, Zhou Z, Zhuang J, Wang X (2010) Pd-Pt random alloy nanocubes with tunable compositions and their enhanced electrocatalytic activities. Chem Commun 46:1491–1493.  https://doi.org/10.1039/b922792j CrossRefGoogle Scholar
  27. 27.
    Zhang Z-C, Hui J-F, Guo Z-G, Yu Q-Y, Xu B, Zhang X, Liu Z-C, Xu C-M, Gao J-S, Wang X (2012) Solvothermal synthesis of Pt-Pd alloys with selective shapes and their enhanced electrocatalytic activities. Nano 4:2633–2639.  https://doi.org/10.1039/c2nr12135b Google Scholar
  28. 28.
    Arjona N, Guerra-Balcazar M, Cuevas-Muniz FM, Alvarez-Contreras L, Ledesma-Garcia J, Arriaga LG (2013) Electrochemical synthesis of flower-like Pd nanoparticles with high tolerance toward formic acid electrooxidation. RSC Adv 3:15727–15733.  https://doi.org/10.1039/C3RA41681J CrossRefGoogle Scholar
  29. 29.
    Maniam KK, Chetty R (2015) Electrochemical synthesis of palladium dendrites on carbon support and their enhanced electrocatalytic activity towards formic acid oxidation. J Appl Electrochem 45:953–962.  https://doi.org/10.1007/s10800-015-0860-x CrossRefGoogle Scholar
  30. 30.
    Kim Y, Jung J, Kim S, Chae W (2013) Cyclic voltammetric and chronoamperometric deposition of CdS. Mater Trans 54:1467–1472CrossRefGoogle Scholar
  31. 31.
    Cooper KR (2009) In situ PEM fuel cell electrochemical surface area and catalyst utilization measurement. Fuel Cell Mag 2:1–3.  https://doi.org/10.1016/S1464-2859(00)80060-7 Google Scholar
  32. 32.
    Barbir F (2013) Front Matter. In: PEM fuel cells theory and practice. Elsevier.  https://doi.org/10.1016/B978-0-12-387710-9.01001-8
  33. 33.
    Muthukumar V, Chetty R (2017) Morphological transformation of electrodeposited Pt and its electrocatalytic activity towards direct formic acid fuel cells. J Appl Electrochem 47:735–745.  https://doi.org/10.1007/s10800-017-1076-z CrossRefGoogle Scholar
  34. 34.
    Ojani R, Hasheminejad E, Raoof JB (2014) Hydrogen evolution assisted electrodeposition of bimetallic 3D nano/micro-porous PtPd films and their electrocatalytic performance. Int J Hydrog Energy 39:8194–8203.  https://doi.org/10.1016/j.ijhydene.2014.03.162 CrossRefGoogle Scholar
  35. 35.
    Plowman BJ, Jones LA, Bhargava SK (2015) Building with bubbles: the formation of high surface area honeycomb-like films via hydrogen bubble templated electrodeposition. Chem Commun 51:4331–4346.  https://doi.org/10.1039/C4CC06638C CrossRefGoogle Scholar
  36. 36.
    Yasin HM, Denuault G, Pletcher D (2009) Studies of the electrodeposition of platinum metal from a hexachloroplatinic acid bath. J Electroanal Chem 633:327–332.  https://doi.org/10.1016/j.jelechem.2009.06.020 CrossRefGoogle Scholar
  37. 37.
    Peera SG, Sahu AK, Arunchander A, Nath K, Bhat SD (2015) Deoxyribonucleic acid directed metallization of platinum nanoparticles on graphite nano fibers as a durable oxygen reduction catalyst for polymer electrolyte fuel cells. J Power Sources 297:379–387.  https://doi.org/10.1016/j.jpowsour.2015.08.009 CrossRefGoogle Scholar
  38. 38.
