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Precious trimetallic single-cluster catalysts for oxygen and hydrogen electrocatalytic reactions: Theoretical considerations

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Abstract

Single cluster catalysts (SCCs), which exhibit remarkable catalytic performance due to their high metal loading and synergy effect between metal atoms, have attracted great attention in research. Herein, by means of density functional theory calculations, the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) performances of precious metal (Pt, Pd, Rh, and Ir) trimetallic single-cluster electrocatalyst (UxVyWz-NG) are investigated. The calculation results show that Pt, Pd, and Ir have significant effect on ORR, OER, and HER, respectively, and all the calculated UxVyWz-NG structures are thermodynamically stable due to the negative formation energies and binding energies. The Pt3-NG, Pd3-NG, and Ir3-NG show the lowest ORR, OER, and HER overpotentials of 0.63, 0.77, and −0.02 V, respectively, among all combinations of UxVyWz-NG. These overpotentials are lower than that of precious metal single atom catalysts (SACs), which indicate better activities of precious trimetallic SCCs than those of SACs. The electronic structure reveals that the O-2p orbital shows strong hybridization strength with Pt-3d orbitals in the system of OH adsorbed Pt3-NG and thus facilitates the electrocatalytic reactions. The results are helpful for the rational design of high-performance triatomic catalysts.

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References

  1. Sun, T. T.; Li, Y. L.; Cui, T. T.; Xu, L. B.; Wang, Y. G.; Chen, W. X.; Zhang, P. P.; Zheng, T. Y.; Fu, X. Z.; Zhang, S. L. et al. Engineering of coordination environment and multiscale structure in single-site copper catalyst for superior electrocatalytic oxygen reduction. Nano Lett. 2020, 20, 6206–6214.

    CAS  Google Scholar 

  2. Ji, S. F.; Qu, Y.; Wang, T.; Chen, Y. J.; Wang, G. F.; Li, X.; Dong, J. C.; Chen, Q. Y.; Zhang, W. Y.; Zhang, Z. D. et al. Rare-earth single erbium atoms for enhanced photocatalytic CO2 reduction. Angew. Chem., Int. Ed. 2020, 59, 10651–10657.

    CAS  Google Scholar 

  3. Wu, D.; Xie, X. B.; Zhang, J. J.; Ma, Y. P.; Hou, C. X.; Sun, X. Q.; Yang, X. Y.; Zhang, Y. P.; Kimura, H.; Du, W. Embedding NiS nanoflakes in electrospun carbon fibers containing NiS nanoparticles for hybrid supercapacitors. Chem. Eng. J. 2022, 446, 137262.

    CAS  Google Scholar 

  4. Zhang, B.; Xie, X. B.; Wang, Y. K.; Hou, C. X.; Sun, X. Q.; Zhang, Y. P.; Yang, X. Y.; Yu, R. H.; Du, W. In situ formation of multiple catalysts for enhancing the hydrogen storage of MgH2 by adding porous Ni3ZnC0.7/Ni loaded carbon nanotubes microspheres. J. Magnes. Alloys, in press, https://doi.org/10.1016/j.jma.2022.07.004.

  5. Debe, M. K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature 2012, 486, 43–51.

    CAS  Google Scholar 

  6. Sun, T. T.; Xu, L. B.; Wang, D. S.; Li, Y. D. Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion. Nano Res. 2019, 12, 2067–2080.

    CAS  Google Scholar 

  7. Zhu, C. Z.; Fu, S. F.; Shi, Q. R.; Du, D.; Lin, Y. H. Single-atom electrocatalysts. Angew. Chem., Int. Ed. 2017, 56, 13944–13960.

    CAS  Google Scholar 

  8. Li, Y. C.; Hu, R. M.; Wan, X.; Shang, J. X.; Wang, F. H.; Shui, J. L. Density functional theory calculation of Zn and N codoped graphene for oxygen reduction and evolution reactions. Adv. Theory Simul. 2020, 3, 2000054.

