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The Electrooxidation of Formic Acid on Pd Nanoparticles: an Investigation of Size-Dependent Performance

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Abstract

Palladium nanoparticles (Pd NPs) were deposited on highly oriented pyrolytic graphite (HOPG) substrates by using a potentiostatic double-pulse technique. The NPs possessed a narrow size distribution and wide dispersion. The particle density was in the order of 109 cm−2. The average height of Pd NPs was controlled in a range of 3 to 50 nm by adjusting the duration of growth pulse. The carbon monoxide (CO) stripping at Pd NPs smaller than 14 nm occurred predominantly at a potential above 1.1 V, which is around 0.2 V more positive than that at bulk Pd and larger Pd NPs, due to the small Pd NPs tending to possess well-ordered (111) facets and a high ratio of edge and corner atoms. The high coverage of adsorbed CO (COads) at small Pd NPs can block the formation of adsorbed hydroxyl (OHads) and drive up the oxidation potential. During formic acid oxidation (FAO), small Pd NPs were quickly poisoned by CO, which was formed initially at edges and corner atoms by electrochemical reduction of FAO product CO2 at low potentials. Based on the overall consideration of the low CO tolerance and the high difficulty to remove CO, it must be stated that Pd NPs smaller than 15 nm without strict shape control are not well suited for FAO.

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References

  1. X. Yu, P.G. Pickup, J. Power Sources 182, 124–132 (2008)

    Article  CAS  Google Scholar 

  2. Y. Zhu, S.Y. Ha, R.I. Masel, J. Power Sources 130, 8–14 (2004)

    Article  CAS  Google Scholar 

  3. C. Rice, S. Ha, R.I. Masel, P. Waszczuk, A. Wieckowski, T. Barnard, J. Power Sources 111, 83–89 (2002)

    Article  CAS  Google Scholar 

  4. A. Mota-Lima, E.R. Gonzalez, M. Eiswirth, J. Braz, Chem. Soc. 25, 1208–1217 (2014)

    CAS  Google Scholar 

  5. S. Uhm, H.J. Lee, J. Lee, Phys. Chem. Chem. Phys. 11, 9326–9336 (2009)

    Article  CAS  Google Scholar 

  6. E. Antolini, Energy Environ. Sci. 2, 915–931 (2009)

    Article  CAS  Google Scholar 

  7. A. Capon, R. Parsons, J. Electroanal. Chemi. Interfacial Electrochem. 44, 293–254 (1973)

    Google Scholar 

  8. M. Arenz, V. Stamenkovic, T.J. Schmidt, K. Wandelt, P.N. Ross, N.M. Markovic, Phys. Chem. Chem. Phys. 5, 4242–4251 (2003)

    Article  CAS  Google Scholar 

  9. K. Jiang, H. Zhang, S. Zou, W. Cai, Phys. Chem. Chem. Phys. 16, 20360–20376 (2014)

    Article  CAS  Google Scholar 

  10. N. Hoshi, M. Nakamura, K. Kida, Electrochem. Commun. 9, 279–282 (2007)

    Article  CAS  Google Scholar 

  11. N. Hoshi, K. Kida, M. Nakamura, M. Nakada, K. Osada, J. Phys. Chem. B, 12480–12484 (2006)

  12. M. Baldauf, D.M. Kolb, J. Phys. Chem. 100, 11375–11381 (1996)

    Article  CAS  Google Scholar 

  13. M. Ren, L. Zou, T. Yuan, Q. Huang, Z. Zou, X. Li, H. Yang, J. Power Sources 267, 527–532 (2014)

    Article  CAS  Google Scholar 

  14. R.K. Pandey, S. Patnaik, V. Lakshminarayanan, Catal. Lett. 144, 965–970 (2014)

    Article  CAS  Google Scholar 

  15. J.-N. Zheng, M. Zhang, F.-F. Li, S.-S. Li, A.-J. Wang, J.-J. Feng, Electrochim. Acta 130, 446–452 (2014)

    Article  CAS  Google Scholar 

  16. X. Xia, S.I. Choi, J.A. Herron, N. Lu, J. Scaranto, H.C. Peng, J. Wang, M. Mavrikakis, M.J. Kim, Y. Xia, J. Am. Chem. Soc. 135, 15706–15709 (2013)

