Hydrogen storage properties of Na-decorated Bn(n = 3–10) clusters

LI Hailing; ZHENG Xiaoping; QI Pengtang; ZHANG Juan

doi:10.7498/aps.74.20250194

Abstract

Hydrogen is widely regarded as an ideal alternative energy source because of its high efficiency, abundance, pollution-free and renewable properties. One of the main challenges is to find efficient materials that can store hydrogen safely with fast kinetics, favorable thermodynamics, and high hydrogen density under ambient conditions. The nanomaterial is one of the most promising hydrogen storage materials because of its high surface-to-volume rate, unique electronic structure and novel chemical and physical properties. In this study, the hydrogen storage properties of Na-decorated B_n (n = 3–10) clusters are investigated using dispersion-corrected density functional theory and atomic density matrix propagation (ADMP) simulations. The results show that Na atoms can stably bind to B_n clusters, forming B_nNa₂ complexes. The average binding energies (1.876–2.967 eV) of Na atoms on the host clusters are significantly higher than the cohesive energy of bulk Na (1.113 eV), which effectively prevents Na atoms from gathering on the cluster surface. Furthermore, when Na atoms bind to B_n (n = 3–10) clusters, electrons transfer from Na to B atoms, resulting in positively charged Na atoms. Hydrogen molecules are moderately polarized under the electric field and adsorbed around Na atoms through electrostatic interactions. The H–H bonds are slightly stretched but not broken. The Na-decorated B_n clusters can adsorb up to 10 hydrogen molecules with average adsorption energies of 0.063–0.095 eV/H₂ and maximum hydrogen storage densities reaching 11.57%–20.45%. Almost no structural change is observed in the host clusters after adsorbing hydrogen. Molecular dynamics simulations reveal that the desorption rate of hydrogen molecules increases with temperature rising. At ambient temperature (300 K), B_nNa₂ (n = 3–8) clusters achieve complete dehydrogenation within 262 fs, while B₉Na₂ and B₁₀Na₂ clusters exhibit a dehydrogenation rate of 90% within 1000 fs. The Na-decorated B_n (n = 3–10) clusters not only exhibit excellent properties for hydrogen storage but also enable efficient dehydrogenation at ambient temperature. Thus, B_nNa₂ (n = 3–10) clusters can be regarded as highly promising candidates for hydrogen storage.

Keywords:

Authors and contacts

1.
State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, School of Materials Science and Engineering, Lanzhou University of Technology, Lanzhou 730050, China
2.
School of Science, Lanzhou University of Technology, Lanzhou 730050, China
3.
School of Mathematics and Physics, Lanzhou Jiaotong University, Lanzhou 730070, China

Corresponding author: ZHENG Xiaoping, zhengxp@lut.edu.cn ; QI Pengtang, qipt@lzjtu.edu.cn ;

Funds: Project supported by the Key Research and Development Programm of Science and Technology Plan of Gansu Province, China (Grant No. 24YFGA027), the Key Project of Natural Science Foundation of Gansu Province, China (Grant No. 22JR5RA313), and the Talent Innovation and Entrepreneurship Project Lanzhou University, China (Grant No. 2018-RC-114).

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References

[1]	Shindell D T, Lee Y, Faluvegi G 2016 Nat. Clim. Change 6 503 Google Scholar
[2]	Ceran B, Mielcarek A, Hassan Q, Teneta J, Jaszczur M 2021 Appl. Energy 297 117161 Google Scholar
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[16]	Satawara A M, Shaikh G A, Gupta S K, Gajjar P N 2024 Int. J. Hydrogen Energy 87 1461 Google Scholar
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[18]	Lu Q L, Huang S G, De Li Y, Wan J G, Luo Q Q 2015 Int. J. Hydrogen Energy 40 13022 Google Scholar
[19]	Tang C M, Zhang X 2016 Int. J. Hydrogen Energy 41 16992 Google Scholar
[20]	Kumar A, Ojha S K, Vyas N, Ojha A K 2022 Int. J. Hydrogen Energy 47 7861 Google Scholar
[21]	Li H R, Zhang C, Ren W B, Wang Y J, Han T 2023 Int. J. Hydrogen Energy 48 25821 Google Scholar
[22]	Olalde-López D, Rodríguez-Kessler P L, Rodríguez-Carrera S, Muñoz-Castro A 2024 Int. J. Hydrogen Energy 107 419
[23]	Si L, Tang C M 2017 Int. J. Hydrogen Energy 42 16611 Google Scholar
[24]	Ruan W, Wu D L, Xie A D, Yu X G 2011 Chin. Phys. B 20 043104 Google Scholar
[25]	Zhang Y F, Cheng X L 2019 Physica E 107 170 Google Scholar
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图 1 B_nNa₂ (n = 3—10)团簇的优化结构

Figure 1. Optimization structures of B_nNa₂ (n = 3–10) cluster.

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图 2 B₃Na₂的总态密度与分态密度, 其中垂直虚线表示HOMO能级的位置

Figure 2. TDOS and PDOS of B₃Na₂, the vertical dashed line indicates the HOMO level.

