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Surface active-site engineering in hierarchical PtNi nanocatalysts for efficient triiodide reduction reaction

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Abstract

Hierarchical Pt-alloys enriched with active sites are highly desirable for efficient catalysis, but their syntheses generally need time-consuming and elaborate annealing treatment at high temperature. We herein report a surface active-site engineering strategy for constructing the hierarchical PtNi nanocatalysts with an atomic Pt-skin layer (PtNi@Pt-SL) towards efficient triiodide reduction reaction (TRR) via an acid-dealloying approach. The facile acid-dealloying process promotes the formation of surface Pt active sites on the hierarchical Pt-alloys, and thus results in good catalytic performance towards TRR. Theoretical calculation reveals that the enhanced catalytic property stems from the moderate energy barriers for iodide atoms on the surface Pt active-sites. The surface active-site engineering strategy paves a new way for the design of active and durable electrocatalysts.

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References

  1. Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; Nørskov, J. K.; Jaramillo, T. F. Combining theory and experiment in electrocatalysis: Insights into materials design. Science 2017, 355, eaad4998.

    Article  Google Scholar 

  2. Wang, Y. H.; Zhang, L.; Hu, C. L.; Yu, S. N.; Yang, P. P.; Cheng, D. F.; Zhao, Z. J.; Gong, J. L. Fabrication of bilayer Pd-Pt nanocages with sub-nanometer thin shells for enhanced hydrogen evolution reaction. Nano Res. 2019, 12, 2268–2274.

    Article  CAS  Google Scholar 

  3. Li, M. F.; Zhao, Z. P.; Cheng, T.; Fortunelli, A.; Chen, C. Y.; Yu, R.; Zhang, Q. H.; Gu, L.; Merinov, B. V.; Lin, Z. Y. et al. Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction. Science 2016, 354, 1414–1419.

    Article  CAS  Google Scholar 

  4. Li, G. R.; Song, J.; Pan, G. L.; Gao, X. P. Highly Pt-like electrocatalytic activity of transition metal nitrides for dye-sensitized solar cells. Energy Environ. Sci. 2011, 4, 1680–1683.

    Article  CAS  Google Scholar 

  5. Chen, C.; Kang, Y. J.; Huo, Z. Y.; Zhu, Z. W.; Huang, W. Y.; Xin, H. L.; Snyder, J. D.; Li, D. G.; Herron, J. A.; Mavrikakis, M. et al. Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces. Science 2014, 343, 1339–1343.

    Article  CAS  Google Scholar 

  6. Huang, X. Q.; Zhao, Z. P.; Cao, L.; Chen, Y.; Zhu, E. B.; Lin, Z. Y.; Li, M. F.; Yan, A. M.; Zettl, A.; Wang, Y. M. et al. High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction. Science 2015, 348, 1230–1234.

    Article  CAS  Google Scholar 

  7. Stamenkovic, V. R.; Mun, B. S.; Arenz, M.; Mayrhofer, K. J. J.; Lucas, C. A.; Wang, G. F.; Ross, P. N.; Markovic, N. M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat. Mater. 2007, 6, 241–247.

    Article  CAS  Google Scholar 

  8. Bu, L. Z.; Zhang, N.; Guo, S. J.; Zhang, X.; Li, J.; Yao, J. L.; Wu, T.; Lu, G.; Ma, J. Y.; Su, D. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 2016, 354, 1410–1414.

    Article  CAS  Google Scholar 

  9. Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G. F.; Ross, P. N.; Lucas, C. A.; Markovic, N. M. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 2007, 315, 493–497.

    Article  CAS  Google Scholar 

  10. Perini, L.; Durante, C.; Favaro, M.; Perazzolo, V.; Agnoli, S.; Schneider, O.; Granozzi, G.; Gennaro, A. Metal-support interaction in platinum and palladium nanoparticles loaded on nitrogen-doped mesoporous carbon for oxygen reduction reaction. ACS Appl. Mater. Inter. 2015, 7, 1170–1179.

    Article  CAS  Google Scholar 

  11. Chen, X. T.; Si, C. H.; Wang, Y.; Ding, Y.; Zhang, Z. H. Multicomponent platinum-free nanoporous Pd-based alloy as an active and methanol-tolerant electrocatalyst for the oxygen reduction reaction. Nano Res. 2016, 9, 1831–1843.

    Article  CAS  Google Scholar 

  12. Zhu, E. B.; Xue, W.; Wang, S. Y.; Yan, X. C.; Zhou, J. X.; Liu, Y.; Cai, J.; Liu, E. S.; Jia, Q. Y.; Duan, X. F. et al. Enhancement of oxygen reduction reaction activity by grain boundaries in platinum nanostructures. Nano Res. 2020, 13, 3310–3314.

