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Catalytic Properties of Pt Monolayer Electrocatalysts

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Platinum Monolayer Electrocatalysts

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Abstract

Platinum monolayer electrocatalysts, i.e., the electrocatalysts with ultimately low Pt loading, are described for various reactions. Various approaches to enhance oxygen reduction kinetics have been shown through numerous examples and explained in terms of combined electronic effect and factors that follow geometric structure. The enhancement of ORR is shown with careful choice of substrate that induces small compressive lateral strain of Pt monolayer and shifts d-band center and binding energies of small adsorbates (O, OH), thus altering the kinetics or ORR. Cores with preferential (111) orientation with minimized low-coordination atoms, single metal cores, nanowires and nanorods, metallic aerogels, intermetallic compounds, nitride-stabilized non-noble metal atoms were tested, and even complete removal of the core atoms was found beneficial for ORR. In addition, replacement of atoms in the Pt shell by an easily oxidized atom may dramatically increase the ORR activity. Examples of PtML in oxidation kinetics of small organic molecules are also shown.

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References

  1. R.R. Adzic, Lima, Platinum monolayer oxygen reduction electrocatalysts, in Handbook of fuel cells: fundamentals technology and applications, ed. by W. Vielstich, A. Lamm, H. A. Gasteiger, H. Yokokawa, (Wiley, New York, 2010)

    Google Scholar 

  2. F.H.B. Lima, J. Zhang, M.H. Shao, K. Sasaki, M.B. Vukmirovic, A. Ticianelli, R.R. Adzic, Catalytic activity – d-band center correlation for the O2 reduction reaction on platinum in alkaline solutions. J. Phys. Chem. C 111, 404–410 (2007)

    CAS  Google Scholar 

  3. Y. Cai, R.R. Adzic, Platinum monolayer electrocatalysts for oxygen reduction reaction: improvements induced by surface and substrate modification of cores. Adv. Phys. Chem., 530397 (2011)

    Google Scholar 

  4. M.H. Shao, T. Huang, P. Liu, J. Zhang, K. Sasaki, M.B. Vukmirovic, R.R. Adzic, Palladium monolayer and palladium alloy electrocatalysts for oxygen reduction. Langmuir 22(25), 10409–10415 (2006)

    CAS  PubMed  Google Scholar 

  5. J. Zhang, M.B. Vukmirovic, Y. Xu, M. Mavrikakis, R.R. Adzic, Controlling the catalytic activity of platinum monolayer electrocatalysts for oxygen reduction with different substrates. Angew. Chem. Int. Ed. 44(14), 2132–2135 (2005)

    CAS  Google Scholar 

  6. B. Hammer, J.K. Norskov, Theoretical surface science and catalysis-calculations and concenpts, in Advances in catalysis, ed. by C. G. Bruce, K. Helmut, vol. 45, (Academic, New York, 2000), pp. 71–129

    Google Scholar 

  7. J. Zhang, Y. Mo, M.B. Vukmirovic, R. Klie, K. Sasaki, R.R. Adzic, Platinum monolayer electrocatalysts for O2 reduction: Pt monolayer on Pd(111) and on carbon-supported Pd nanoparticles. J. Phys. Chem. B 108(30), 10955–10964 (2004)

    CAS  Google Scholar 

  8. J. Zhang, M.B. Vukmirovic, K. Sasaki, A.U. Nilekar, M. Mavrikakis, R.R. Adzic, Mixed metal Pt-monolayer electrocatalysts for enhanced oxygen reduction kinetics. J. Am. Chem. Soc. 127(36), 12480–12481 (2005)

    CAS  PubMed  Google Scholar 

  9. H.I. Karan, K. Sasaki, K. Kuttiyiel, C.A. Farberow, M. Mavrikakis, R.R. Adzic, Catalytic activity of platinum monolayer on iridium and rhenium alloy nanoparticles for the oxygen reduction reaction. ACS Catal. 2, 817–824 (2012)

    CAS  Google Scholar 

  10. Y. Xu, M. Shao, M. Mavrikakis, R.R. Adzic, Recent developments in the O2 reduction reaction, in Fuel cell catalysts, ed. by M. Koper, (Wiley, 2000), p. 267

    Google Scholar 

  11. R.R. Adzic, J. Zhang, K. Sasaki, M.B. Vukmirovic, M. Shao, J.X. Wang, A. Nilekar, J.A. Valerio, F. Uribe, Platinum monolayer fuel cell electrocatalysts. Top. Catal. 46, 249–262 (2007)