    CAS  Google Scholar 

  9. Li, W. H.; Yang, J. R.; Wang, D. S. Long-range interactions in diatomic catalysts boosting electrocatalysis. Angew. Chem., Int. Ed. 2022, 61, e202213318.

    CAS  Google Scholar 

  10. Zhao, S. Z.; Wen, Y. F.; Liu, X. J.; Pen, X. Y.; Lü, F.; Gao, F. Y.; Xie, X. Z.; Du, C. C.; Yi, H. H.; Kang, D. J. et al. Formation of active oxygen species on single-atom Pt catalyst and promoted catalytic oxidation of toluene. Nano Res. 2020, 13, 1544–1551.

    CAS  Google Scholar 

  11. Wang, L. N.; Wan, X.; Liu, S. Y.; Xu, L.; Shui, J. L. Fe-N-C catalysts for PEMFC: Progress towards the commercial application under DOE reference. J. Energy Chem. 2019, 39, 77–87.

    CAS  Google Scholar 

  12. Tang, W. K.; Liu, X. F.; Li, Y.; Pu, Y. H.; Lu, Y.; Song, Z. M.; Wang, Q.; Yu, R. H.; Shui, J. L. Boosting electrocatalytic water splitting via metal-metalloid combined modulation in quaternary Ni-Fe-P-B amorphous compound. Nano Res. 2020, 13, 447–454.

    CAS  Google Scholar 

  13. Li, Y. C.; Hu, R. M.; Chen, Z. B.; Wan, X.; Shang, J. X.; Wang, F. H.; Shui, J. L. Effect of Zn atom in Fe-N-C catalysts for electro-catalytic reactions: Theoretical considerations. Nano Res. 2021, 14, 611–619.

    CAS  Google Scholar 

  14. Li, X. Y.; Rong, H. P.; Zhang, J. T.; Wang, D. S.; Li, Y. D. Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance. Nano Res. 2020, 13, 1842–1855.

    CAS  Google Scholar 

  15. Zhuang, Z. C.; Kang, Q.; Wang, D. S.; Li, Y. D. Single-atom catalysis enables long-life, high-energy lithium-sulfur batteries. Nano Res. 2020, 13, 1856–1866.

    CAS  Google Scholar 

  16. Xiong, Y.; Sun, W. M.; Han, Y. H.; Xin, P. Y.; Zheng, X. S.; Yan, W. S.; Dong, J. C.; Zhang, J.; Wang, D. S.; Li, Y. D. Cobalt single atom site catalysts with ultrahigh metal loading for enhanced aerobic oxidation of ethylbenzene. Nano Res. 2021, 14, 2418–2423.

    CAS  Google Scholar 

  17. Liu, J.; Cao, D.; Xu, H. X.; Cheng, D. J. From double-atom catalysts to single-cluster catalysts: A new frontier in heterogeneous catalysis. Nano Sel. 2021, 2, 251–270.

    CAS  Google Scholar 

  18. Jiao, J. Q.; Lin, R.; Liu, S. J.; Cheong, W. C.; Zhang, C.; Chen, Z.; Pan, Y.; Tang, J. G.; Wu, K. L.; Hung, S. F. et al. Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO2. Nat. Chem. 2019, 11, 222–228.

    CAS  Google Scholar 

  19. Chen, C. H.; Wu, D. Y.; Li, Z.; Zhang, R.; Kuai, C. G.; Zhao, X. R.; Dong, C. K.; Qiao, S. Z.; Liu, H.; Du, X. W. Ruthenium-based single-atom alloy with high electrocatalytic activity for hydrogen evolution. Adv. Energy Mater. 2019, 9, 1803913.

    Google Scholar 

  20. Song, P.; Luo, M.; Liu, X. Z.; Xing, W.; Xu, W. L.; Jiang, Z.; Gu, L. Zn single atom catalyst for highly efficient oxygen reduction reaction. Adv. Funct. Mater. 2017, 27, 1700802.