    Article  CAS  Google Scholar 

  17. M. Shao, J. Odell, M. Humbert, T. Yu, Y. Xia, J. Phys. Chem. C 117, 4172–4180 (2013)

    Article  CAS  Google Scholar 

  18. N. Tian, Z.Y. Zhou, N.F. Yu, L.Y. Wang, S.G. Sun, J. Am. Chem. Soc. 132, 7580–7581 (2010)

    Article  CAS  Google Scholar 

  19. W. Hong, Y. Fang, J. Wang, E. Wang, J. Power Sources 248, 553–559 (2014)

    Article  CAS  Google Scholar 

  20. L. Wang, J.-J. Zhai, K. Jiang, J.-Q. Wang, W.-B. Cai, Int. J. Hydrog. Energy 40, 1726–1734 (2015)

    Article  CAS  Google Scholar 

  21. M. Vafaei, M. Rezaei, S.H. Tabaian, F. Mahboubi, D.F. Haghshenas, J. Solid State Electrochem. 19, 289–298 (2015)

    Article  CAS  Google Scholar 

  22. L. Zuopeng, L. Muwu, H. Mingjia, Z. Jianhuang, L. Yuexia, G. Yanqin, L. Shijun, J. Power Sources 254, 183–189 (2014)

    Article  Google Scholar 

  23. S. Yiyi, L. Zhouguang, F. Wenguang, S. Jewell, M.K.H. Leung, J. Mater. Chem. A 2, 3894–3898 (2014)

    Article  Google Scholar 

  24. D. Wu, M. Cao, M. Shen, R. Cao, Chem. Cat. Chem. 6, 1731–1736 (2014)

    CAS  Google Scholar 

  25. R. Liu, F. Liu, D. Fu, Y. Bai, G. Han, Y. Tian, M. Li, Y. Xiao, Y. Li, Catal. Commun. 46, 146–149 (2014)

    Article  CAS  Google Scholar 

  26. Z. Bai, L. Yang, L. Li, J. Lv, K. Wang, J. Zhang, J. Phys. Chem. C 113, 10568–10573 (2009)

    Article  CAS  Google Scholar 

  27. D. Chen, P. Cui, H. He, H. Liu, J. Yang, J. Power Sources 272, 152–159 (2014)

    Article  CAS  Google Scholar 

  28. S. Li, D. Cheng, X. Qiu, D. Cao, Electrochim. Acta 143, 44–48 (2014)

    Article  CAS  Google Scholar 

  29. D. Chen, P. Cui, H. Liu, J. Yang, Electrochim. Acta 153, 461–467 (2015)

    Article  CAS  Google Scholar 

  30. M.T. Koper, Nanoscale 3, 2054–2073 (2011)

    Article  CAS  Google Scholar 

  31. W. Zhou, A. Lewera, R. Larsen, R.I. Masel, P.S. Bagus, A. Wieckowski, J. Phys. Chem. B 110, 13393–13398 (2006)

    Article  CAS  Google Scholar 

  32. W. Zhou, J.Y. Lee, J. Phys. Chem. C 112, 3789–3793 (2008)

    Article  CAS  Google Scholar 

  33. Y. Suo, I.M. Hsing, Electrochim. Acta 55, 210–217 (2009)

    Article  CAS  Google Scholar 

  34. F.J. Vidal-Iglesias, R.M. Aran-Ais, J. Solla-Gullon, E. Garnier, E. Herrero, A. Aldaz, J.M. Feliu, Phys. Chem. Chem. Phys. 14, 10258–10265 (2012)

    Article  CAS  Google Scholar 

  35. S. Chumillas, C. Busó-Rogero, J. Solla-Gullón, F.J. Vidal-Iglesias, E. Herrero, J.M. Feliu, Electrochem. Commun. 13, 1194–1197 (2011)

    Article  CAS  Google Scholar 

  36. W. Ju, T. Brülle, M. Favaro, L. Perini, C. Durante, O. Schneider, U. Stimming, Chem. Electron. Chem. 2, 547–558 (2015)

    CAS  Google Scholar 

  37. I. Horcas, R. Fernandez, J.M. Gomez-Rodriguez, J. Colchero, J. Gomez-Herrero, A.M. Baro, Rev. Sci. Instrum. 78, 013705 (2007)

