FIRST-PRINCIPLE CALCULATIONS OF THE SYNERGISTIC CATALYTIC PERFORMANCE OF GRAPHENE AND TRANSITION METALS FOR MGH2 DEHYDROGENATION
Keywords:
hydrogen storage materials, MgH2, graphene, first-principles calculations
Abstract
To address the challenges of high dehydrogenation temperature and sluggish kinetics in magnesium hydride (MgH2), this study systematically investigates the synergistic catalytic effects of transition metals (Ni, Fe, Cu, Cr, Sc) anchored on monolayer graphene in enhancing the dehydrogenation performance of magnesium-based hydrogen storage materials. First-principles calculations were performed using density functional theory (DFT) within the generalized gradient approximation (GGA), combined with a double numerical plus polarization (DNP) basis set. The computational results demonstrate that Ni-, Cr-, and Cu-modified graphene substrates significantly reduce both the dehydrogenation enthalpy and reaction energy barrier of Mg4H8 clusters. Charge density analysis, density of states, and differential charge density calculations were employed to elucidate the electronic interactions and charge redistribution within these systems. These analyses confirm a substantial weakening of the Mg–H bonds in Mg4H8, which effectively facilitates hydrogen desorption. Comprehensive evaluation based on thermodynamic and kinetic parameters, including dehydrogenation enthalpy, activation energy, and electronic structure features, establishes that the Cu/graphene composite doping exhibits the most pronounced improvement, achieving the optimal dehydrogenation performance of MgH2. This work provides valuable theoretical insights and predictive guidance for the rational design of high-efficiency catalytic systems in magnesium-based hydrogen storage applications.
References
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28. Huan QQ, Zhu YF, Wei LJ. Hydrogen storage properties of Mg–Ni/graphene composites. Rare Metal Mater Eng. 2014;43(2):356-60.
29. Zhang J, Yu X F, Mao C, Long CG, Chen J, Zhou DW. Influences and mechanisms of graphene-dopingon dehydrogenation properties of MgHz: Experimental and first-principlesstudies. Energy. 2015;89:957-64. doi: 10.1016/j.energy.2015.06.037.
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31. Dong S, Lv E, Wang J, Li C, Ma K, Gao Z, et al. Construction of transition metal-decorated boron doped twin graphene for hydrogen storage: A theoretical prediction. Fuel. 2021;304:121351. doi: 10.1016/j.fuel.2021.121351.
32. He Y, Ding L, Wu XL, Li Q, Li Z, Zhang W, et al. Hydrogen release mechanisms of MgH2 over NiN4-embedded graphene nanosheet: first-principles calculations. Intern J Hydrogen Energy. 2022;47(93):39549-62. doi: 10.1016/j.ijhydene.2022.09.102.
33. Zhang HP, Luo XG, Lin XY, Tang P, Lu X, Fang L, et al. Modulatingthe interactions between MgH2 and grapheneusing different dopants. Chem Phys Lett. 2015;623:82-8. doi: 10.1016/j.cplett.2015.01.052.
2. Zhao JF, Jiang YQ, Zhan X. Research progress on the impact of aerosol pollution on crops in China. Adv Meteorol Sci Technol. 2018;8(05):6-10.
3. Zou JX, Ding WJ. Research hotspots of magnesium-based hydrogen storage materials in 2023: a retrospective. Sci Technol Rev. 2024;42(1):204-16.
4. Zhang JQ. Current Situation of Hydrogen Energy Industry Technology Development in China. Boiler Manufacturing. 2025;(05):56-8.
5. Qin Y, Huang XL, Lin L. Text Analysis of China's Hydrogen Energy Policies Based on the LDA Topic Model. Resources and Industries, 1-23 [2025-09-08]. Available from: https://doi.org/10.13776/j.cnki.resourcesindustries.20250901.002.
6. Ruan XL, Liao XD, Liu SY, He P, Li MK. Performance Improvement and Research Progress of Magnesium-based Hydrogen Storage Materials. Dongfang Electric Rev. 2025;39(4):5-14. doi:10.13661/j.cnki.issn1001-9006.2025.04.003.
