First-Principles Study of Projected Berry Phase and Hydrogen Evolution Catalysis in Pt7Sb

doi:10.11900/0412.1961.2022.00129

Acta Metall Sin

2024, Vol. 60

Issue (6): 837-847 DOI: 10.11900/0412.1961.2022.00129

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First-Principles Study of Projected Berry Phase and Hydrogen Evolution Catalysis in Pt₇Sb

ZHOU Yanyu¹^,², LI Jiangxu¹, LIU Chen¹^,², LAI Junwen¹^,², GAO Qiang¹, MA Hui¹^,², SUN Yan¹^,²(

), CHEN Xingqiu¹^,²

1 Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China

Cite this article:

ZHOU Yanyu, LI Jiangxu, LIU Chen, LAI Junwen, GAO Qiang, MA Hui, SUN Yan, CHEN Xingqiu. First-Principles Study of Projected Berry Phase and Hydrogen Evolution Catalysis in Pt₇Sb. Acta Metall Sin, 2024, 60(6): 837-847.

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Abstract

With the increase of global energy consumption and related environment pollution, new types of renewable clean energy resources and carriers are desirable. Given its high gravimetric energy density and combustion product (i.e., water), molecular hydrogen has attracted considerable attention. Obtaining molecular hydrogen from water splitting is the ideal strategy because inputs and outputs are carbon-free clean matter. In achieving this process, a suitable and highly efficient catalyst is a crucial parameter. Novel metal Pt is an excellent catalyst with high efficiency and chemical stability. However, owing to its high cost and insufficient reserves on Earth, the wide application of Pt in catalysis is strongly limited. Correspondingly, the design of a highly efficient hydrogen evolution reaction (HER) catalyst with low Pt loading is an important task for electrochemical water splitting in the field of renewable energy resources. Understanding the hidden mechanism is essential for the guiding principle of such a design. In this study, an excellent HER catalyst in cubic Pt₇Sb is proposed, in which Gibbs free energy for hydrogen adsorption ( $Δ G H *$ ) is smaller than that from Pt. Thus, together with its good chemical stability, a better HER catalytic activity with reduced Pt loading can be obtained. Based on the analysis of electronic structures, a good agreement between the two descriptors of $Δ G H *$ and the projected Berry phase (PBP) is revealed. Considering that the PBP is purely decided by the bulk state, such an agreement indicates a strong relationship between the good catalytic performance and the topological nature of the intrinsic electronic structure. This work provides an excellent HER catalytic candidate with reduced Pt loading and a good example to show the role of the intrinsic topological nature in catalysts.

Key words: hydrogen evolution reaction catalyst projected Berry phase first-principles calculation

Received: 22 March 2022

ZTFLH:

TG111.1

Fund: National Natural Science Foundation of China(51901228;52271016;52188101);Liao-ning Revitalization Talents Program(XLYC2203080)

Corresponding Authors: SUN Yan, professor, Tel: (024)23975362, E-mail: sunyan@imr.ac.cn

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	ZHOU Yanyu
	LI Jiangxu
	LIU Chen
	LAI Junwen
	GAO Qiang
	MA Hui
	SUN Yan
	CHEN Xingqiu

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https://www.ams.org.cn/EN/10.11900/0412.1961.2022.00129 OR https://www.ams.org.cn/EN/Y2024/V60/I6/837

Fig.1 Pt₇Sb slab models with the different lattice orientations and terminations (a) and the corresponding surface energy variations with relative chemical potential ( $μ S b - μ S b b u l k$ ) (b) (The surface energies of six situations with lattice orientation along with three high symmetrical directions of (100), (110), and (111), respectively; A and B indicate different types of terminations, with A representing Pt-Sb mixed termination and B representing pure Pt termination; $μ S b$ is the chemical potential of Sb in the Pt₇Sb bulk structure and $μ S b b u l k$ is the chemical potential of Sb in the monomer)

Fig.2 Crystal structure diagrams of Pt₇Sb and Pt, schematic of different adsorption sites on Pt₇Sb (111) surface, and the band structures of Pt₇Cu, Pt, and Pt₇Sb
(a, b) crystal structures of cubic Pt₇Sb (a) and Pt (b)
(c) (111) surface of Pt₇Sb with different surface adsorption sites labeled by crosses (The most stable site locates at the face-cubic center, as highlighted by the red cross)
(d-f) bulk band structures of Pt₇Cu (d), Pt (e), and Pt₇Sb (f), respectively (E is the energy, E_f is the Fermi level, and the horizontal coordinate represents the point of high symmetry in the inverse space)

Fig.3 Pt₇Cu slab models with the different lattice orientations and terminations (a) and the corresponding surface energy variations with relative chemical potential ( $μ C u - μ C u$ (bulk)) (b) (The surface energies of six situations with lattice orientations along the three high symmetrical directions of (100), (110), and (111), respectively; A and B indicate the different types of terminations, with A representing Pt-Cu mixed termination and B representing pure Pt termination; $μ C u$ is the chemical potential of Cu in the Pt₇Cu bulk structure and $μ C u b u l k$ is the chemical potential of Cu in the monomer)

Fig.4 Step diagrams of Pt₇Sb, Pt₇Cu, and Pt; and the volcano plot (exchange current density i₀vs the free energy for hydrogen adsorption ( $Δ G H *$ )) obtained by comparison with literatures
(a) calculated free energy diagram for hydrogen evolution reaction (HER) at a potential U = 0 V relative to the standard hydrogen electrode at pH = 0 (The free energy of H⁺ + e^- is defined as the same as that of 1/2H₂ at standard conditions)
(b) volcano plot for the HER of Pt₇Sb and Pt₇Cu in comparison with various pure metals (The experimental^[37] and calculated^[42] data of Pt, Pd, Co, Ag, and Cu), topological Weyl semimetals (The calculated data of NbP, NbAs, and TaAs^[20]), and other candidates (the theoretical data of TaS₂(2H) and TaS₂(1T)^[20])

Fig.5 Bulk structure electronic densities of states and charge density difference analyses of Pt, Pt₇Sb, and Pt₇Cu (PDOS—projected electronic densities of states)
(a) PDOS for bulk Pt₇Sb, fcc Pt, and Sb, respectively
(b) PDOS for bulk Pt₇Cu, fcc Pt, and Cu, respectively
(c-e) top and side views of electron charge density differences for the hydrogen adsorption on Pt (c), Pt₇Sb (d), and Pt₇Cu (e) surfaces, respectively (Color code: Pt—grey; Sb—orange; H—red. The charge accumulation and depletion are depicted by the yellow and light blue regions, respectively. The isosurface levels are set to ± 0.002)

Fig.6 PDOS for Pt₇Sb (a, b), Pt (c, d), Pt₇Cu (e, f) in the cases before (a, c, e) and after (b, d, f) hydrogen evolution

Fig.7 Projected Berry phases (γ) and Berry curvatures (F_xy ) projected of Pt₇Sb and Pt₇Cu
(a, d) the curves of the projected Berry phase (PBP) of Pt₇Sb (a) and Pt₇Cu (d) with energy
(b, c, e, f) electronic band structures (b, e) and local distributions of PBP (c, f) of Pt₇Sb (b, c) and Pt₇Cu (e, f)
(g) the theoretical results (red star) of PBP vs exchange current density of Pt₇Sb in comparison with various pure metals (the experimental data (solid blue points) of Pt^[43], Pd^[44], Rh^[45], Ir, Au, Cu^[39], and Ag) and compounds (the theoretical data^[24] of Pt₇Cu (purple hollow dots)) with space group Fm $3 ¯$ m

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