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Nano Research 2023, 16(7): 9968-9976 https://doi.org/10.1007/s12274-023-5484-6
Communication | Issue | Published: 02 March 2023

Temperature-driven phase transformation and element segregation in Pd-Ru immiscible alloy nanoparticles: Spatial resolving of elements and insights for electrocatalysis

Show Author's Information Hui Li1,2,§,  Zheng Hu1,§,  Yu Zhang1,2,  Wenbo Zhao1,  Yuyao Zeng3,  Wei Zhou4,  Shi Hu1,2( )
Department of Chemistry, School of Science, Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, Tianjin 300072, China
Institute of Energy, Hefei Comprehensive National Science Center, Hefei 230031, China
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China
Department of Physics, School of Science, Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, Tianjin 300072, China

§ Hui Li and Zheng Hu contributed equally to this work.

Keywords:
hydrogen evolution reaction, Pd-Ru alloy, short-range order, local element segregation
Topics:
Binary alloysElectrocatalysis Electron microscopy
Cite this article:
Li H, Hu Z, Zhang Y, et al. Temperature-driven phase transformation and element segregation in Pd-Ru immiscible alloy nanoparticles: Spatial resolving of elements and insights for electrocatalysis. Nano Research, 2023, 16(7): 9968-9976. https://doi.org/10.1007/s12274-023-5484-6
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Abstract Full text Electronic supplementary material About this article

Bimetallic alloys could form three typical structures including solid solution, heterostructure, and intermetallic compound, depending on the interactions between identical and different atoms. Although the trend can be predicted by the types of binary phase diagram, different synthetic protocols will trap the system in various kinetic intermediates among the three typical structures. Herein, we studied the phase evolution and elemental segregation in the alloy nanoparticles of immiscible Pd-Ru before and after thermal annealing. By developing an analysis method of local element segregation (LES) based on the energy dispersive spectroscopy (EDS) mapping signals, we were able to quantify the mixing of Pd and Ru atoms during the gradual phase transition from face-centered cubic (fcc) to hexagonal close packed (hcp). Density functional theory was also applied to calculate the energies of all possible PdRu4 structures (93 fcc models and 267 hcp models), which helps to rationalize the phase transition and element segregation. The annealing process also leads to the change of the electronic structure, which further influences the performance in the electrocatalytic hydrogen evolution reaction. The highest activity of PdRu4-400 was largely attributed to the proper interface between the Pd-rich fcc phase and Ru-rich hcp phase, as revolved by the above methods.


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Abstract
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Electronic supplementary material
About this article

Temperature-driven phase transformation and element segregation in Pd-Ru immiscible alloy nanoparticles: Spatial resolving of elements and insights for electrocatalysis

Show Author's information Hui Li1,2,§, Zheng Hu1,§, Yu Zhang1,2, Wenbo Zhao1, Yuyao Zeng3, Wei Zhou4, Shi Hu1,2( )
Department of Chemistry, School of Science, Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, Tianjin 300072, China
Institute of Energy, Hefei Comprehensive National Science Center, Hefei 230031, China
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China
Department of Physics, School of Science, Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, Tianjin 300072, China

§ Hui Li and Zheng Hu contributed equally to this work.

Abstract

Bimetallic alloys could form three typical structures including solid solution, heterostructure, and intermetallic compound, depending on the interactions between identical and different atoms. Although the trend can be predicted by the types of binary phase diagram, different synthetic protocols will trap the system in various kinetic intermediates among the three typical structures. Herein, we studied the phase evolution and elemental segregation in the alloy nanoparticles of immiscible Pd-Ru before and after thermal annealing. By developing an analysis method of local element segregation (LES) based on the energy dispersive spectroscopy (EDS) mapping signals, we were able to quantify the mixing of Pd and Ru atoms during the gradual phase transition from face-centered cubic (fcc) to hexagonal close packed (hcp). Density functional theory was also applied to calculate the energies of all possible PdRu4 structures (93 fcc models and 267 hcp models), which helps to rationalize the phase transition and element segregation. The annealing process also leads to the change of the electronic structure, which further influences the performance in the electrocatalytic hydrogen evolution reaction. The highest activity of PdRu4-400 was largely attributed to the proper interface between the Pd-rich fcc phase and Ru-rich hcp phase, as revolved by the above methods.