7. Yuan Q, Wang LY, Lü YJ, Liu GQ. Research Progress of Magnesium-based Hydrogen Storage Materials. Chem Ind Eng. 2025;42(3):57-72. doi:10.13353/j.issn.1004.9533.20240525.
8. Sadhasivam T, Kim HT, Jung SH, Roh SH, Park JH, Jung HY. Dimensional effects of nanostructured Mg/MgH2 for hydrogen storage applications: a review. Renew Sustain Energy Rev. 2017;72:523-34. doi:10.1016/j.rser.2017.01.107.
9. Aguey-Zinsou KF, Ares-Fernandez J. Hydrogen in magnesium: new perspectives to ward functional stores. Energy Environ Sci. 2010;3(5):526-43. doi:10.1039/B921645F.
10. Yang MJ, Zhu XQ, Zhou LL, Deng Q, Wei C. Hydrogen Storage Performance of Graphene and Its Application in Magnesium-based Hydrogen Storage Materials. New Chem Mater. 2021;49(1):23-7. doi: 10.19817/j.cnki.issn1006-3536.2021.01.006.
11. Liu G, Wang Y, Jiao L, Yuan H. Understanding the role of few-layer graphene nanosheets in enhancing the hydrogen sorption kinetics of magnesium hydride. ACS Appl Mater Interfaces. 2014;6(14):11038-46. doi:10.1021/am502755s.
12. Liu MJ, Zhao SC, Xiao XZ, Chen M, Sun C, Yao Z, et al. Novel 1D carbon nanotubes uniformly wrapped nanoscale MgH2, for efficient hydrogen storage cycling performances with extreme high gravimetric and volumetric capacities. Nano Energy. 2019;61:540-9. doi:10.1016/j.nanoen.2019.04.094.
13. Hu MM, Xie XB, Chen M, Zhu C, Liu T. TiCX-decorated Mg nanoparticles confined in carbon shell: preparation and catalytic mechanism for hydrogen storage. J Alloys Compd. 2020;817:152813. doi: 10.1016/j.jallcom.2019.152813.
14. Zhu GS, Du XM. Effects of Sc/Cu and Sc/Zn co-doping on the hydrogenation/dehydrogenation properties of Mg-based hydrogen storage materials: A theoretical study. Int J Hydrogen Energy. 2024;60:515-23. doi:10.1016/j.ijhydene.2024.02.134.
15. Zhu GS, Du XM, Li F. Effect of Sc on the hydrogen-storage performance of Mg₂Ni: A first-principles study. Mater Tehnol. 2024;58(1):95-101. doi:10.17222/mit.2023.980.
16. Du XM, Zhu GS, Sun DD. First-principles investigation of the effects of Y/Cu and Y/Zn co-doping on the hydrogenation/dehydrogenation properties of Mg2Ni alloy. J Phys Chem Solids. 2025;202:112661. doi:10.1016/j.jpcs.2025.112661.
17. Khatabi ME, Bhihi M, Naji S, Labrim H, Benyoussef A, El Kenz A, et al. Study of doping effects with 3d and4d-transition metals on the hydrogen storage properties of MgH2. Int J Hydrogen Energy. 2016;41(8):4712-8. doi: 10.1016/j.ijhydene.2016.01.001.
18. Xia GL, Tan YB, Chen XW, Sun D, Guo Z, Liu H, et al. Monodisperse magnesium hydride nanoparticles uniformly self-assembled on graphene. Adv Mater. 2015;27(39):5981-8. doi: 10.1002/adma.201502005.
19. Cui J, Wang H, Liu J, Ouyang L, Zhang Q, Sun D, et al. Remarkable enhancement in dehydrogenation of MgH2 by a nano-coating of multi-valence Ti-based catalysts. J Mater Chem A. 2013;1(18):5603-11. doi: 10.1039/C3TA01332D.
20. Zhang J, Ou H, Wu G, Song LB, Yu XF, Zhou DW. Remarkably enhanced dehydrogen ation propertiesand mechanisms of MgH2 by sequential-doping of nickel and graphene. Int J Hydrogen Energy. 2016;41(39):17433-41. doi: 10.1016/j.ijhydene.2016.07.204.
