Abstract
Lithium borohydride (LiBH4) is a promising hydrogen carrier owing to its high hydrogen storage capacity. However, the low reactivity of its dehydrogenation products, boron and LiH, towards dihydrogen molecules makes the re-generation of borohydrides extremely challenging. Here we theoretically unravel that the dissociation of H2 into H atoms and its adsorption by the active Bspike atoms (surface-protruding boron atoms with low coordination and high reactivity) is a prerequisite for the formation of B–H bond, rather than the direct reaction between H2 and B. Moreover, the proportion of Bspike atoms increases exponentially as the size of B clusters decreases, indicating that reducing B particle size to the ultrasmall scale is critical for enhancing hydrogenation reactivity. Thereby, we experimentally synthesize nanocomposites consisting of ultrafine LiBH4 nanoparticles decorated with 3 nm Ni catalytic clusters for hydrogen storage. Upon dehydrogenation, these nanocomposites form B and LiH clusters in close proximity at 5–10 nm scale, while the Ni clusters remain intact. The Ni clusters not only facilitate the dissociation of H2 into H atoms but also strongly interact with the B clusters, weakening B–B bond, which enables the hydrogenation of B/LiH back to LiBH4 at temperatures as low as 30 °C under 100 bar H2.
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Data availability
All numerical data of this study are available within the paper and its Supplementary Information files. Additional raw data are available from the corresponding authors upon request. Source data are provided with this paper.
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Acknowledgements
In memory of Yongfeng Liu, whose passion for science and invaluable contributions continue to inspire us. This work was supported by the National Key R&D Program of China (2021YFB3802400 (G.X.)), the National Outstanding Youth Foundation of People’s Republic of China (52125104 (Y. Liu)), the National Natural Science Foundation of People’s Republic of China (52531007 (X.Z.), 52471238 (X.Z.) and 52471241 (M.G.)), the Natural Science Foundation of Zhejiang Province, People’s Republic of China (LZ23E010002 (M.G.)), the Fundamental Research Funds for the Central Universities (226-2024-00075 (Y. Liu)), the National Youth Top-Notch Talent Support Program (Y. Liu), Two-Chain Integration Key Project of Shaanxi Province (2021LLRH-09 (H.P.)) and the Australian Research Council’s Discovery Projects funding scheme (DP250103803 and DP250102613 (Z.H.)).
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X.Z., Y. Liu, G.X., W. Sun and H.P. proposed the concept and designed the research. X.Z. and Y. Liu performed the experiments. G.X., C.L., W. Shen and Y. Lu conducted the theoretical calculations. W.Z. and H.L. provided support on material characterizations. All authors contributed to the analyses and discussion of the results. X.Z., C.L., Y. Liu and Z.H. wrote the original paper. X.Z., Y. Liu, G.X. and M.G. revised the final paper. M.G. and H.P. supervised the project.
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Extended data
Extended Data Fig. 1 MD simulation results.
Changes in the structure during an MD simulation of large boron cluster (slab) and small boron cluster (B72) under hydrogen environment at T = 300 and 1000 K (B and H are represented by pink and white spheres, respectively).
Extended Data Fig. 2 The effect of hydrogen absorption on B-B bonds with different cluster sizes (\(\overline{CN}\) = 4.83).
a,b, The crystal orbital Hamiltonian population (COHP) analysis of Bslab (a) and B228 (b). c, Comparison of the integral value of crystal orbital Hamiltonian population (ICOHP) between B-B Bonds in Bslab and B228.
Extended Data Fig. 3 The effect of surface hydrogenation on B-B bonds with different cluster sizes.
a, Structures of B slab, B528, B228 and B72 after hydrogenation of Bspike atoms. b, Comparison of the integral value of crystal orbital Hamiltonian population (ICOHP) between B-B Bonds in surface hydrogenated Bslab, B528, B228 and B72.
Extended Data Fig. 4 FTIR spectrum of LiBH4@30Ni sample with different solvothermal time.
To investigate the solvothermal synthesis process, the products after heating 1, 2, 4, 6 and 12 h were collected and characterized. The B-H vibrations in FTIR spectrum appeared after 4 h indicating the appearance of LiBH4.
Extended Data Fig. 5 TEM images of nano-LiBH4@Ni samples.
5 wt% Ni (a), 10 wt% Ni (b), 20 wt% Ni (c) and 40 wt% Ni (d). TEM images reveals that the particle size of LiBH4 decreased from 30 nm (nano-LiBH4@5Ni) to 10 nm (nano-LiBH4@40Ni) with the increasing content of nano-Ni.
Extended Data Fig. 6 Non-isothermal hydrogenation curves.
a, Non-isothermal hydrogenation curves of the dehydrogenated LiBH4 nanocomposite with different content of Ni and graphene at 25-185 °C. b, Non-isothermal hydrogenation curves of the dehydrogenated LiBH4@30Ni and LiBH4/30Ni@10 G at 25-300 °C.
Extended Data Fig. 7 Adsorption of B clusters on graphene.
a, Structure and energy changes of B72 before and after adsorption on graphene. b, Changes in hydrogen adsorption energy of B sites after adsorption of B72 on graphene. c, Charge density difference of B72 adsorbed on graphene. The yellow and blue isosurfaces indicate electron accumulation and loss, respectively. All the results are plotted with an isovalue of 0.005 e/Bohr3. d,e, The partial density of state (PDOS) of B228@Graphene (d) and B72 (e).
Extended Data Fig. 8 Molecular dynamics simulation of the hydrogen absorption process on Ni-decorated boron clusters.
Ni cluster exhibits a strong affinity for B cluster, leading to a marked structural distortion of the B framework. MD simulation conducted at 500 K reveals that a substantial amount of H2 underwent adsorption and dissociation on the Ni cluster. The resultant H atoms subsequently migrated across the Ni surface, with a probability of transferring to boron atoms to form B-H bonds. This process gives rise to a pronounced hydrogen spillover effect. (H atoms are light yellow and white spheres, Ni atoms are blue spheres, B atoms are light red spheres, respectively).
Extended Data Fig. 9 Enthalpy change calculation for the dehydrogenation reaction of nano-LiBH4@30Ni.
Pressure-composition-isotherm (PCI) curves measured at 270-300 °C (a) and van’t Hoff plot (b) of nano-LiBH4@30Ni. The dehydrogenation equilibrium pressure values of nano-LiBH4@30Ni obtained by PCI were 0.69, 0.85, 1.13 and 1.36 bar at 270, 280, 290 and 300 °C, respectively. Fitting the van’t Hoff plot gives a dehydrogenation reaction enthalpy of 60 kJ mol−1 H2 for nano-LiBH4@30Ni.
Extended Data Fig. 10 Structural stability of nano-LiBH4@30Ni upon cycling.
a, TEM image and corresponding EDS mapping; and b, HRTEM image of nano-LiBH4@30Ni after 20 cycles.
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Zhang, X., Xia, G., Li, C. et al. Room-temperature hydrogen storage of boron nanoclusters. Nat. Nanotechnol. 21, 689–698 (2026). https://doi.org/10.1038/s41565-026-02150-z
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DOI: https://doi.org/10.1038/s41565-026-02150-z