    Article  CAS  Google Scholar 

  13. Fichtner, J.; Garlyyev, B.; Watzele, S.; El-Sayed, H. A.; Schwämmlein, J. N.; Li, W. J.; Maillard, F. M.; Dubau, L.; Michalička, J.; Macak, J. M. et al. Top-down synthesis of nanostructured platinum-lanthanide alloy oxygen reduction reaction catalysts: PtxPr/C as an example. ACS Appl. Mater. Inter. 2019, 11, 5129–5135.

    Article  CAS  Google Scholar 

  14. Hagfeldt, A.; Boschloo, G.; Sun, L. C.; Kloo, L.; Pettersson, H. Dye-sensitized solar cells. Chem. Rev. 2010, 110, 6595–6663.

    Article  CAS  Google Scholar 

  15. Wu, J. H.; Lan, Z.; Lin, J. M.; Huang, M. L.; Huang, Y. F.; Fan, L. Q.; Luo, G. G.; Lin, Y.; Xie, Y. M.; Wei, Y. L. Counter electrodes in dye-sensitized solar cells. Chem. Soc. Rev. 2017, 46, 5975–6023.

    Article  CAS  Google Scholar 

  16. Bu, L. Z.; Shao, Q.; E, B.; Guo, J.; Yao, J. L.; Huang, X. Q. PtPb/PtNi intermetallic core/atomic layer shell octahedra for efficient oxygen reduction electrocatalysis. J. Am. Chem. Soc. 2017, 139, 9576–9582.

    Article  CAS  Google Scholar 

  17. Lu, S. Q.; Zhuang, Z. B. Investigating the influences of the adsorbed species on catalytic activity for hydrogen oxidation reaction in alkaline electrolyte. J. Am. Chem. Soc. 2017, 139, 5156–5163.

    Article  CAS  Google Scholar 

  18. Zhang, Z. C.; Liu, G. G.; Cui, X. Y.; Chen, B.; Zhu, Y. H.; Gong, Y.; Saleem, F.; Xi, S. B.; Du, Y. H.; Borgna, A. et al. Crystal phase and architecture engineering of lotus-thalamus-shaped Pt-Ni anisotropic superstructures for highly efficient electrochemical hydrogen evolution. Adv. Mater. 2018, 30, 1801741.

    Article  Google Scholar 

  19. Duan, Y.; Yu, Z. Y.; Yang, L.; Zheng, L. R.; Zhang, C. T.; Yang, X. T.; Gao, F. Y.; Zhang, X. L.; Yu, X. X.; Liu, R. et al. Bimetallic nickelmolybdenum/tungsten nanoalloys for high-efficiency hydrogen oxidation catalysis in alkaline electrolytes. Nat. Commun. 2020, 11, 4789.

    Article  CAS  Google Scholar 

  20. Mao, J. J.; Chen, W. X.; He, D. S.; Wan, J. W.; Pei, J. J.; Dong, J. C.; Wang, Y.; An, P. F.; Jin, Z.; Xing, W. et al. Design of ultrathin Pt-Mo-Ni nanowire catalysts for ethanol electrooxidation. Sci. Adv. 2017, 3, e1603068.

    Article  Google Scholar 

  21. Liu, B.; Aydil, E. S. Growth of oriented single-crystalline rutile TiO2 nanorods on transparent conducting substrates for dye-sensitized solar cells. J. Am. Chem. Soc. 2009, 131, 3985–3990.

    Article  CAS  Google Scholar 

  22. Gong, F.; Wang, H.; Xu, X.; Zhou, G.; Wang, Z. S. In situ growth of Co0.85Se and Ni0.85Se on conductive substrates as high-performance counter electrodes for dye-sensitized solar cells. J. Am. Chem. Soc. 2012, 134, 10953–10958.

    Article  CAS  Google Scholar 

  23. Wu, M. X.; Lin, X.; Wang, Y. D.; Wang, L.; Guo, W.; Qi, D. D.; Peng, X. J.; Hagfeldt, A.; Grätzel, M.; Ma, T. L. Economical Pt-free catalysts for counter electrodes of dye-sensitized solar cells. J. Am. Chem. Soc. 2012, 134, 3419–3428.

    Article  CAS  Google Scholar 

  24. Xue, Y. H.; Liu, J.; Chen, H.; Wang, R. G.; Li, D. Q.; Qu, J.; Dai, L. M. Nitrogen-doped graphene foams as metal-free counter electrodes in high-performance dye-sensitized solar cells. Angew. Chem., Int. Ed. 2012, 51, 12124–12127.

    Article  CAS  Google Scholar 

  25. Duan, Y. Y.; Tang, Q. W.; Liu, J.; He, B. L.; Yu, L. M. Transparent metal selenide alloy counter electrodes for high-efficiency bifacial dye-sensitized solar cells. Angew. Chem., Int. Ed. 2014, 53, 14569–14574.

    Article  CAS  Google Scholar 

  26. Tang, Q. W.; Zhang, H. H.; Meng, Y. Y.; He, B. L.; Yu, L. M. Dissolution engineering of platinum alloy counter electrodes in dye-sensitized solar cells. Angew. Chem., Int. Ed. 2015, 54, 11448–11452.