    Google Scholar 

  21. Xiao, M. L.; Zhang, H.; Chen, Y. T.; Zhu, J. B.; Gao, L. Q.; Jin, Z.; Ge, J. J.; Jiang, Z.; Chen, S. L.; Liu, C. P. et al. Identification of binuclear Co2N5 active sites for oxygen reduction reaction with more than one magnitude higher activity than single atom CoN4 site. Nano Energy 2018, 46, 396–403.

    CAS  Google Scholar 

  22. Xiong, Y.; Sun, W. M.; Xin, P. Y.; Chen, W. X.; Zheng, X. S.; Yan, W. S.; Zheng, L. R.; Dong, J. C.; Zhang, J.; Wang, D. S. et al. Gramscale synthesis of high-loading single-atomic-site Fe catalysts for effective epoxidation of styrene. Adv. Mater. 2020, 32, 2000896.

    CAS  Google Scholar 

  23. Wang, Y. N.; Wan, X.; Liu, J. Y.; Li, W. W.; Li, Y. C.; Guo, X.; Liu, X. F.; Shang, J. X.; Shui, J. L. Catalysis stability enhancement of Fe/Co dual-atom site via phosphorus coordination for proton exchange membrane fuel cell. Nano Res. 2022, 15, 3082–3089.

    CAS  Google Scholar 

  24. Pei, W.; Zhou, S.; Zhao, J. J.; Xu, X.; Du, Y.; Dou, S. X. Immobilized trimeric metal clusters: A family of the smallest catalysts for selective CO2 reduction toward multi-carbon products. Nano Energy 2020, 76, 105049.

    CAS  Google Scholar 

  25. Wang, J.; You, R.; Zhao, C.; Zhang, W.; Liu, W.; Fu, X. P.; Li, Y. Y.; Zhou, F. Y.; Zheng, X. S.; Xu, Q. et al. N-coordinated dual-metal single-site catalyst for low-temperature CO oxidation. ACS Catal. 2020, 10, 2754–2761.

    CAS  Google Scholar 

  26. Zheng, X. B.; Li, B. B.; Wang, Q. S.; Wang, D. S.; Li, Y. D. Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis. Nano Res. 2022, 15, 7806–7839.

    CAS  Google Scholar 

  27. Chen, M.; Pu, Y. H.; Li, Z. Y.; Huang, G.; Liu, X. F.; Lu, Y.; Tang, W. K.; Xu, L.; Liu, S. Y.; Yu, R. H. et al. Synergy between metallic components of MoNi alloy for catalyzing highly efficient hydrogen storage of MgH2. Nano Res. 2020, 13, 2063–2071.

    CAS  Google Scholar 

  28. Zheng, X. N.; Yao, Y.; Wang, Y.; Liu, Y. Tuning the electronic structure of transition metals embedded in nitrogen-doped graphene for electrocatalytic nitrogen reduction: A first-principles study. Nanoscale 2020, 12, 9696–9707.

    CAS  Google Scholar 

  29. Hu, R. M.; Li, Y. C.; Zeng, Q. W.; Shang, J. X. Role of active sites in N-coordinated Fe-Co dual-metal doped graphene for oxygen reduction and evolution reactions: A theoretical insight. Appl. Surf. Sci. 2020, 525, 146588.

    CAS  Google Scholar 

  30. Wang, J.; Liu, W.; Luo, G.; Li, Z. J.; Zhao, C.; Zhang, H. R.; Zhu, M. Z.; Xu, Q.; Wang, X. Q.; Zhao, C. M. et al. Synergistic effect of well-defined dual sites boosting the oxygen reduction reaction. Energy Environ. Sci. 2018, 11, 3375–3379.