    Xu Y, Lin X (2007) Facile fabrication and electrocatalytic activity of Pt0.9Pd0.1 alloy film catalysts. J Power Sources 170:13–19.  https://doi.org/10.1016/j.jpowsour.2007.03.064 CrossRefGoogle Scholar
  39. 39.
    Lee C-L, Chiou H-P (2012) Methanol-tolerant Pd nanocubes for catalyzing oxygen reduction reaction in H2SO4 electrolyte. Appl Catal B Environ 117–118:204–211.  https://doi.org/10.1016/j.apcatb.2012.01.012 CrossRefGoogle Scholar
  40. 40.
    Meng H, Xie F, Chen J, Shen PK (2011) Electrodeposited palladium nanostructure as novel anode for direct formic acid fuel cell. J Mater Chem 21:11352–11358.  https://doi.org/10.1039/c1jm10361j CrossRefGoogle Scholar
  41. 41.
    Antolini E (2009) Palladium in fuel cell catalysis. Energy Environ Sci 2:915–931.  https://doi.org/10.1039/b820837a CrossRefGoogle Scholar
  42. 42.
    Taurino I, Sanzó G, Mazzei F, Favero G, De Micheli G, Carrara S (2015) Fast synthesis of platinum nanopetals and nanospheres for highly-sensitive non-enzymatic detection of glucose and selective sensing of ions. Sci Rep 5:15277–15287.  https://doi.org/10.1038/srep15277 CrossRefGoogle Scholar
  43. 43.
    Xu W, Du D, Lan R, Humphreys J, Miller DN, Walker M, Wu Z, Irvine JTS, Tao S (2017) Electrodeposited NiCu bimetal on carbon paper as stable non-noble anode for efficient electrooxidation of ammonia. Appl Catal B Environ 3:1–9.  https://doi.org/10.1016/j.apcatb.2016.11.003 Google Scholar
  44. 44.
    Zhou Y, Neyerlin K, Olson TS, Pylypenko S, Bult J, Dinh HN, Gennett T, Shao Z, O’Hayre R (2010) Enhancement of Pt and Pt-alloy fuel cell catalyst activity and durability via nitrogen-modified carbon supports. Energy Environ Sci 3:1437–1446.  https://doi.org/10.1039/c003710a CrossRefGoogle Scholar
  45. 45.
    Watt-Smith MJ, Friedrich JM, Rigby SP, Ralph TR, Walsh FC (2008) Determination of the electrochemically active surface area of Pt/C PEM fuel cell electrodes using different adsorbates. J Phys D Appl Phys 41:174004–174011.  https://doi.org/10.1088/0022-3727/41/17/174004 CrossRefGoogle Scholar
  46. 46.
    Zadick A, Dubau L, Demirci UB, Chatenet M (2016) Effects of Pd nanoparticle size and solution reducer strength on Pd/C electrocatalyst stability in alkaline electrolyte. J Electrochem Soc 163:F781–F787.  https://doi.org/10.1149/2.0141608jes CrossRefGoogle Scholar
  47. 47.
    Liu X-Y, Zhang Y, Gong M-X, Tang Y-W, Lu T-H, Chen Y, Lee J-M (2014) Facile synthesis of corallite-like Pt–Pd alloy nanostructures and their enhanced catalytic activity and stability for ethanol oxidation. J Mater Chem A 2:13840–13844.  https://doi.org/10.1039/C4TA02522A CrossRefGoogle Scholar
  48. 48.
    Lv J-J, Mei L-P, Weng X, Wang A-J, Chen L-L, Liu X-F, Feng J-J (2015) Facile synthesis of three-dimensional Pt–Pd alloyed multipods with enhanced electrocatalytic activity and stability for ethylene glycol oxidation. Nano 7:5699–5705.  https://doi.org/10.1039/C5NR00174A Google Scholar
  49. 49.