    Article  CAS  Google Scholar 

  27. Cui, X. J.; Xiao, J. P.; Wu, Y. H.; Du, P. P.; Si, R.; Yang, H. X.; Tian, H. F.; Li, J. Q.; Zhang, W. H.; Deng, D. H. et al. A graphene composite material with single cobalt active sites: A highly efficient counter electrode for dye-sensitized solar cells. Angew. Chem., Int. Ed. 2016, 55, 6708–6712.

    Article  CAS  Google Scholar 

  28. Lu, W. L.; Jiang, R.; Yin, X.; Wang, L. Y. Porous N-doped-carbon coated CoSe2 anchored on carbon cloth as 3D photocathode for dye-sensitized solar cell with efficiency and stability outperforming Pt. Nano Res. 2019, 12, 159–163.

    Article  CAS  Google Scholar 

  29. Wang, Y. Q.; Gao, X. L.; Song, B.; Gu, Y. L.; Sun, Y. M. Photoelectrochemical properties of MWCNT-TiO2 hybrid materials as a counter electrode for dye-sensitized solar cells. Chin. Chem. Lett. 2014, 25, 491–495.

    Article  CAS  Google Scholar 

  30. Li, Z. X.; Liu, S. A.; Li, L. D.; Qi, W. K.; Lai, W. D.; Li, L.; Zhao, X. H.; Zhang, Y. C.; Zhang, W. M. In situ grown MnCo2O4@NiCo2O4 layered core-shell plexiform array on carbon paper for high efficiency counter electrode materials of dye-sensitized solar cells. Sol. Energy Mater. Sol. Cells 2021, 220, 110859.

    Article  CAS  Google Scholar 

  31. Sarkar, A.; Chakraborty, A. K.; Bera, S. NiS/rGO nanohybrid: An excellent counter electrode for dye sensitized solar cell. Sol. Energy Mater. Sol. Cells 2018, 182, 314–320.

    Article  CAS  Google Scholar 

  32. Ma, P.; Lu, W. L.; Yan, X. Y.; Li, W. D.; Li, L.; Fang, Y. Y.; Yin, X.; Liu, Z. G.; Lin, Y. Heteroatom tri-doped porous carbon derived from waste biomass as Pt-free counter electrode in dye-sensitized solar cells. RSC Adv. 2018, 8, 18427–18433.

    Article  CAS  Google Scholar 

  33. Hou, Y.; Wang, D.; Yang, X. H.; Fang, W. Q.; Zhang, B.; Wang, H. F.; Lu, G. Z.; Hu, P.; Zhao, H. J.; Yang, H. G. Rational screening low-cost counter electrodes for dye-sensitized solar cells. Nat. Commun. 2013, 4, 1583.

    Article  Google Scholar 

  34. Wang, X. W.; Xie, Y.; Bateer, B.; Pan, K.; Jiao, Y. Q.; Xiong, N.; Wang, S.; Fu, H. G. Selenization of Cu2ZnSnS4 Enhanced the performance of dye-sensitized solar cells: Improved zinc-site catalytic activity for I3−. ACS Appl. Mater. Inter. 2017, 9, 37662–37670.

    Article  CAS  Google Scholar 

  35. Wan, J. W.; Fang, G. J.; Yin, H. J.; Liu, X. F.; Liu, D.; Zhao, M. T.; Ke, W. J.; Tao, H.; Tang, Z. Y. Pt-Ni alloy nanoparticles as superior counter electrodes for dye-sensitized solar cells: Experimental and theoretical understanding. Adv. Mater. 2014, 26, 8101–8106.

    Article  CAS  Google Scholar 

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Acknowledgements

The research was financially supported by the National Natural Science Foundation of China (No. 21771019), the National Key Research and Development Program of China (No. 2018YFA0702002), and the Fundamental Research Funds for the Central Universities (Nos. XK1901 and buctrc202023). P. Ma is funded by China Postdoctoral Science Foundation (No. 2020M672772). We are thankful for 1W1B in Beijing Electron Positron Collider II (BSRF) for X-ray absorption spectroscopy (XAS) measurements.

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  1. Jiabin Cui and Pin Ma contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Chemical Resource Engineering, Innovation Centre for Soft Matter Science and Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029, China

    Jiabin Cui, Weidan Li, Rui Jiang, Chang Guo, Xiong Yin & Leyu Wang

  2. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Pin Ma & Yuan Lin

  3. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China

    Lirong Zheng

  4. Pillar of Engineering Product Development, Singapore University of Technology and Design, Singapore, 487372, Singapore

    Pin Ma

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  1. Jiabin Cui
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Correspondence to Chang Guo or Xiong Yin.

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Cui, J., Ma, P., Li, W. et al. Surface active-site engineering in hierarchical PtNi nanocatalysts for efficient triiodide reduction reaction. Nano Res. 14, 4714–4718 (2021). https://doi.org/10.1007/s12274-021-3410-y

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