Keywords: hydrogen evolution reaction, Pd-Ru alloy, short-range order, local element segregation

References(50)

[1]

Liu, L. C.; Corma, A. Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981–5079.
DOI Google Scholar
[2]

Wang, D. S.; Li, Y. D. Bimetallic nanocrystals: Liquid-phase synthesis and catalytic applications. Adv. Mater. 2011, 23, 1044–1060.
DOI Google Scholar
[3]

Cargnello, M.; Doan-Nguyen, V. V. T.; Gordon, T. R.; Diaz, R. E.; Stach, E. A.; Gorte, R. J.; Fornasiero, P.; Murray, C. B. Control of metal nanocrystal size reveals metal-support interface role for ceria catalysts. Science 2013, 341, 771–773.
DOI Google Scholar
[4]

Luo, M. C.; Zhao, Z. L.; Zhang, Y. L.; Sun, Y. J.; Xing, Y.; Lv, F.; Yang, Y.; Zhang, X.; Hwang, S.; Qin, Y. N. et al. PdMo bimetallene for oxygen reduction catalysis. Nature 2019, 574, 81–85.
DOI Google Scholar
[5]

Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.
DOI Google Scholar
[6]

Xie, C. L.; Niu, Z. Q.; Kim, D.; Li, M. F.; Yang, P. D. Surface and interface control in nanoparticle catalysis. Chem. Rev. 2020, 120, 1184–1249.
DOI Google Scholar
[7]

Gilroy, K. D.; Ruditskiy, A.; Peng, H. C.; Qin, D.; Xia, Y. N. Bimetallic nanocrystals: Syntheses, properties, and applications. Chem. Rev. 2016, 116, 10414–10472.
DOI Google Scholar
[8]

Bligaard, T.; Nørskov, J. K.; Dahl, S.; Matthiesen, J.; Christensen, C. H.; Sehested, J. The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis. J. Catal. 2004, 224, 206–217.
DOI Google Scholar
[9]

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.
DOI Google Scholar
[10]

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.
DOI Google Scholar
[11]

Chen, Y.; Lai, Z. C.; Zhang, X.; Fan, Z. X.; He, Q. Y.; Tan, C. L.; Zhang, H. Phase engineering of nanomaterials. Nat. Rev. Chem. 2020, 4, 243–256.
DOI Google Scholar
[12]

Stamenković, V.; Schmidt, T. J.; Ross, P. N.; Marković, N. M. Surface composition effects in electrocatalysis: Kinetics of oxygen reduction on well-defined Pt3Ni and Pt3Co alloy surfaces. J. Phys. Chem. B 2002, 106, 11970–11979.
DOI Google Scholar
[13]

Huang, J.; Peng, B. S.; Stracensky, T.; Liu, Z. Y.; Zhang, A.; Xu, M. J.; Liu, Y.; Zhao, Z. P.; Duan, X. F.; Jia, Q. Y. et al. 1D PtCo nanowires as catalysts for PEMFCs with low Pt loading. Sci. China Mater. 2022, 65, 704–711.
DOI Google Scholar
[14]

Baskaran, S.; Xu, C. Q.; Wang, Y. G.; Garzón, I. L.; Li, J. Catalytic mechanism and bonding analyses of Au-Pd single atom alloy (SAA): CO oxidation reaction. Sci. China Mater. 2020, 63, 993–1002.
DOI Google Scholar
[15]

Kobayashi, H.; Kusada, K.; Kitagawa, H. Creation of novel solid-solution alloy nanoparticles on the basis of density-of-states engineering by interelement fusion. Acc. Chem. Res. 2015, 48, 1551–1559.
DOI Google Scholar
[16]

Durst, J.; Siebel, A.; Simon, C.; Hasché, F.; Herranz, J.; Gasteiger, H. A. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ. Sci. 2014, 7, 2255–2260.
DOI Google Scholar
[17]