    Article  CAS  Google Scholar 

  38. R.M. Penner, J. Phys. Chem. B 106, 3339–3353 (2002)

    Article  CAS  Google Scholar 

  39. M. Grdeń, M. Łukaszewski, G. Jerkiewicz, A. Czerwiński, Electrochim. Acta 53, 7583–7598 (2008)

    Article  Google Scholar 

  40. L.-l. Fang, Q. Tao, M.-f. Li, L.-w. Liao, D. Chen, Y.-x. Chen, Chin. J. Chem. Phys. 23, 543–548 (2010)

    Article  CAS  Google Scholar 

  41. T. Brülle, W. Ju, P. Niedermayr, A. Denisenko, O. Paschos, O. Schneider, U. Stimming, Molecules 16, 10059–10077 (2011)

    Article  Google Scholar 

  42. H. Liu, F. Favier, K. Ng, M.P. Zach, R.M. Penner, Electrochim. Acta 47, 671–677 (2001)

    Article  CAS  Google Scholar 

  43. J.V. Zoval, J. Lee, S. Gorer, R.M. Penner, J. Phys. Chem. B 102, 1166–1175 (1998)

    Article  CAS  Google Scholar 

  44. J.V. Zoval, R.M. Stiger, P.R. Biernacki, R.M. Penner, J. Phys. Chem. 100, 837–844 (1996)

    Article  CAS  Google Scholar 

  45. M. Raşa, B.W.M. Kuipers, A.P. Philipse, J. Colloid Interf. Sci. 250, 303–315 (2002)

    Article  Google Scholar 

  46. M. Hara, U. Linke, T. Wandlowski, Electrochim. Acta 52, 5733–5748 (2007)

    Article  CAS  Google Scholar 

  47. B.R. Shrestha, A. Nishikata, T. Tsuru, Electrochim. Acta 70, 42–49 (2012)

    Article  CAS  Google Scholar 

  48. N.M. Markovic, P.N. Ross, Surf. Sci. Rep. 45, 117–229 (2002)

    Article  CAS  Google Scholar 

  49. H. Conrad, G. Ertl, J. Küppers, Surf. Sci. 76, 323–342 (1978)

    Article  CAS  Google Scholar 

  50. T.H.M. Housmans, C.G.M. Hermse, M.T.M. Koper, J. Electroanal. Chem. 607, 69–82 (2007)

    Article  CAS  Google Scholar 

  51. F. Maillard, M. Eikerling, O.V. Cherstiouk, S. Schreier, E. Savinova, U. Stimming, Faraday Discuss. 125, 357–377 (2004)

    Article  CAS  Google Scholar 

  52. N. Hoshi, K. Kagaya, Y. Hori, J. Electroanal. Chem. 485, 55–60 (2000)

    Article  CAS  Google Scholar 

  53. N. Hoshi, M. Kuroda, Y. Hori, J. Electroanal. Chem. 521, 155–160 (2002)

    Article  CAS  Google Scholar 

  54. A. Hitotsuyanagi, S. Kondo, M. Nakamura, N. Hoshi, J. Electroanal. Chem. 657, 123–127 (2011)

    Article  CAS  Google Scholar 

  55. T.H.M. Housmans, M.T.M. Koper, J. Electroanal. Chem. 575, 39–51 (2005)

    Article  CAS  Google Scholar 

  56. A.M. El-Aziz, L.A. Kibler, J. Electroanal. Chem. 534, 107–114 (2002)

    Article  CAS  Google Scholar 

  57. G.A. Tritsaris, J. Greeley, J. Rossmeisl, J.K. Nørskov, Catal. Lett. 141, 909–913 (2011)

    Article  CAS  Google Scholar 

  58. C.R. Henry, Surf. Sci. Rep. 31, 231–325 (1998)

    Article  CAS  Google Scholar 

  59. R. Van Hardeveld, F. Hartog, Surf. Sci. 15, 189–230 (1969)

    Article  Google Scholar 

  60. B. Hammer, J.K. Nørskov, Theoretical surface science and catalysis—calculations and concepts, in: H.K. Bruce C. Gates (Ed.) Advances in Catalysis, Academic Press2000, pp. 71–129