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图 3 B_nNa₂ (n = 3—10)团簇的吸氢结构

Figure 3. Adsorption configurations of hydrogen molecules on B_nNa₂ (n = 3–10) clusters.

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图 4 氢分子的平均吸附能随吸附氢分子数量的变化

Figure 4. The variation of the average adsorption energy with the number of adsorbed H₂ molecules.

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图 5 在77, 200和300 K温度下B₃Na₂(H₂)₁₀团簇的脱附状态

Figure 5. The desorption states of the B₃Na₂(H₂)₁₀ cluster at 77, 200 and 300 K.

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图 6 在300 K下, 第1个和最后1个氢分子脱离B_nNa₂(H₂)₁₀ (n = 3—10)团簇的时间

Figure 6. Desorption times of the first and last H₂ molecules from B_nNa₂(H₂)₁₀ (n = 3–10) clusters at 300 K.

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图 7 在77, 200和300 K下, B_nNa₂(H₂)₁₀体系的势能随时间的变化关系

Figure 7. The potential energy versus time for the B_nNa₂(H₂)₁₀ system at 77, 200 and 300 K.

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表 1 在B_nNa₂(n = 3—10)团簇中, Na原子的平均结合能(E_b), HOMO-LUMO能隙(E_g), Na—B平均距离(d_Na—B), Na—Na平均距离(d_Na—Na), Na原子的NBO电荷(Q_Na)

Table 1. The average binding energy (E_b) of Na atoms, HOMO-LUMO energy gap (E_g), average bond lengths of natrium-boron (d_Na—B), natrium-natrium (d_Na—Na) and NBO charge of Na atoms (Q_Na) in the B_nNa₂ (n = 3–10) clusters.

团簇	E_b/eV	E_g/eV	d_Na—B/Å	d_Na—Na/Å	Q_Na/e
B₃Na₂	1.876	2.807	2.519	4.332	0.837
B₄Na₂	1.756	1.901	2.355	4.043	0.868
B₅Na₂	1.859	1.867	2.406	4.440	0.899
B₆Na₂	2.520	2.745	2.536	5.189	0.902
B₇Na₂	2.162	2.474	2.646	5.079	0.894
B₈Na₂	2.967	3.320	2.424	4.849	0.979
B₉Na₂	2.572	3.546	2.669	4.667	0.972
B₁₀Na₂	2.120	2.348	2.359	6.574	0.979

DownLoad: CSV

表 2 在B_nNa₂(H₂)₁₀ (n = 3—10)团簇中, 氢分子的平均吸附能(E_ads), 氢分子的平均键长(d_H—H), 氢分子与Na原子之间的平均距离(d_Na—H2), Na—B平均距离(d_Na—B)以及储氢密度

Table 2. The average adsorption energy (E_ads), average bond lengths of hydrogen-hydrogen (d_H—H), natrium-hydrogen molecule (d_Na—H2), natrium-boron (d_Na—B) and gravimetric density of H₂ of B_nNa₂(H₂)₁₀ (n = 3–10) cluster.

饱和吸氢结构	E_ads/eV	d_H—H/Å	d_Na—H2/Å	d_Na—B/Å	H₂/%
B₃Na₂(H₂)₁₀	0.063	0.749	2.561	2.550	20.45
B₄Na₂(H₂)₁₀	0.066	0.749	2.578	2.379	18.43
B₅Na₂(H₂)₁₀	0.073	0.749	2.569	2.474	16.77
B₆Na₂(H₂)₁₀	0.085	0.749	2.552	2.672	15.39
B₇Na₂(H₂)₁₀	0.077	0.748	2.590	2.620	14.22
B₈Na₂(H₂)₁₀	0.088	0.748	2.553	2.477	13.21
B₉Na₂(H₂)₁₀	0.087	0.748	2.583	2.668	12.33
B₁₀Na₂(H₂)₁₀	0.095	0.749	2.535	2.433	11.57

DownLoad: CSV

表 3 B_nNa₂ (n = 3—10)团簇吸附氢分子前后每个原子上的平均NBO电荷

Table 3. Average NBO charges on each atom before and after H₂ adsorption of B_nNa₂ (n = 3–10) clusters.