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.
DOI Google Scholar
[18]
Baker, H. ASM Handbook. Volume 3. Alloy Phase Diagrams; 10th ed. ASM International: Materials Park, Ohio, 1992.
[19]

Zugic, B.; Wang, L. C.; Heine, C.; Zakharov, D. N.; Lechner, B. A. J.; Stach, E. A.; Biener, J.; Salmeron, M.; Madix, R. J.; Friend, C. M. Dynamic restructuring drives catalytic activity on nanoporous gold-silver alloy catalysts. Nat. Mater. 2017, 16, 558–564.
DOI Google Scholar
[20]

Kim, D.; Xie, C. L.; Becknell, N.; Yu, Y.; Karamad, M.; Chan, K.; Crumlin, E. J.; Nørskov, J. K.; Yang, P. D. Electrochemical activation of CO2 through atomic ordering transformations of AuCu nanoparticles. J. Am. Chem. Soc. 2017, 139, 8329–8336.
DOI Google Scholar
[21]

Huang, J. F.; Mensi, M.; Oveisi, E.; Mantella, V.; Buonsanti, R. Structural sensitivities in bimetallic catalysts for electrochemical CO2 reduction revealed by Ag-Cu nanodimers. J. Am. Chem. Soc. 2019, 141, 2490–2499.
DOI Google Scholar
[22]

Yang, C. P.; Ko, B. H.; Hwang, S.; Liu, Z. Y.; Yao, Y. G.; Luc, W.; Cui, M. J.; Malkani, A. S.; Li, T. Y.; Wang, X. Z. et al. Overcoming immiscibility toward bimetallic catalyst library. Sci. Adv. 2020, 6, eaaz6844.
DOI Google Scholar
[23]

Wang, D. L.; Xin, H. L.; Hovden, R.; Wang, H. S.; Yu, Y. C.; Muller, D. A.; DiSalvo, F. J.; Abruña, H. D. Structurally ordered intermetallic platinum-cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts. Nat. Mater. 2013, 12, 81–87.
DOI Google Scholar
[24]

Yang, C. L.; Wang, L. N.; Yin, P.; Liu, J. Y.; Chen, M. X.; Yan, Q. Q.; Wang, Z. S.; Xu, S. L.; Chu, S. Q.; Cui, C. H. et al. Sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells. Science 2021, 374, 459–464.
DOI Google Scholar
[25]

Ding, K. L.; Cullen, D. A.; Zhang, L. B.; Cao, Z.; Roy, A. D.; Ivanov, I. N.; Cao, D. M. A general synthesis approach for supported bimetallic nanoparticles via surface inorganometallic chemistry. Science 2018, 362, 560–564.
DOI Google Scholar
[26]

Guo, H. Y.; Li, H.; Jarvis, K.; Wan, H. Q.; Kunal, P.; Dunning, S. G.; Liu, Y. L.; Henkelman, G.; Humphrey, S. M. Microwave-assisted synthesis of classically immiscible Ag-Ir alloy nanoparticle catalysts. ACS Catal. 2018, 8, 11386–11397.
DOI Google Scholar
[27]

Kim, D.; Nam, H.; Cho, Y. H.; Yeo, B. C.; Cho, S. H.; Ahn, J. P.; Lee, K. Y.; Lee, S. Y.; Han, S. S. Unlocking the potential of nanoparticles composed of immiscible elements for direct H2O2 synthesis. ACS Catal. 2019, 9, 8702–8711.
DOI Google Scholar
[28]

Yang, X. C.; Li, Z. P.; Kitta, M.; Tsumori, N.; Guo, W. H.; Zhang, Z. T.; Zhang, J. B.; Zou, R. Q.; Xu, Q. Solid-solution alloy nanoclusters of the immiscible gold-rhodium system achieved by a solid ligand-assisted approach for highly efficient catalysis. Nano Res. 2020, 13, 105–111.
DOI Google Scholar
[29]

