FeCoNiCrMo high entropy alloy nanosheets catalyzed magnesium hydride for solid-state hydrogen storage

Abstract

The catalytic effect of FeCoNiCrMo high entropy alloy nanosheets on the hydrogen storage performance of magnesium hydride (MgH₂) was investigated for the first time in this paper. Experimental results demonstrated that 9wt% FeCoNiCrMo doped MgH₂ started to de-hydrogenate at 200°C and discharged up to 5.89wt% hydrogen within 60 min at 325°C. The fully dehydrogenated composite could absorb 3.23wt% hydrogen in 50 min at a temperature as low as 100°C. The calculated de/hydrogenation activation energy values decreased by 44.21%/55.22% compared with MgH₂, respectively. Moreover, the composite’s hydrogen capacity dropped only 0.28wt% after 20 cycles, demonstrating remarkable cycling stability. The microstructure analysis verified that the five elements, Fe, Co, Ni, Cr, and Mo, remained stable in the form of high entropy alloy during the cycling process, and synergistically serving as a catalytic union to boost the de/hydrogenation reactions of MgH₂. Besides, the FeCoNiCrMo nanosheets had close contact with MgH₂, providing numerous non-homogeneous activation sites and diffusion channels for the rapid transfer of hydrogen, thus obtaining a superior catalytic effect.

Keywords

hydrogen storage / magnesium hydride / high entropy alloy / nano-sheets / catalysis

References

[1] Wang TZ, Cao XJ, Jiao LF. Ni₂P/NiMoP heterostructure as a bifunctional electrocatalyst for energy-saving hydrogen production. eScience, 2021, 1(1): 69.

[2] Song MC, Zhang LT, Wu FY, et al. Recent advances of magnesium hydride as an energy storage material. J. Mater. Sci. Technol., 2023, 149, 99.

[3] Z.Q. Lan, H.R. Liang, X.B. Wen, et al., Experimental and theoretical studies on two-dimensional vanadium carbide hybrid nanomaterials derived from V₄AlC₃ as excellent catalyst for MgH₂, J. Magnes. Alloys, (2022). https://doi.org/10.1016/j.jma.2022.09.019

[4] Jia YX, Wang XC, Hu LJ, et al. Carbon composite support improving catalytic effect of NbC nanoparticles on the low-temperature hydrogen storage performance of MgH₂. J. Mater. Sci. Technol., 2023, 150, 65.

[5] Zang L, Sun WY, Liu S, et al. Enhanced hydrogen storage properties and reversibility of LiBH₄ confined in two-dimensional Ti₃C₂. ACS Appl. Mater. Interfaces, 2018, 10(23): 19598.

[6] Sazelee NA, Ismail M. Recent advances in catalyst-enhanced LiAlH₄ for solid-state hydrogen storage: A review. Int. J. Hydrogen Energy, 2021, 46(13): 9123.

[7] Wang T, Aguey-Zinsou KF. Controlling the growth of NaBH₄ nanoparticles for hydrogen storage. Int. J. Hydrogen Energy, 2020, 45(3): 2054.

[8] Luo Q, Li JD, Li B, Liu B, Shao HY, Li Q. Kinetics in Mg-based hydrogen storage materials: Enhancement and mechanism. J. Magnes. Alloys, 2019, 7(1): 58.

[9] Luo Q, Guo YL, Liu B, et al. Thermodynamics and kinetics of phase transformation in rare earth-magnesium alloys: A critical review. J. Mater. Sci. Technol., 2020, 44, 171.

[10] Guemou S, Gao DQ, Wu FY, et al. Enhanced hydrogen storage kinetics of MgH₂ by the synergistic effect of Mn₃O₄/ZrO₂ nanoparticles. Dalton Trans., 2023, 52(3): 609.

[11] Zhou SM, Wei D, Wan HY, et al. Efficient catalytic effect of the page-like MnCo₂O_4.5 catalyst on the hydrogen storage performance of MgH₂. Inorg. Chem. Front., 2022, 9(21): 5495.

[12] X.L. Zhang, Y.F. Liu, X. Zhang, J.J. Hu, M.X. Gao, and H.G. Pan, Empowering hydrogen storage performance of MgH₂ by nanoengineering and nanocatalysis, Mater. Today Nano, 9(2020), art. No. 100064.

[13] Ding Z, Li YT, Yang H, et al. Tailoring MgH₂ for hydrogen storage through nanoengineering and catalysis. J. Magnes. Alloys, 2022, 10(11): 2946.

[14] Strozi RB, Leiva DR, Huot J, Botta WJ, Zepon G. Synthesis and hydrogen storage behavior of Mg-V-Al-Cr-Ni high entropy alloys. Int. J. Hydrogen Energy, 2021, 46(2): 2351.

[15] Cermak J, Kral L, Roupcova P. Hydrogen storage in TiVCrMo and TiZrNbHf multiprinciple-element alloys and their catalytic effect upon hydrogen storage in Mg. Renew. Energy, 2022, 188, 411.