    CAS  Google Scholar 

  31. Zheng, X. B.; Yang, J. R.; Xu, Z. F.; Wang, Q. S.; Wu, J. B.; Zhang, E. H.; Dou, S. X.; Sun, W. P.; Wang, D. S.; Li, Y. D. Ru—Co pair sites catalyst boosts the energetics for the oxygen evolution reaction. Angew. Chem., Int. Ed. 2022, 61, e202205946.

    CAS  Google Scholar 

  32. Zheng, X. N.; Liu, Y.; Yao, Y. Trimetallic single-cluster catalysts for electrochemical nitrogen reduction reaction: Activity prediction, mechanism, and electronic descriptor. Chem. Eng. J. 2021, 426, 130745.

    CAS  Google Scholar 

  33. Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.

    CAS  Google Scholar 

  34. Li, R. Z.; Wang, D. S. Understanding the structure—performance relationship of active sites at atomic scale. Nano Res. 2022, 15, 6888–6923.

    CAS  Google Scholar 

  35. Vorobyeva, E.; Fako, E.; Chen, Z. P.; Collins, S. M.; Johnstone, D.; Midgley, P. A.; Hauert, R.; Safonova, O. V.; Vilé, G.; López, N. Atom-by-atom resolution of structure—function relations over low-nuclearity metal catalysts. Angew. Chem. 2019, 131, 8816–8821.

    Google Scholar 

  36. Ji, S. F.; Chen, Y. J.; Fu, Q.; Chen, Y. F.; Dong, J. C.; Chen, W. X.; Li, Z.; Wang, Y.; Gu, L.; He, W. et al. Confined pyrolysis within metal-organic frameworks to form uniform Ru3 clusters for efficient oxidation of alcohols. J. Am. Chem. Soc. 2017, 139, 9795–9798.

    CAS  Google Scholar 

  37. Ye, W.; Chen, S. M.; Lin, Y.; Yang, L.; Chen, S. J.; Zheng, X. S.; Qi, Z. M.; Wang, C. M.; Long, R.; Chen, M. et al. Precisely tuning the number of Fe atoms in clusters on N-doped carbon toward acidic oxygen reduction reaction. Chem 2019, 5, 2865–2878.

    CAS  Google Scholar 

  38. Saidaminov, M. I.; Abdelhady, A. L.; Murali, B.; Alarousu, E.; Burlakov, V. M.; Peng, W.; Dursun, I.; Wang, L. F.; He, Y.; Maculan, G. et al. High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization. Nat. Commun. 2015, 6, 7586.

    Google Scholar 

  39. Armel, V.; Hindocha, S.; Salles, F.; Bennett, S.; Jones, D.; Jaouen, F. Structural descriptors of zeolitic-imidazolate frameworks are keys to the activity of Fe-N-C catalysts. J. Am. Chem. Soc. 2017, 139, 453–464.

    CAS  Google Scholar 

  40. Xu, J. T.; Lin, Y.; Connell, J. W.; Dai, L. M. Nitrogen-doped holey graphene as an anode for lithium-ion batteries with high volumetric energy density and long cycle life. Small 2015, 11, 6179–6185.

    CAS  Google Scholar 

  41. Luo, G. X.; Liu, L. Z.; Zhang, J. F.; Li, G. B.; Wang, B. L.; Zhao, J. J. Hole defects and nitrogen doping in graphene: Implication for supercapacitor applications. ACS Appl. Mater. Interfaces 2013, 5, 11184–11193.

    CAS  Google Scholar 

  42. Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.

    CAS  Google Scholar 

  43. Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.

    CAS  Google Scholar 

  44. Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.

    CAS  Google Scholar 

  45. Martyna, G. J.; Klein, M. L.; Tuckerman, M. Nosé-Hoover chains: The canonical ensemble via continuous dynamics. J. Chem. Phys. 1992, 97, 2635–2643.

