Bilayer borophene: an efficient catalyst for hydrogen evolution reaction

doi:10.1007/s11705-024-2389-1

Front. Chem. Sci. Eng.

2024, Vol. 18

Issue (3) : 26 https://doi.org/10.1007/s11705-024-2389-1

Bilayer borophene: an efficient catalyst for hydrogen evolution reaction

Na Xing¹, Nan Gao³, Panbin Ye³, Xiaowei Yang²(

), Haifeng Wang¹(

), Jijun Zhao²

¹. College of Sciences/Xinjiang Production & Construction Corps Key Laboratory of Advanced Energy Storage Materials and Technologies, Shihezi University, Shihezi 832000, China
². Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Ministry of Education), Dalian University of Technology, Dalian 116024, China
³. School of Materials Science and Engineering, Taizhou University, Taizhou 318000, China

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Abstract

The electrocatalytic hydrogen evolution reaction is a crucial technique for green hydrogen production. However, finding affordable, stable, and efficient catalyst materials to replace noble metal catalysts remains a significant challenge. Recent experimental breakthroughs in the synthesis of two-dimensional bilayer borophene provide a theoretical framework for exploring their physical and chemical properties. In this study, we systematically considered nine types of bilayer borophenes as potential electrocatalysts for the hydrogen evolution reaction. Our first-principles calculations revealed that bilayer borophenes exhibit high stability and excellent conductivity, possessing a relatively large specific surface area with abundant active sites. Both surface boron atoms and the bridge sites between two boron atoms can serve as active sites, displaying high activity for the hydrogen evolution reaction. Notably, the Gibbs free energy change associated with adsorption for these bilayer borophenes can reach as low as ‒0.002 eV, and the Tafel reaction energy barriers are lower (0.70 eV) than those on Pt. Moreover, the hydrogen evolution reaction activity of these two-dimensional bilayer borophenes can be described by engineering their work function. Additionally, we considered the effect of pH on hydrogen evolution reaction activity, with significant activity observed in an acidic environment. These theoretical results reveal the excellent catalytic performance of two-dimensional bilayer borophenes and provide crucial guidance for the experimental exploration of multilayer boron for various energy applications.

Keywords bilayer borophene hydrogen evolution reaction work function pH effect

Corresponding Author(s): Xiaowei Yang,Haifeng Wang

Just Accepted Date: 12 December 2023 Issue Date: 05 February 2024

Cite this article:

Na Xing,Nan Gao,Panbin Ye, et al. Bilayer borophene: an efficient catalyst for hydrogen evolution reaction[J]. Front. Chem. Sci. Eng., 2024, 18(3): 26.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2389-1
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I3/26

Fig.1 (a?i) Top and side views of bilayer borophenes (the boron atoms on the top and bottom layers are labeled in pink and light purple, respectively).

Tab.1 Structural and electronic parameters of BL-x borophene (x = α, β, i, l, m, n, o, s, t) substrates, including optimized lattice parameters, system symmetry, interlayer distance (d), p-band center (ε_p) and work function of the structures (Φ)

Fig.2 AIMD simulation results indicating the time evolution of the energy and temperature of (a) BL-β borophene, (b) BL-i borophene, and (c) BL-s borophene at 300 K after 10 ps (The insets show snapshot structures of BL-β borophene, BL-i borophene, and BL-s borophene catalysts).

Fig.3 Heat map of ?G_H* of BL-x borophene (x = β, i, s, t, m, n, α) catalysts (Bluer regions indicate better catalytic activity for HER).

Fig.4 Free energy diagram of the hydrogen evolution process of BL-x borophene (x = β, i, s) catalysts at zero potential and pH = 0: (a) top site of BL-β borophene; (b) bridge site of BL-β borophene; (c) top site of BL-i borophene; (d) bridge site of BL-i borophene; (e) top site of BL-s borophene and (f) bridge site of BL-s borophene, respectively.

Fig.5 Observations and analyses of BL-x borophene (x = β, i, s) catalysts: (a?c) distribution of Bader charge transfer and coordination numbers relative to ?G_H* on the BL-β borophene, BL-i borophene and BL-s borophene; (d?f) the adsorption energies of reaction molecules by considering an implicit solvent model on BL-β borophene, BL-i borophene and BL-s borophene catalysts.

Tab.2 Calculation of the better ?G_H* ranging from ?0.10 to 0.10 eV at pH = 0?7 for H adsorption in acidic media

Fig.6 Free energy profiles of the Tafel reaction for H₂ formation on the (a) BL-β borophene, (b) BL-i borophene, and (c) BL-s borophene (The side views of the BL-β borophene BL-i borophene and BL-s borophene are shown (from left to right) for the initial, transition, and final states, respectively. The H and B atoms are shown in white and pink colors, respectively. The blue numbers indicate the energy barrier).

Fig.7 Electronic structure and relationship between work function and HER activity: (a?c) band structure and PDOS of BL-β borophene, BL-i borophene and BL-s borophene; (d) ?G_H* of BL-x borophene (x = α, β, i, m, n, s, t) as a function of work function (Φ).

Fig.8 Electrocatalytic mechanism of the BL borophenes: (a) values of the E_f and E_vac of BL-x borophene (x = α, β, i, m, n, s, t), respectively; (b) E_f of BL-x borophene (x = α, β, i, m, n, s, t) as a function of the total charge transfer number (Q).

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