    CAS  Google Scholar 

  12. M. Shao, P. Liu, J. Zhang, R. Adzic, Origin of enhanced activity in palladium alloy electrocatalysts for oxygen reduction reaction. J. Phys. Chem. B 111(24), 6772 (2007)

    CAS  PubMed  Google Scholar 

  13. K. Sasaki, H. Naohara, Y.M. Choi, Y. Cai, W.-H. Chen, P. Liu, R.R. Adzic, Highly stable Pt monolayer on PdAu nanoparticle electrocatalysts for the oxygen reduction reaction. Nat. Commun. 3, 1115 (2012)

    PubMed  Google Scholar 

  14. T. Ghosh, M.B. Vukmirovic, F.J. DiSalvo, R.R. Adzic, Intermetallics as novel supports for Pt monolayer O2 reduction electrocatalysts: Potential for significantly improving properties. J. Am. Chem. Soc. 132, 906–907 (2010)

    CAS  PubMed  Google Scholar 

  15. K. Gong, D. Su, R.R. Adzic, Platinum-monolayer shell on AuNi0.5Fe nanoparticle core electrocatalyst with high activity and stability for the oxygen reduction reaction. J. Am. Chem. Soc. 132(41), 14364–14366 (2010)

    CAS  PubMed  Google Scholar 

  16. W.P. Zhou, X. Yang, M.B. Vukmirovic, B. Koel, J. Jiao, G. Peng, M. Mavrikakis, R.R. Adzic, Improving electrocatalysts for O2 reduction by fine-tuning the Pt-support interaction: Pt monolayer on the surfaces of a Pd3Fe(111) single-crystal alloy. J. Am. Chem. Soc. 131(35), 12755–12762 (2009)

    CAS  PubMed  Google Scholar 

  17. M.B. Vukmirovic, S.T. Bliznakov, K. Sasaki, J.X. Wang, R.R. Adzic, Electrodeposition of metals in catalyst synthesis: The case of platinum monolayer electrocatalysts. The Electrochemical Society Interface 20(2), 33–40 (2011)

    CAS  Google Scholar 

  18. K.A. Kuttiyiel, K. Sasaki, Y.M. Choi, D. Su, P. Liu, R.R. Adzic, Bimetallic IrNi core platinum monolayer shell electrocatalysts for the oxygen reduction reaction. Energy Environ. Sci. 5(1), 5297–5304 (2012)

    CAS  Google Scholar 

  19. S.L. Knupp, M.B. Vukmirovic, P. Haldar, J.A. Herron, M. Mavrikakis, R.R. Adzic, Platinum monolayer electrocatalysts for O2 reduction: Pt monolayer on carbon-supported PdIr nanoparticles. Electrocatalysis 1(4), 211–223 (2010)

    Google Scholar 

  20. Y. Xing, Y. Cai, M.B. Vukmirovic, W.-P. Zhou, H. Karan, J.X. Wang, R.R. Adzic, Enhancing oxygen reduction reaction activity via Pd-Au alloy sublayer mediation of Pt monolayer electrocatalysts. J. Phys. Chem. Lett. 1(21), 3238–3242 (2010)

    CAS  Google Scholar 

  21. J. Zhang, K. Sasaki, E. Sutter, R.R. Adzic, Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters. Science 315(5809), 220–222 (2007)

    CAS  PubMed  Google Scholar 

  22. J.X. Wang, C. Ma, Y.M. Choi, D. Su, Y. Zhu, P. Liu, R. Si, M.B. Vukmirovic, Y. Zhang, R.R. Adzic, Kirkendall effect and lattice contraction in nanocatalysts: Strategy to enhance sustainable activity. J. Am. Chem. Soc. 133(34), 13551–13557 (2011)

    CAS  PubMed  Google Scholar 

  23. Y.D. Yin, R.M. Rioux, C.K. Erdonmez, S. Hughes, G.A. Somorjai, A.P. Alivisatos, Formation of hollow nanocrystals through the nanoscale Kirkendall effect. Science 304(5671), 711–714 (2004)

    CAS  PubMed  Google Scholar 

  24. J.X. Wang, H. Inada, L. Wu, Y.M. Choi, P. Liu, W.P. Zhou, R.R. Adzic, Oxygen reduction on well-defined core-shell nanoparticles: Particle size, facet, and Pt shell thickness effects. J. Am. Chem. Soc. 131(47), 17298–17302 (2009)