团簇	吸氢前		饱和吸氢后
团簇	Q_B/e	Q_Na/e	Q_B/e	Q_Na/e	Q_H/e
B₃Na₂	–0.558	0.837	–0.565	0.848	0.001
B₄Na₂	–1.023	0.938	–0.896	0.866	0.001
B₅Na₂	–0.837	0.899	–0.685	0.878	0.001
B₆Na₂	–0.675	0.902	–0.483	0.889	0.005
B₇Na₂	–0.258	0.894	–0.381	0.891	0.006
B₈Na₂	–0.146	0.979	–0.132	0.919	0.005
B₉Na₂	–0.109	0.972	–0.087	0.912	0.007
B₁₀Na₂	–0.376	0.979	–0.317	0.912	0.005

DownLoad: CSV

[1]	Shindell D T, Lee Y, Faluvegi G 2016 Nat. Clim. Change 6 503 Google Scholar
[2]	Ceran B, Mielcarek A, Hassan Q, Teneta J, Jaszczur M 2021 Appl. Energy 297 117161 Google Scholar
[3]	Wróbel K, Wróbel J, Tokarz W, Lach J, Podsadni K, Czerwiński A 2022 Energies 15 8937 Google Scholar
[4]	Okolie J A, Patra B R, Mukherjee A, Nanda S, Dalai A K, Kozinski J A 2021 Int. J. Hydrogen Energy 46 8885 Google Scholar
[5]	Ousaleh H A, Mehmood S, Baba Y F, Bürger I, Linder M, Faik A 2024 Int. J. Hydrogen Energy 52 1182 Google Scholar
[6]	https://www.energy.gov/eere/fuelcells/hydrogen-and-fuel-cell-technologies-office [2025-2-1]
[7]	Liu X Y, He J, Yu J X, Li Z X, Fan Z Q 2014 Chin. Phys. B 23 067303 Google Scholar
[8]	Mohan M, Sharma V K, Kumar E A, Gayathri V 2019 Energy Storage 1 e35 Google Scholar
[9]	Kumar A, Vyas N, Ojha A K 2020 Int. J. Hydrogen Energy 45 12961 Google Scholar
[10]	Tang C M, Wang Z G, Zhang X, Wen N H 2016 Chem. Phys. Lett. 661 161 Google Scholar
[11]	Durgun E, Ciraci S, Zhou W, Yildirim T 2006 Phys. Rev. Lett. 97 226102 Google Scholar
[12]	Duraisamy P D, S P M P, Gopalan P, Angamuthu A 2024 Struct. Chem. 35 681 Google Scholar
[13]	Aal S A, Alfuhaidi A K 2021 Vacuum 183 109838 Google Scholar
[14]	Ma L C, Wang L C, Sun Y R, Ma L, Zhang J M 2021 Physica E 128 114588 Google Scholar
[15]	Banerjee P, Pathak B, Ahuja R, Das G P 2016 Int. J. Hydrogen Energy 41 14437 Google Scholar
[16]	Satawara A M, Shaikh G A, Gupta S K, Gajjar P N 2024 Int. J. Hydrogen Energy 87 1461 Google Scholar
[17]	Muthu R N, Rajashabala S, Kannan R 2016 Renew. Energ. 85 387 Google Scholar
[18]	Lu Q L, Huang S G, De Li Y, Wan J G, Luo Q Q 2015 Int. J. Hydrogen Energy 40 13022 Google Scholar
[19]	Tang C M, Zhang X 2016 Int. J. Hydrogen Energy 41 16992 Google Scholar
[20]	Kumar A, Ojha S K, Vyas N, Ojha A K 2022 Int. J. Hydrogen Energy 47 7861 Google Scholar
[21]	Li H R, Zhang C, Ren W B, Wang Y J, Han T 2023 Int. J. Hydrogen Energy 48 25821 Google Scholar
[22]	Olalde-López D, Rodríguez-Kessler P L, Rodríguez-Carrera S, Muñoz-Castro A 2024 Int. J. Hydrogen Energy 107 419
[23]	Si L, Tang C M 2017 Int. J. Hydrogen Energy 42 16611 Google Scholar
[24]	Ruan W, Wu D L, Xie A D, Yu X G 2011 Chin. Phys. B 20 043104 Google Scholar
[25]	Zhang Y F, Cheng X L 2019 Physica E 107 170 Google Scholar
[26]	Becke A D 1992 J. Chem. Phys. 96 2155 Google Scholar
[27]	Lee C, Yang W, Parr R G 1988 Phys. Rev. B 37 785 Google Scholar
[28]	Miehlich B, Savin A, Stoll H, Preuss H 1989 Chem. Phys. Lett. 157 200 Google Scholar
[29]	Ruan W, Wu D L, Luo W L, Yu X G, Xie A D 2014 Chin. Phys. B 23 023102 Google Scholar
[30]	Lu T, Chen F W 2012 J. Comput. Chem. 33 580 Google Scholar
[31]	Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Scalmani G, Barone V, Petersson G A, Nakatsuji H, Li X 2016 Gaussian 16 Rev. C. 01. Wallingford, CT
[32]	Atış M, Özdoğan C, Güvenç Z B 2007 Int. J. Quantum Chem. 107 729 Google Scholar
[33]	Ye X J, Teng Z W, Yang X L, Liu C S 2018 J. Saudi Chem. Soc. 22 84 Google Scholar
[34]	Li Y Y, Hu Y F, Lai Q, Yuan Y Q, Huang T X, Li Q Y, Huang H B 2023 Mol. Phys. 121 e2166881 Google Scholar
[35]	Ray S S, Sahoo S R, Sahu S 2019 Int. J. Hydrogen Energy 44 6019 Google Scholar

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