Bilayer borophene: an efficient catalyst for hydrogen evolution reaction

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.

Key words： bilayer borophene; hydrogen evolution reaction; work function; pH effect

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 12264043 and 11864033) and the Supercomputing Center of Dalian University of Technology.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at http://doi.org/10.1007/s11705-024-2389-1 and is accessible for authorized users.

References

1 Turner J A . Sustainable hydrogen production. Science, 2004, 305(5686): 972–974

2 Schlapbach L , Zuttel A . Hydrogen-storage materials for mobile applications. Nature, 2001, 414(6861): 353–358

3 Bhavsar S , Najera M , Solunke R , Veser G . Chemical looping: to combustion and beyond. Catalysis Today, 2014, 228: 96–105

4 Liu J , Yu G , Huang X , Chen W . The crucial role of strained ring in enhancing the hydrogen evolution catalytic activity for the 2D carbon allotropes: a high-throughput first-principles investigation. 2D Materials, 2020, 7(1): 15015

5 Adamska L , Sadasivam S , Foley J J IV , Darancet P , Sharifzadeh S . First-principles investigation of borophene as a monolayer transparent conductor. Journal of Physical Chemistry C, 2018, 122(7): 4037–4045

6 Huang Y , Shirodkar S N , Yakobson B I . Two-dimensional boron polymorphs for visible range plasmonics: a first-principles exploration. Journal of the American Chemical Society, 2017, 139(47): 17181–17185

7 Fan F , Wang R , Zhang H , Wu W . Emerging beyond-graphene elemental 2D materials for energy and catalysis applications. Chemical Society Reviews, 2021, 50(19): 10983–11031

8 Zhang X , Hou L , Ciesielski A , Samorì P . 2D materials beyond graphene for high-performance energy storage applications. Advanced Energy Materials, 2016, 6(23): 1600671

9 Feng B , Zhang J , Ito S , Arita M , Cheng C , Chen L , Wu K , Komori F , Sugino O , Miyamoto K . . Discovery of 2D anisotropic dirac cones. Advanced Materials, 2018, 30(2): 1704025

10 Yang X , Shang C , Zhou S , Zhao J . MBenes: emerging 2D materials as efficient electrocatalysts for the nitrogen reduction reaction. Nanoscale Horizons, 2020, 5(7): 1106–1115

11 Zhang X , Wu T , Wang H , Zhao R , Chen H , Wang T , Wei P , Luo Y , Zhang Y , Sun X . Boron nanosheet: an elemental two-dimensional (2D) material for ambient electrocatalytic N₂-to-NH₃ fixation in neutral media. ACS Catalysis, 2019, 9(5): 4609–4615

12 Tai G , Xu M , Hou C , Liu R , Liang X , Wu Z . Borophene nanosheets as high-efficiency catalysts for the hydrogen evolution reaction. ACS Applied Materials & Interfaces, 2021, 13(51): 60987–60994

13 Qun F , Choi C , Yan C , Liu Y , Qiu J , Hong S , Jung Y , Sun Z . High-yield production of few-layer boron nanosheets for efficient electrocatalytic N₂ reduction. Chemical Communications, 2019, 55(29): 4246–4249

14 De la Barrera S C , Sinko M R , Gopalan D P , Sivadas N , Seyler K L , Watanabe K , Taniguchi T , Tsen A W , Xu X , Xiao D . . Tuning lsing superconductivity with layer and spin-orbit coupling in two-dimensional transition-metal dichalcogenides. Nature Communications, 2018, 9(1): 14–27

15 Kumar P , Liu J , Motlag M , Tong L , Hu Y , Huang X , Bandopadhyay A , Pati S K , Ye L , Irudayaraj J . . Laser shock tuning dynamic interlayer coupling in graphene-boron nitride moiré superlattices. Nano Letters, 2019, 19(1): 283–291

16 Gao N , Wu X , Jiang X , Bai Y , Zhao J . Structure and stability of bilayer borophene: the roles of hexagonal holes and interlayer bonding. FlatChem, 2018, 7: 48–54

17 Li D , Tang Q , He J , Li B , Ding G , Feng C , Zhou H , Zhang G . From two- to three-dimensional van der Waals layered structures of boron crystals: an ab initio study. ACS Omega, 2019, 4(5): 8015–8021

18 Xu Y , Xuan X , Yang T , Zhang Z , Li S , Guo W . Quasi-freestanding bilayer borophene on Ag (111). Nano Letters, 2022, 22(8): 3488–3494

19 Liu X , Li Q , Ruan Q , Rahn M S , Yakobson B I , Hersam M C . Borophene synthesis beyond the single-atomic-layer limit. Nature Materials, 2022, 21(1): 35–40

20 Chen C , Lv H , Zhang P , Zhuo Z , Wang Y , Ma C , Li W , Wang X , Feng B , Cheng P . . Synthesis of bilayer borophene. Nature Chemistry, 2022, 14(1): 25–31

21 Sutter P , Sutter E . Large-scale layer-by-layer synthesis of borophene on Ru (0001). Chemistry of Materials, 2021, 33(22): 8838–8843

22 Gao N , Ye P , Chen J , Xiao J , Yang X . Density functional theory study of bilayer borophene-based anode material for rechargeable lithium ion batteries. Langmuir, 2023, 39(29): 10270–10279

23 Gao N , Li J , Chen J , Yang X . Interaction between bilayer borophene and metal or inert substrates. Applied Surface Science, 2023, 626: 157157