    CAS  PubMed  Google Scholar 

  25. E. Budevski, G. Staikov, W.J. Lorentz, Electrochemical Phase Formation and Growth – An Introduction to the Initial Stages of Metal Deposition (VCH Verlagsgesellschaft mbH, Winheim, 1996), pp. 1–410. ISBN 3-527-29422-8

    Google Scholar 

  26. H.A. Gasteiger, S.S. Kocha, B. Sompalli, F.T. Wagner, Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl. Catal. B Environ. 56, 9–35 (2005)

    CAS  Google Scholar 

  27. K. Gong, Y. Choi, M.B. Vukmirovic, P. Liu, M. Chao, D. Su, R.R. Adzic, Tetrahedral palladium nanocrystals: A new support for platinum monolayer electrocatalysts with high activity and stability in the oxygen reduction reaction. Z. Phys. Chem. 226(9–10), 1025–1038 (2012)

    CAS  Google Scholar 

  28. C. Koeningsmann, E. Sutter, R.R. Adzic, Size- and composition-dependent enhancement of electrocatalytic oxygen reduction performance in ultrathin palladium-gold (Pd1-xAux) nanowires. J. Phys. Chem. C 116(29), 15297–15306 (2012)

    Google Scholar 

  29. C. Koeningsmann, E. Sutter, T.C. Chiesa, R.R. Adzic, S.S. Wong, Highly enhanced electrocatalytic oxygen reduction performance observed in bimetallic palladium-based nanowires prepared under ambient, surfactantless conditions. Nano Lett. 12(4), 2013–2020 (2012)

    Google Scholar 

  30. Y. Zhang, C. Mab, Y. Zhu, R. Si, Y. Cai, J.X. Wang, R.R. Adzic, Hollow core supported Pt monolayer catalysts for oxygen reduction. Catal. Today 202, 50–54 (2013)

    CAS  Google Scholar 

  31. K. Sasaki, N.S. Marinkovic, H. Isaacs, R.R. Adzic, Synchrotron-based in situ characterization of carbon-supported platinum and platinum monolayer electrocatalysts. ACS Catal. 6(1), 69–76 (2016)

    CAS  Google Scholar 

  32. B. Cai, R. Hubner, K. Sasaki, Y. Zhang, D. Su, C. Ziegler, M.B. Vukmirovic, B. Rellinghaus, R.R. Adzic, A. Eismuller, Core–Shell structuring of pure metallic aerogels towards highly efficient platinum utilization for the oxygen reduction reaction. Angew. Chem. Int. Ed. 57, 2963–2966 (2017)

    Google Scholar 

  33. K. Sasaki, H. Naohara, Y. Cai, Y.M. Choi, P. Liu, M.B. Vukmirovic, J.X. Wang, R.R. Adzic, Core-protected platinum monolayer shell high-stability electrocatalysts for fuel-cell cathodes. Angew. Chem. Int. Ed. 49, 8602–8607 (2010)

    CAS  Google Scholar 

  34. L. Song, Z. Liang, M.B. Vukmirovic, R.R. Adzic, Enhanced oxygen reduction reaction activity on Pt-monolayer-Shell PdIr/Ni-core catalysts. J. Electrochem. Soc. 165(15), J3288–J32943 (2018)

    CAS  Google Scholar 

  35. M.B. Vukmirovic, W.-P. Zhou, W. Chen, K. Sasaki, J. Jiao, M. Mavrikakis, R.R. Adzic, Abstract 843, 216TH ECS meeting (Vienna, Austria, 2009)

    Google Scholar 

  36. C. Yun, R.R. Adzic, Platinum monolayer electrocatalysts for the oxygen reduction reaction: Improvements induced by surface and subsurface modifications of cores. Adv Phys Chem (2011., Article ID 530397). https://doi.org/10.1155/2011/530397

  37. X.L. Tian, J.M. Luo, H.X. Nan, H.B. Zou, R. Chen, T. Shu, X.H. Li, Y.W. Li, H.Y. Song, S.J. Liao, R.R. Adzic, Transition metal nitride coated with atomic layers of Pt as a low-cost, highly stable electrocatalyst for the oxygen reduction reaction. J. Am. Chem. Soc. 138, 1575–1583 (2016)