[16] Grill A, Horky J, Panigrahi A, Krexner G, Zehetbauer M. Long-term hydrogen storage in Mg and ZK60 after Severe Plastic Deformation. Int. J. Hydrogen Energy, 2015, 40(47): 17144.

[17] Marquez JJ, Soyama J, Silva RDA, et al. Processing of MgH₂ by extensive cold rolling under protective atmosphere. Int. J. Hydrogen Energy, 2017, 42(4): 2201.

[18] Zhong Y, Wan XF, Ding Z, Shaw LL. New dehydrogenation pathway of LiBH₄ + MgH₂ mixtures enabled by nanoscale LiBH4. Int. J. Hydrogen Energy, 2016, 41(47): 22104.

[19] Mulas G, Campesi R, Garroni S, et al. Hydrogen storage in 2NaBH₄ + MgH₂ mixtures: Destabilization by additives and nanoconfinement. J. Alloys Compd., 2012, 536(Suppl. 1): S236.

[20] Lu ZY, He JH, Song MC, et al. Bullet-like vanadium-based MOFs as a highly active catalyst for promoting the hydrogen storage property in MgH₂. Int. J. Miner. Metall. Mater., 2023, 30(1): 44.

[21] Lu ZY, Yu HJ, Lu X, et al. Two-dimensional vanadium nanosheets as a remarkably effective catalyst for hydrogen storage in MgH₂. Rare Met., 2021, 40(11): 3195.

[22] N. Sazelee, M.F.M. Din, and M. Ismail, Ni_0.6Zn_0.4O synthes-ised via a solid-state method for promoting hydrogen sorption from MgH₂, Materials, 16(2023), No. 6, art. No. 2176.

[23] Duan XQ, Li GX, Zhang WH, et al. Ti₃AlCN MAX for tailoring MgH₂ hydrogen storage material: From performance to mechanism. Rare Met., 2023, 42(6): 1923.

[24] G.B. Tian, F.Y. Wu, H.Y. Zhang, J. Wei, H. Zhao, and L.T. Zhang, Boosting the hydrogen storage performance of MgH₂ by Vanadium based complex oxides, J. Phys. Chem. Solids, 174(2023), art. No. 111187.

[25] M.M. Jiang, J. Xu, P. Munroe, and Z.H. Xie, First-principles study on the hydrogen storage properties of MgH₂(101) surface by CuNi co-doping, Chem. Phys., 565(2023), art. No. 111760.

[26] Pighin SA, Capurso G, Russo SL, Peretti HA. Hydrogen sorption kinetics of magnesium hydride enhanced by the addition of Zr₈Ni₂₁ alloy. J. Alloys Compd., 2012, 530, 111.

[27] X. Lu, L.T. Zhang, H.J. Yu, et al., Achieving superior hydrogen storage properties of MgH₂ by the effect of TiFe and carbon nanotubes, Chem. Eng. J., 422(2021), art. No. 130101.

[28] Y.Y. Zhao, Y.F. Zhu, J.C. Liu, et al., Enhancing hydrogen storage properties of MgH₂ by core-shell CoNi@C, J. Alloys Compd., 862(2021), art. No. 158004.

[29] Singh S, Bhatnagar A, Shukla V, et al. Ternary transition metal alloy FeCoNi nanoparticles on graphene as new catalyst for hydrogen sorption in MgH₂. Int. J. Hydrogen Energy, 2020, 45(1): 774.

[30] Manjón AG, Lö;ffler T, Meischein M, et al. Sputter deposition of highly active complex solid solution electrocatalysts into an ionic liquid library: Effect of structure and composition on oxygen reduction activity. Nanoscale, 2020, 12(46): 23570.

[31] Wu DS, Kusada K, Yamamoto T, et al. On the electronic structure and hydrogen evolution reaction activity of platinum group metal-based high-entropy-alloy nanoparticles. Chem. Sci., 2020, 11(47): 12731.

[32] Qiu HJ, Fang G, Gao JJ, et al. Noble metal-free nanoporous high-entropy alloys as high efficient electrocatalysts for oxygen evolution reaction. ACS Materials Lett., 2019, 1(5): 526.

[33] Y.G. Yao, Z.Y. Liu, P.F. Xie, et al., Computationally aided, entropy-driven synthesis of highly efficient and durable multi-elemental alloy catalysts, Sci. Adv., 6(2020), No. 11, art. No. eaaz0510.

[34] Meena P, Singh R, Sharma VK, Jain IP. Role of NiMn_9.3Al_4.0Co_14.1Fe_3.6 alloy on dehydrogenation kinetics of MgH₂. J. Magnes. Alloys, 2018, 6(3): 318.

[35] El-Eskandarany MS, Ahmed SA, Shaban E. Metallic glassy V₄₅Zr₂₀Ni₂₀Cu₁₀Al₃Pd₂ alloy powders for superior hydrogenation/dehydrogenation kinetics of MgH₂. Mater. Today, 2018, 5(5): 13718.