Fan, J. C.; Wu, J. D.; Cui, X. Q.; Gu, L.; Zhang, Q. H.; Meng, F. Q.; Lei, B. H.; Singh, D. J.; Zheng, W. T. Hydrogen stabilized RhPdH 2D bimetallene nanosheets for efficient alkaline hydrogen evolution. J. Am. Chem. Soc. 2020, 142, 3645–3651.
DOI Google Scholar
[30]

Wu, D. S.; Zheng, Z. L.; Gao, S. Y.; Cao, M. N.; Cao, R. Mixed-phase PdRu bimetallic structures with high activity and stability for formic acid electrooxidation. Phys. Chem. Chem. Phys. 2012, 14, 8051–8057.
DOI Google Scholar
[31]

Wang, F. L.; Kusada, K.; Wu, D. S.; Yamamoto, T.; Toriyama, T.; Matsumura, S.; Nanba, Y.; Koyama, M.; Kitagawa, H. Solid-solution alloy nanoparticles of the immiscible iridium-copper system with a wide composition range for enhanced electrocatalytic applications. Angew. Chem., Int. Ed. 2018, 57, 4505–4509.
DOI Google Scholar
[32]

Zhang, Q.; Kusada, K.; Wu, D. S.; Yamamoto, T.; Toriyama, T.; Matsumura, S.; Kawaguchi, S.; Kubota, Y.; Kitagawa, H. Selective control of fcc and hcp crystal structures in Au-Ru solid-solution alloy nanoparticles. Nat. Commun. 2018, 9, 510.
DOI Google Scholar
[33]

Kusada, K.; Wu, D. S.; Yamamoto, T.; Toriyama, T.; Matsumura, S.; Xie, W.; Koyama, M.; Kawaguchi, S.; Kubota, Y.; Kitagawa, H. Emergence of high ORR activity through controlling local density-of-states by alloying immiscible Au and Ir. Chem. Sci. 2019, 10, 652–656.
DOI Google Scholar
[34]

Qin, X. P.; Zhang, L. L.; Xu, G. L.; Zhu, S. Q.; Wang, Q.; Gu, M.; Zhang, X. Y.; Sun, C. J.; Balbuena, P. B.; Amine, K. et al. The role of Ru in improving the activity of Pd toward hydrogen evolution and oxidation reactions in alkaline solutions. ACS Catal. 2019, 9, 9614–9621.
DOI Google Scholar
[35]

Huang, B.; Kobayashi, H.; Yamamoto, T.; Matsumura, S.; Nishida, Y.; Sato, K.; Nagaoka, K.; Haneda, M.; Kawaguchi, S.; Kubota, Y. et al. Coreduction methodology for immiscible alloys of CuRu solid-solution nanoparticles with high thermal stability and versatile exhaust purification ability. Chem. Sci. 2020, 11, 11413–11418.
DOI Google Scholar
[36]

Huang, B.; Kobayashi, H.; Yamamoto, T.; Toriyama, T.; Matsumura, S.; Nishida, Y.; Sato, K.; Nagaoka, K.; Haneda, M.; Xie, W. et al. A CO adsorption site change induced by copper substitution in a ruthenium catalyst for enhanced CO oxidation activity. Angew. Chem., Int. Ed. 2019, 58, 2230–2235.
DOI Google Scholar
[37]

Huang, B.; Kobayashi, H.; Yamamoto, T.; Matsumura, S.; Nishida, Y.; Sato, K.; Nagaoka, K.; Kawaguchi, S.; Kubota, Y.; Kitagawa, H. Solid-solution alloying of immiscible Ru and Cu with enhanced CO oxidation activity. J. Am. Chem. Soc. 2017, 139, 4643–4646.
DOI Google Scholar
[38]

Komatsu, T.; Kobayashi, H.; Kusada, K.; Kubota, Y.; Takata, M.; Yamamoto, T.; Matsumura, S.; Sato, K.; Nagaoka, K.; Kitagawa, H. First-principles calculation, synthesis, and catalytic properties of Rh-Cu alloy nanoparticles. Chem.—Eur. J. 2017, 23, 57–60.
DOI Google Scholar
[39]

