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Communication

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

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.

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Graphical Abstract

Local element segregation (LES) analysis was developed to differentiate microstructures between annealed samples based on the outlier analysis of two elemental distribution figures. Through the density functional theory (DFT) computation and electrochemical evaluation, mixing index obtained from LES analysis was proved to be an essential descriptor to rationally design alloy materials for energy catalysis.

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

Pd-Ru alloyshort-range orderlocal element segregationhydrogen evolution reaction

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Nano Research
Volume 16 Issue 7,
July 2023
Pages 9968-9976
DOI: 10.1007/s12274-023-5484-6
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
Topics:
Binary alloysElectrocatalysis Electron microscopy

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Received: 05 September 2022
Revised: 07 January 2023
Accepted: 10 January 2023
Published: 02 March 2023
© Tsinghua University Press 2023
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