[36] Edalati P, Floriano R, Mohammadi A, et al. Reversible room temperature hydrogen storage in high-entropy alloy TiZrCrMn-FeNi. Scripta Mater., 2020, 178, 387.

[37] Floriano R, Zepon G, Edalati K, et al. Hydrogen storage in TiZrNbFeNi high entropy alloys, designed by thermodynamic calculations. Int. J. Hydrogen Energy, 2020, 45(58): 33759.

[38] Floriano R, Zepon G, Edalati K, et al. Hydrogen storage properties of new A₃B₂-type TiZrNbCrFe high-entropy alloy. Int. J. Hydrogen Energy, 2021, 46(46): 23757.

[39] A. Mohammadi, Y. Ikeda, P. Edalati, et al., High-entropy hydrides for fast and reversible hydrogen storage at room temperature: Binding-energy engineering via first-principles calculations and experiments, Acta Mater., 236(2022), art. No. 118117.

[40] Muraleedharan RV. On Johnson-Mehl-Avrami equation. J. Therm. Anal., 1991, 37(11): 2729.

[41] Xu E, Li H, You XM, et al. Influence of micro-amount O₂ or N₂ on the hydrogenation/dehydrogenation kinetics of hydrogen-storage material MgH₂. Int. J. Hydrogen Energy, 2017, 42(12): 8057.

[42] Ismail M, Yahya MS, Sazelee NA, Ali NA, Yap FAH, Mustafa NS. The effect of K₂SiF₆ on the MgH₂ hydrogen storage properties. J. Magnes. Alloys, 2020, 8(3): 832.

[43] El-Eskandarany MS, Shaban E, Al-Matrouk H, et al. Structure, morphology and hydrogen storage kinetics of nanocomposite MgH₂/10wt% ZrNi₅ powdess. Mater. Today Energy, 2017, 3, 60.

[44] Yahya MS, Ismail M. Catalytic effect of SrTiO₃ on the hydrogen storage behaviour of MgH₂. J. Energy Chem., 2019, 28, 46.

[45] J.Q. Zhang, Q.H. Hou, X.T. Guo, and X.L. Yang, Achieve high-efficiency hydrogen storage of MgH₂ catalyzed by nanosheets CoMoO₄ and rGO, J. Alloys Compd., 911(2022), art. No. 165153.

[46] Zhou CS, Bowman RC Jr., Fang ZZ, et al. Amorphous TiCu-based additives for improving hydrogen storage properties of magnesium hydride. ACS Appl. Mater. Interfaces, 2019, 11(42): 38868.

[47] Yahya MS, Sulaiman NN, Mustafa NS, Yap FAH, Ismail M. Improvement of hydrogen storage properties in MgH₂ catalysed by K₂NbF₇. Int. J. Hydrogen Energy, 2018, 43(31): 14532.

[48] M.S. El-Eskandarany, F. Al-Ajmi, and M. Banyan, Mechanically-induced catalyzation of MgH₂ powders with Zr₂Ni-ball milling media, Catalysts, 9(2019), No. 4, art. No. 382.

[49] Zhang LT, Cai ZL, Zhu XQ, et al. Two-dimensional ZrCo nanosheets as highly effective catalyst for hydrogen storage in MgH₂. J. Alloys Compd., 2019, 805, 295.

[50] Song MC, Zhang LT, Yao ZD, et al. Unraveling the degradation mechanism for the hydrogen storage property of Fe nanocatalyst-modified MgH₂. Inorg. Chem. Front., 2022, 9(15): 3874.

[51] Zhang LT, Yu HJ, Lu ZY, et al. The effect of different Co phase structure (FCC/HCP) on the catalytic action towards the hydrogen storage performance of MgH₂. Chin. J. Chem. Eng., 2022, 43, 343.

[52] Xu N, Yuan ZR, Ma ZH, et al. Effects of highly dispersed Ni nanoparticles on the hydrogen storage performance of MgH₂. Int. J. Miner. Metall. Mater., 2023, 30(1): 54.

[53] Bystrzycki J, Czujko T, Varin RA. Processing by controlled mechanical milling of nanocomposite powders Mg + X (X = Co, Cr, Mo, V, Y, Zr) and their hydrogenation properties. J. Alloys Compd., 2005, 404–406, 507.

[54] Han ZY, Zhou SX, Chen HP, Niu HL, Wang NF. Enhancement of the hydrogen storage properties of Mg/C nanocomposites prepared by reactive milling with molybdenum. J. Wuhan Univ. Technol. Mater. Sci. Ed., 2017, 32(2): 299.

[55] N.K. Katiyar, K. Biswas, J.W. Yeh, S. Sharma, and C.S. Tiwary, A perspective on the catalysis using the high entropy alloys, Nano Energy, 88(2021), art. No. 106261.