  61. I.V. Yudanov, R. Sahnoun, K.M. Neyman, N. Rösch, J. Phys. Chem. B 107, 255–264 (2003)

    Article  CAS  Google Scholar 

  62. K.A. Friedrich, F. Henglein, U. Stimming, W. Unkauf, Electrochim. Acta 45, 3283–3293 (2000)

    Article  CAS  Google Scholar 

  63. C.D. Zeinalipour-Yazdi, D.J. Willock, L. Thomas, K. Wilson, A.F. Lee, Surf. Sci., (2015)

  64. S. Choi, J.A. Herron, J. Scaranto, H. Huang, Y. Wang, X. Xia, T. Lv, J. Park, H.C. Peng, M. Mavrikakis, Y. Xia, Chem. Cat. Chem. 7, 2077–2084 (2015)

    CAS  Google Scholar 

  65. A. Capon, R. Parsons, J. Electroanal. Chemi. Interfacial Electrochem. 45, 205–231 (1973)

    Article  CAS  Google Scholar 

  66. A. Capon, R. Parsons, J. Electroanal. Chemi. Interfacial Electrochem. 44, 1–7 (1973)

    Article  CAS  Google Scholar 

  67. C. Rice, S. Ha, R.I. Masel, A. Wieckowski, J. Power Sources 115, 229–235 (2003)

    Article  CAS  Google Scholar 

  68. X. Yu, P.G. Pickup, J. Power Sources 187, 493–499 (2009)

    Article  CAS  Google Scholar 

  69. X. Yu, P.G. Pickup, Electrochem. Commun. 11, 2012–2014 (2009)

    Article  CAS  Google Scholar 

  70. M.D. Obradović, S.L. Gojković, Electrochim. Acta 88, 384–389 (2013)

    Article  Google Scholar 

  71. J.Y. Wang, H.X. Zhang, K. Jiang, W.B. Cai, J. Am. Chem. Soc. 133, 14876–14879 (2011)

    Article  CAS  Google Scholar 

  72. C.M.Y. Yue, K.H. Lim, Catal. Lett. 128, 221–226 (2008)

    Article  Google Scholar 

  73. D. Gao, H. Zhou, J. Wang, S. Miao, F. Yang, G. Wang, J. Wang, X. Bao, J. Am. Chem. Soc. 137, 4288–4291 (2015)

    Article  CAS  Google Scholar 

  74. H. Wang, L.R. Alden, F.J. DiSalvo, H.D. Abruna, Langmuir 25, 7725–7735 (2009)

    Article  CAS  Google Scholar 

  75. X. Zhang, T. Arikawa, Y. Murakami, K. Yahikozawa, Y. Takasu, Electrochim. Acta 40, 1889–1897 (1995)

    Article  CAS  Google Scholar 

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Acknowledgment

The research has partially received funding from the European Union’s Seventh Framework Programme (FP7/2007-2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under grant agreement number [303492], which is gratefully acknowledged. We thank Prof. A. Knoll (TUM Informatics), Prof. U. Heiz (TUM Physical Chemistry), and Prof. A. Bandarenka (TUM Physics) for use of their facilities. W.J. thanks the China Scholarship Council for financial support. We would like to thank Dr. Hongjiao Li for the helpful discussions.

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Authors and Affiliations

  1. Physik-Department, Technische Universität München, 85748, Garching, Germany

    Wenbo Ju

  2. Institut für Informatik VI, Technische Universität München, 85748, Garching, Germany

    Roudabeh Valiollahi & Oliver Schneider

  3. Faculty of Chemistry, University of Mazandaran, 47416-95447, Babolsar, Iran

    Roudabeh Valiollahi & Reza Ojani

  4. School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU, United Kingdom

    Ulrich Stimming

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  1. Wenbo Ju
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  2. Roudabeh Valiollahi
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Correspondence to Oliver Schneider.

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Ju, W., Valiollahi, R., Ojani, R. et al. The Electrooxidation of Formic Acid on Pd Nanoparticles: an Investigation of Size-Dependent Performance. Electrocatalysis 7, 149–158 (2016). https://doi.org/10.1007/s12678-015-0293-7

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