Wu, D. S.; Kusada, K.; Kitagawa, H. Recent progress in the structure control of Pd-Ru bimetallic nanomaterials. Sci. Technol. Adv. Mater. 2016, 17, 583–596.
DOI Google Scholar
[40]

Kusada, K.; Kobayashi, H.; Ikeda, R.; Kubota, Y.; Takata, M.; Toh, S.; Yamamoto, T.; Matsumura, S.; Sumi, N.; Sato, K. et al. Solid solution alloy nanoparticles of immiscible Pd and Ru elements neighboring on Rh: Changeover of the thermodynamic behavior for hydrogen storage and enhanced CO-oxidizing ability. J. Am. Chem. Soc. 2014, 136, 1864–1871.
DOI Google Scholar
[41]

Antillon, E.; Woodward, C.; Rao, S. I.; Akdim, B.; Parthasarathy, T. A. Chemical short range order strengthening in a model fcc high entropy alloy. Acta Mater. 2020, 190, 29–42.
DOI Google Scholar
[42]

Antillon, E.; Woodward, C.; Rao, S. I.; Akdim, B. Chemical short range order strengthening in bcc complex concentrated alloys. Acta Mater. 2021, 215, 117012.
DOI Google Scholar
[43]

Zhang, R. P.; Zhao, S. T.; Ding, J.; Chong, Y.; Jia, T.; Ophus, C.; Asta, M.; Ritchie, R. O.; Minor, A. M. Short-range order and its impact on the CrCoNi medium-entropy alloy. Nature 2020, 581, 283–287.
DOI Google Scholar
[44]

Zhang, F. X.; Zhao, S. J.; Jin, K.; Xue, H.; Velisa, G.; Bei, H.; Huang, R.; Ko, J. Y. P.; Pagan, D. C.; Neuefeind, J. C. et al. Local structure and short-range order in a NiCoCr solid solution alloy. Phys. Rev. Lett. 2017, 118, 205501.
DOI Google Scholar
[45]

Yuan, Y. K.; Kim, D. S.; Zhou, J. H.; Chang, D. J.; Zhu, F.; Nagaoka, Y.; Yang, Y.; Pham, M.; Osher, S. J.; Chen, O. et al. Three-dimensional atomic packing in amorphous solids with liquid-like structure. Nat. Mater. 2022, 21, 95–102.
DOI Google Scholar
[46]

Chen, P. C.; Gao, M. Y.; Yu, S.; Jin, J. B.; Song, C. Y.; Salmeron, M.; Scott, M. C.; Yang, P. D. Revealing the phase separation behavior of thermodynamically immiscible elements in a nanoparticle. Nano Lett. 2021, 21, 6684–6689.
DOI Google Scholar
[47]

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.
DOI Google Scholar
[48]

Wu, D. S.; Kusada, K.; Aspera, S. M.; Nakanishi, H.; Chen, Y. N.; Seo, O.; Song. C.; Kim, J.; Hiroi, S. et al. Phase control of solid-solution nanoparticles beyond the phase diagram for enhanced catalytic properties. ACS Mater. Au. 2022, 2, 110–116.
DOI Google Scholar
[49]

Lee, K. S.; Jeon, T. Y.; Yoo, S. J.; Park, I. S.; Cho, Y. H.; Kang, S. H.; Choi, K. H.; Sung, Y. E. Effect of PtRu alloying degree on electrocatalytic activities and stabilities. Appl. Catal. B: Environ. 2011, 102, 334–342.
DOI Google Scholar
[50]

Li, Y. T.; Zhang, L. A.; Qin, Y.; Chu, F. Q.; Kong, Y.; Tao, Y. X.; Li, Y. X.; Bu, Y. F.; Ding, D.; Liu, M. L. Crystallinity dependence of ruthenium nanocatalyst toward hydrogen evolution reaction. ACS Catal. 2018, 8, 5714–5720.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 05 September 2022
Revised: 07 January 2023
Accepted: 10 January 2023
Published: 02 March 2023
Issue date: July 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of Tianjin, China (No. 22175127) and Institute of Energy, Hefei Comprehensive National Science Center (No. 19KZS207).

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