    Jow J, Yang S, Chen H, Wu M, Ling T, Wei T (2009) Co-electrodeposition of Pt–Ru electrocatalysts in electrolytes with varying compositions by a double-potential pulse method for the oxidation of MeOH and CO. Int J Hydrog Energy 34:665–671.  https://doi.org/10.1016/j.ijhydene.2008.11.032 CrossRefGoogle Scholar
  50. 50.
    El-Deab MS (2012) Platinum nanoparticles-manganese oxide nanorods as novel binary catalysts for formic acid oxidation. J Adv Res 3:65–71.  https://doi.org/10.1016/j.jare.2011.04.002 CrossRefGoogle Scholar
  51. 51.
    Ji X, Lee KT, Holden R, Zhang L, Zhang J, Botton GA, Couillard M, Nazar LF (2010) Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. Nat Chem 2:286–293.  https://doi.org/10.1038/nchem.553 CrossRefGoogle Scholar
  52. 52.
    Maciá MD, Herrero E, Feliu JM (2003) Formic acid oxidation on Bi-Pt(111) electrode in perchloric acid media. A kinetic study. J Electroanal Chem 554–555:25–34.  https://doi.org/10.1016/S0022-0728(03)00023-8 CrossRefGoogle Scholar
  53. 53.
    Maniam KK, Chetty R (2013) Electrodeposited palladium nanoflowers for electrocatalytic applications. Fuel Cells 13:1196–1204.  https://doi.org/10.1002/fuce.201200162 CrossRefGoogle Scholar
  54. 54.
    Blair S, Lycke D, Coca I (2006) Palladium-platinum alloy anode catalysts for direct formic acid fuels. ECS Trans 3:1325–1332CrossRefGoogle Scholar
  55. 55.
    Lee SJ, Mukerjee S, McBreen J, Rho YW, Kho YT, Lee TH (1998) Effects of Nafion impregnation on performances of PEMFC electrodes. Electrochim Acta 43:3693–3701.  https://doi.org/10.1016/S0013-4686(98)00127-3 CrossRefGoogle Scholar
  56. 56.
    Myles TD, Kim S, Maric R, Mustain WE (2015) Application of a coated film catalyst layer model to a high temperature polymer electrolyte membrane fuel cell with low catalyst loading produced by reactive spray deposition technology. Catalysts 5:1673–1691.  https://doi.org/10.3390/catal5041673 CrossRefGoogle Scholar
  57. 57.
    Fan X, Shi Y, Cui Y, Li D (2015) A facile electrochemical synthesis of three-dimensional porous Sn-Cu alloy/carbon nanotube nanocomposite as anode of high-power lithium-ion battery. Ionics 21:1909–1917.  https://doi.org/10.1007/s11581-015-1372-8 CrossRefGoogle Scholar
  58. 58.
    Ren F, Wang H, Zhai C, Zhu M, Yue R, Du Y, Yang P, Xu J, Lu W (2014) Clean method for the synthesis of reduced graphene oxide-supported PtPd alloys with high electrocatalytic activity for ethanol oxidation in alkaline medium. ACS Appl Mater Interfaces 6:3607–3614.  https://doi.org/10.1021/am405846h CrossRefGoogle Scholar
  59. 59.
    Zhu C, Guo S, Dong S (2012) PdM (M = Pt, Au) bimetallic alloy nanowires with enhanced electrocatalytic activity for electro-oxidation of small molecules. Adv Mater 24:2326–2331.  https://doi.org/10.1002/adma.201104951 CrossRefGoogle Scholar
  60. 60.
    Joo J, Uchida T, Cuesta A, Koper MTM, Osawa M (2014) The effect of pH on the electrocatalytic oxidation of formic acid/formate on platinum: a mechanistic study by surface-enhanced infrared spectroscopy coupled with cyclic voltammetry. Electrochim Acta 129:127–136.  https://doi.org/10.1016/j.electacta.2014.02.04 CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Chemical Engineering DepartmentIndian Institute of Technology MadrasChennaiIndia

Personalised recommendations