24 Chang Y , Liu J , Liu H , Zhang Y W , Gao J , Zhao J . Robust sandwiched B/TM/B structures by metal intercalating into bilayer borophene leading to excellent hydrogen evolution reaction. Advanced Energy Materials, 2023, 13(29): 2301331

25 Kresse G , Furthmuller J . Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B: Condensed Matter, 1996, 54(16): 11169–11186

26 Kresse G , Joubert D . From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B: Condensed Matter, 1999, 59(3): 1758–1775

27 Perdew J P , Burke K , Ernzerhof M . Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868

28 Grimme S , Antony J , Ehrlich S , Krieg H . A consistent and accurateab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. Journal of Chemical Physics, 2010, 132(15): 154104

29 Carrasco J , Hodgson A , Michaelides A . A molecular perspective of water at metal interfaces. Nature Materials, 2012, 11(8): 667–674

30 Dalsaniya M H , Gajaria T K , Som N N , Jha P K . Electron density modulation of a metallic GeSb monolayer by pnictogen doping for excellent hydrogen evolution. Physical Chemistry Chemical Physics, 2020, 22(35): 19823–19836

31 Guha A , Veettil Vineesh T , Sekar A , Narayanaru S , Sahoo M , Nayak S , Chakraborty S , Narayanan T N . Mechanistic insight into enhanced hydrogen evolution reaction activity of ultrathin hexagonal boron nitride-modified Pt electrodes. ACS Catalysis, 2018, 8(7): 6636–6644

32 Henkelman G , Uberuaga B P , Jónsson H . A climbing image nudged elastic band method for finding saddle points and minimum energy paths. Journal of Chemical Physics, 2000, 113(22): 9901–9904

33 Henkelman G , Arnaldsson A , Jónsson H . A fast and robust algorithm for Bader decomposition of charge density. Computational Materials Science, 2006, 36(3): 354–360

34 Parrinello M , Rahman A . Crystal structure and pair potentials: a molecular-dynamics. Physical Review Letters, 1980, 45(14): 1196–1199

35 Chodvadiya D , Dalsaniya M H , Som N N , Chakraborty B , Kurzydłowski D , Kurzydłowski K J , Jha P K . Defects and doping engineered two-dimensional o-B₂N₂ for hydrogen evolution reaction catalyst: insights from DFT simulation. International Journal of Hydrogen Energy, 2023, 48(13): 5138–5151

36 Hansen J N , Prats H , Toudahl K K , Mørch Secher N , Chan K , Kibsgaard J , Chorkendorff I . Is there anything better than Pt for HER?. ACS Energy Letters, 2021, 6(4): 1175–1180

37 Luo Y , Zhang Z , Yang F , Li J , Liu Z , Ren W , Zhang S , Liu B . Stabilized hydroxide-mediated nickel-based electrocatalysts for high-current-density hydrogen evolution in alkaline media. Energy & Environmental Science, 2021, 14(8): 4610–4619

38 Luo M , Yang J , Li X , Eguchi M , Yamauchi Y , Wang Z . Insights into alloy/oxide or hydroxide interfaces in Ni–Mo-based electrocatalysts for hydrogen evolution under alkaline conditions. Chemical Science, 2023, 14(13): 3400–3414

39 Fajin J L . DS Cordeiro M N, Gomes J R. Density functional theory study of the water dissociation on platinum surfaces: general trends. Journal of Physical Chemistry A, 2014, 118(31): 5832–5840

40 Nie S , Feibelman P J , Bartelt N C , Thürmer K . Pentagons and heptagons in the first water layer on Pt (111). Physical Review Letters, 2010, 105(2): 026102

41 Donadio D , Ghiringhelli L M , Delle Site L . Autocatalytic and cooperatively stabilized dissociation of water on a stepped platinum surface. Journal of the American Chemical Society, 2012, 134(46): 19217–19222

42 Zhang P , Sun L . Electrocatalytic hydrogenation and oxidation in aqueous conditions. Chinese Journal of Chemistry, 2020, 38(9): 996–1004

43 Mathew K , Sundararaman R , Letchworth-Weaver K , Arias T A , Hennig R G . Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. Journal of Chemical Physics, 2014, 140(8): 084106

44 Zhang Q , Asthagiri A . Solvation effects on DFT predictions of ORR activity on metal surfaces. Catalysis Today, 2019, 323: 35–43

45 Yang X , Gao N , Zhou S , Zhao J . MXene nanoribbons as electrocatalysts for the hydrogen evolution reaction with fast kinetics. Physical Chemistry Chemical Physics, 2018, 20(29): 19390–19397

46 Skúlason E , Tripkovic V , Björketun M E , Gudmundsdóttir S , Karlberg G , Rossmeisl J , Bligaard T , Jónsson H , Nørskov J K . Modeling the electrochemical hydrogen oxidation and evolution reactions on the basis of density functional theory calculations. Journal of Physical Chemistry C, 2010, 114(42): 18182–18197

47 Michaelson H B . The work function of the elements and its periodicity. Journal of Applied Physics, 1977, 48(11): 4729–4733

48 Qian Y , Zheng B , Xie Y , He J , Chen J , Yang L , Lu X , Yu H . Imparting α-borophene with high work function by fluorine adsorption: a first-principles investigation. Langmuir, 2021, 37(37): 11027–11040

49 Liu N , Zhao Y , Zhou S , Zhao J . CO₂ reduction on p-block metal oxide overlayers on metal substrates—2D MgO as a prototype. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2020, 8(11): 5688–5698

50 Shan B , Cho K . First principles study of work functions of single wall carbon nanotubes. Physical Review Letters, 2005, 94(23): 236602