    Google Scholar 

  46. Chadi, D. J. Special points for Brillouin-zone integrations. Phys. Rev. B 1977, 16, 1746–1747.

    Google Scholar 

  47. Kattel, S.; Atanassov, P.; Kiefer, B. Stability, electronic and magnetic properties of in-plane defects in graphene: A first-principles study. J. Phys. Chem. C 2012, 116, 8161–8166.

    CAS  Google Scholar 

  48. Xu, H. X.; Cheng, D. J.; Cao, D. P.; Zeng, X. C. A universal principle for a rational design of single-atom electrocatalysts. Nat. Catal. 2018, 1, 339–348.

    CAS  Google Scholar 

  49. Choi, C.; Back, S.; Kim, N. Y.; Lim, J.; Kim, Y. H.; Jung, Y. Suppression of hydrogen evolution reaction in electrochemical N2 reduction using single-atom catalysts: A computational guideline. ACS Catal. 2018, 8, 7517–7525.

    CAS  Google Scholar 

  50. Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 2004, 108, 17886–17892.

    Google Scholar 

  51. Nørskov, J. K.; Bligaard, T.; Logadottir, A.; Kitchin, J.; Chen, J. G.; Pandelov, S.; Stimming, U. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 2005, 152, J23.

    Google Scholar 

  52. Medford, A. J.; Vojvodic, A.; Hummelshøj, J. S.; Voss, J.; Abild-Pedersen, F.; Studt, F.; Bligaard, T.; Nilsson, A.; Nørskov, J. K. From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis. J. Catal. 2015, 328, 36–42.

    CAS  Google Scholar 

  53. Wang, Y. R.; Hu, R. M.; Li, Y. C.; Wang, F. H.; Shang, J. X.; Shui, J. L. High-throughput screening of carbon-supported single metal atom catalysts for oxygen reduction reaction. Nano Res. 2022, 15, 1054–1060.

    CAS  Google Scholar 

  54. Lai, Q. X.; Zheng, L. R.; Liang, Y. Y.; He, J. P.; Zhao, J. X.; Chen, J. H. Metal-organic-framework-derived Fe-N/C electrocatalyst with five-coordinated Fe-Nx sites for advanced oxygen reduction in acid media. ACS Catal. 2017, 7, 1655–1663.

    CAS  Google Scholar 

  55. Nørskov, J. K.; Abild-Pedersen, F.; Studt, F.; Bligaard, T. Density functional theory in surface chemistry and catalysis. Proc. Natl. Acad. Sci. USA 2011, 108, 937–943.

    Google Scholar 

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Acknowledgements

This work was supported by the 2022 Youth Scientific Research Fund Project of Qinghai University (No. 2022-QGY-2), Qinghai Provincial Key Laboratory of New Light Alloys (No. 2022-ZJ-Y20), and Kunlun Talent Project Program of Qinghai Province.

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Authors and Affiliations

  1. Qinghai Provincial Key Laboratory of New Light Alloys, Qinghai Provincial engineering Research Center of High Performance Light Metal Alloys and Forming, Qinghai University, Xining, 810016, China

    Xiaochuan Shi, Yongcheng Li, Shan Zhang, Shuang Gao & Peipeng Jin

  2. Qinghai Communications Technical College, Xining, 810003, China

    Xiaochuan Shi

  3. Institute for Smart Materials & Engineering, University of Jinan, Jinan, 250022, China

    Riming Hu

  4. School of Materials Science and Engineering, Beihang University, Beijing, 100191, China

    Jiaxiang Shang & Jianglan Shui

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  1. Xiaochuan Shi
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  2. Yongcheng Li
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Correspondence to Yongcheng Li or Jianglan Shui.

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Precious trimetallic single-cluster catalysts for oxygen and hydrogen electrocatalytic reactions: Theoretical considerations

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Shi, X., Li, Y., Zhang, S. et al. Precious trimetallic single-cluster catalysts for oxygen and hydrogen electrocatalytic reactions: Theoretical considerations. Nano Res. 16, 8042–8050 (2023). https://doi.org/10.1007/s12274-022-5347-6

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