21. Giannozzi P, Baroni S, Bonini N, Calandra M, Car R, Cavazzoni C, et al. QUANTUM ESPRESSO: a modular and open-source software project for quantumsimulations of materials. J Phys: Condens Matter. 2009;21(39):395502. doi: 10.1088/0953-8984/21/39/395502.
22. Perdew JP, Chevary JA, Vosko SH, Jackson KA, Pederson MR, Singh DJ, et al. Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Phys Rev B. 1992;46(11):6671-87. doi: 10.1103/PhysRevB.46.6671.
23. Nosir MA, Martin-Gondre L, Bocan GA, Muiño RD. Adsorption dynamics of molecular nitrogen at an Fe (111) surface. Phys Chem Chem Phys. 2017;19(10):7370-9. doi: 10.1039/C6CP07174K.
24. Majid A, Tasawar S, Raza H, et al. Uncovering the Potential of Two-Dimensional SrRuO₃ as anode material in Li, Na, Mg, Ca, K, and Zn ion Batteries: First-Principles investigations of structural, electronic and electrochemical properties. Journal of Energy Storage, 2025;105: 114634.
25. Jiang Y, Adams JB. First principle calculations of benzotriazole adsorption onto clean Cu(1 1 1). Surf Sci. 2003;529(3):428-42. doi: 10.1016/S0039-6028(03)00277-2.
26. Züttel A. Materials for hydrogen storage. Mater Today. 2003;6(9):24-33. doi: 10.1016/S1369-7021(03)00922-2.
27. Hanada N, Ichikawa T, Fujii H. Catalytic effect of nanoparticle 3d-transitionmetals on hydrogen storage properties in magnesium hydrogen MgH2 preparedby mechanical milling. J Phys Chem B. 2005;109(15):7188-94. doi: 10.1021/jp044576c.
28. Huan QQ, Zhu YF, Wei LJ. Hydrogen storage properties of Mg–Ni/graphene composites. Rare Metal Mater Eng. 2014;43(2):356-60.
29. Zhang J, Yu X F, Mao C, Long CG, Chen J, Zhou DW. Influences and mechanisms of graphene-dopingon dehydrogenation properties of MgHz: Experimental and first-principlesstudies. Energy. 2015;89:957-64. doi: 10.1016/j.energy.2015.06.037.
30. Henkelman G, Uberuaga B P, Jónsson H. A climbing image nudged elasticband method for finding saddle points andminimum energy paths. Chem Phys. 2000;113(22):9901-4. doi: 10.1063/1.1329672.
31. Dong S, Lv E, Wang J, Li C, Ma K, Gao Z, et al. Construction of transition metal-decorated boron doped twin graphene for hydrogen storage: A theoretical prediction. Fuel. 2021;304:121351. doi: 10.1016/j.fuel.2021.121351.
32. He Y, Ding L, Wu XL, Li Q, Li Z, Zhang W, et al. Hydrogen release mechanisms of MgH2 over NiN4-embedded graphene nanosheet: first-principles calculations. Intern J Hydrogen Energy. 2022;47(93):39549-62. doi: 10.1016/j.ijhydene.2022.09.102.
33. Zhang HP, Luo XG, Lin XY, Tang P, Lu X, Fang L, et al. Modulatingthe interactions between MgH2 and grapheneusing different dopants. Chem Phys Lett. 2015;623:82-8. doi: 10.1016/j.cplett.2015.01.052.
Published
2026-04-09
How to Cite
1.
Du X, Yin X, Liang H, Li T. FIRST-PRINCIPLE CALCULATIONS OF THE SYNERGISTIC CATALYTIC PERFORMANCE OF GRAPHENE AND TRANSITION METALS FOR MGH2 DEHYDROGENATION. MatTech [Internet]. 2026Apr.9 [cited 2026Jul.14];60(2):217–227. Available from: https://mater-tehnol.si/index.php/MatTech/article/view/1604
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