    CAS  PubMed  Google Scholar 

  38. J. Hu, K.A. Kuttiyiel, K. Sasaki, D. Su, T.H. Yang, G.G. Park, C.X. Zhang, G.Y. Chen, R.R. Adzic, Pt monolayer shell on nitrided alloy core-a path to highly stable oxygen reduction catalyst. Catalysts 5, 1321–1332 (2015)

    CAS  Google Scholar 

  39. K.A. Kuttiyiel, Y. Choi, S.M. Hwang, G.G. Park, T.H. Yang, D. Su, K. Sasaki, P. Liu, R.R. Adzic, Enhancement of the oxygen reduction on nitride stabilized Pt-M (M=Fe, Co, and Ni) core-shell nanoparticle electrocatalysts. Nano Energy 13, 442–449 (2015)

    CAS  Google Scholar 

  40. K.A. Kuttiyiel, K. Sasaki, Y.M.S.D. Choi, P. Liu, R.R. Adzic, Nitride stabilized PtNi core−shell nanocatalyst for high oxygen reduction activity. Nano Lett. 12(12), 6266–6271 (2012)

    CAS  PubMed  Google Scholar 

  41. X.L. Tian, H. Tang, J. Luo, H. Nan, T. Shu, L. Du, J. Zeng, S. Liao, R.R. Adzic, High-performance core−shell catalyst with nitride nanoparticles as a core: Well-defined titanium copper nitride coated with an atomic Pt layer for the oxygen reduction reaction. ACS Catal. 7(6), 2010–2017 (2017)

    Google Scholar 

  42. K. Sasaki, Y. Mo, J.X. Wang, M. Balasubramanian, F. Uribe, J. McBreen, R.R. Adzic, Pt sub monolayers on metal nanoparticles novel electrocatalysts for H2 oxidation and O2 reduction. Electrochim. Acta 48, 3841–3849 (2003)

    CAS  Google Scholar 

  43. M. Li, P. Liu, R.R. Adzic, Platinum monolayer electrocatalysts for anodic oxidation of alcohols. J. Phys. Chem. Lett. 3(23), 3480–3485 (2012)

    CAS  PubMed  Google Scholar 

  44. M. Li, K. Kuttiyiel, F. Lu, O. Gang, R.R. Adzic, Platinum monolayer electrocatalysts for methanol oxidation. J. Electrochem. Soc. 166(7), F3300–F3304 (2019)

    CAS  Google Scholar 

  45. R. Loukrakpama, S.R. Brankovic, P. Strasser, A study of au/C nanoparticles with Pt monolayer and sub-monolayer electrocatalysts for ethanol oxidation reaction. ECS Trans. 58(1), 1733–1736 (2013)

    Google Scholar 

  46. A. Kowal, M. Li, M. Shao, K. Sasaski, M.B. Vukmirovic, J. Zhang, N.S. Marinkovic, P. Liu, A.I. Frenkel, R.R. Adzic, Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2. Nat. Mater. 8, 325–330 (2009)

    CAS  PubMed  Google Scholar 

  47. M. Li, A. Kowal, K. Sasaki, N.S. Marinkovic, D. Su, E. Korach, P. Liu, R.R. Adzic, Ethanol oxidation on the ternary Pt-Rh-SnO2/C electrocatalysts with varied Pt:Rh:Sn ratios. Electrochim. Acta 55, 4331–4338 (2010)

    CAS  Google Scholar 

  48. M.H. Shao, J. Warren, N.S. Marinkovic, P.W. Faguy, R.R. Adzic, In situ ATR-SEIRAS study of electrooxidation of dimethyl ether on a Pt electrode in acid solutions. Electrochem. Commun. 7, 459–465 (2005)

    CAS  Google Scholar 

  49. D.A.J. Rand, R. Woods, Cyclic voltammetric study on iridium electrodes in sulfuric acid solutions-nature of oxygen layer and metal dissolution. J. Electroanal. Chem. 55, 375–381 (1974)

    CAS  Google Scholar 

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Authors and Affiliations

  1. Chemistry Dept Bldg 555, Brookhaven National Laboratory, Upton, NY, USA

    Radoslav Adzic

  2. Synchrotron Catalysis Consortium and Department of Chemical Engineering, Columbia University, New York, NY, USA

    Nebojsa Marinkovic

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  1. Radoslav Adzic
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  2. Nebojsa Marinkovic
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Adzic, R., Marinkovic, N. (2020). Catalytic Properties of Pt Monolayer Electrocatalysts. In: Platinum Monolayer Electrocatalysts . Springer, Cham. https://doi.org/10.1007/978-3-030-49566-4_8

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