构建负载于石墨烯纳米片的FeOOH纳米粒子用于改善氢化镁的储氢性能

宋孟臣; 张刘挺; 郑家广; 于子冬; 王胜男

doi:10.1007/s12613-021-2393-0

Volume 29 Issue 7

Jul. 2022

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文章导航 > 矿物冶金与材料学报（英文） > 2022 > 29(7): 1464-1473

Mengchen Song, Liuting Zhang, Jiaguang Zheng, Zidong Yu, and Shengnan Wang, Constructing graphene nanosheet-supported FeOOH nanodots for hydrogen storage of MgH₂, Int. J. Miner. Metall. Mater., 29(2022), No. 7, pp. 1464-1473. https://doi.org/10.1007/s12613-021-2393-0

Cite this article as:

Mengchen Song, Liuting Zhang, Jiaguang Zheng, Zidong Yu, and Shengnan Wang, Constructing graphene nanosheet-supported FeOOH nanodots for hydrogen storage of MgH2, Int. J. Miner. Metall. Mater., 29(2022), No. 7, pp. 1464-1473. https://doi.org/10.1007/s12613-021-2393-0

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研究论文

构建负载于石墨烯纳米片的FeOOH纳米粒子用于改善氢化镁的储氢性能

1)
江苏科技大学能源与动力学院，镇江 212003，中国
2)
中国工程物理研究院化工材料研究所，绵阳 621999，中国

通讯作者:
张刘挺 E-mail: zhanglt89@just.edu.cn

王胜男 E-mail: shengnan@caep.cn

文章亮点

(1) 通过水热法成功构筑了石墨烯纳米片负载的FeOOH纳米粒子(FeOOH NDs@G)。

(2) FeOOH NDs@G有效降低了MgH₂的放氢活化能和吸氢活化能，且复合体系20次循环后仍保持初始容量的98.5%。

(3) FeOOH NDs@G对MgH₂的催化活性归因于石墨烯纳米片与原位生成的Fe之间的协同作用。

中文摘要

氢能具有热值高、零碳排放和来源丰富等优点，被认为是一种能有效替代化石燃料、实现碳中和目标的能源载体。然而，安全高效的储氢技术仍然是大规模应用氢能的关键挑战之一。氢化镁（MgH₂）因其储氢量高(7.6wt%)、可逆性好而备受关注。本工作采用水热法成功制备了石墨烯纳米片负载的FeOOH纳米点(FeOOH NDs@G)，并通过机械球磨法将其掺杂到MgH₂中。研究结果表明， MgH₂–10wt%FeOOH NDs@G复合材料在229.8°C开始放氢，比纯MgH₂的放氢温度降低了106.8°C。在3.2 MPa的氢气压力下，完全放氢的MgH₂–10wt%FeOOH NDs@G样品可在200°C、60 min内吸收6.0wt%氢气。加入FeOOH NDs@G后，MgH₂的放氢活化能和吸氢活化能分别降至125.03和58.20 kJ·mol^–1 (纯MgH₂的脱氢活化能分别为156.05和82.80 kJ·mol^–1)。此外，MgH₂ –10wt%FeOOH NDs@G复合材料的储氢容量在20次循环后仍保持初始容量的98.5%，表现出良好的循环稳定性。FeOOH NDs@G对MgH₂的催化作用归因于石墨烯纳米片与原位生成的Fe之间的协同作用，在阻碍Mg/MgH₂颗粒团聚的同时加速了氢的扩散速率，从而使MgH₂–10wt%FeOOH NDs@G复合材料展现出良好的储氢性能。

关键词:

储氢;
氢化镁;
FeOOH NDs@G;
催化

Research Article

Constructing graphene nanosheet-supported FeOOH nanodots for hydrogen storage of MgH₂

+ Author Affiliations

Abstract

Abstract

Novel graphene-supported FeOOH nanodots (FeOOH NDs@G) were successfully prepared by a facile hydrothermal method and doped into MgH₂ through mechanical ball-milling. MgH₂ with 10wt% FeOOH NDs@G began to release hydrogen at 229.8°C, which is 106.8°C lower than that of pure MgH₂. The MgH₂–10wt% FeOOH NDs@G composite could reversibly absorb 6.0wt% hydrogen at 200°C under a 3.2 MPa hydrogen pressure within 60 min. With the addition of FeOOH NDs@G, the dehydrogenation and hydrogenation activation energy of MgH₂ was decreased to 125.03 and 58.20 kJ·mol⁻¹ (156.05 and 82.80 kJ·mol⁻¹ for pure MgH₂), respectively. Furthermore, the hydrogen capacity of the FeOOH NDs@G composite retained 98.5% of the initial capacity after 20 cycles, showing good cyclic stability. The catalytic action of FeOOH NDs@G towards MgH₂ could be attributed to the synergistic effect between graphene nanosheets and in-situ formed Fe, which prevented the aggregation of Mg/MgH₂ particles and accelerated the hydrogen diffusion during cycling, thus enabling the MgH₂–10wt% FeOOH NDs@G composite to exhibit excellent hydrogen storage performance.
- hydrogen storage;
- MgH₂;
- FeOOH NDs@G;
- catalysis

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References

[1]	L. Maugeri, Oil: never cry wolf—Why the petroleum age is far from over, Science, 304(2004), No. 5674, p. 1114. doi: 10.1126/science.1096427
[2]	C. Wan, L. Zhou, and S.M. Xu, et al., Defect engineered mesoporous graphitic carbon nitride modified with AgPd nanoparticles for enhanced photocatalytic hydrogen evolution from formic acid, Chem. Eng. J., 429(2022), art. No. 132388. doi: 10.1016/j.cej.2021.132388
[3]	Y.H. Zhang, W. Zhang, and X.P. Song, et al., Effects of spinning rate on structures and electrochemical hydrogen storage performances of RE–Mg–Ni–Mn-based AB₂-type alloys, Trans. Nonferrous Met. Soc. China, 26(2016), No. 12, p. 3219. doi: 10.1016/S1003-6326(16)64454-0
[4]	L. Schlapbach and A. Züttel, Hydrogen-storage materials for mobile applications, Nature, 414(2001), No. 6861, p. 353. doi: 10.1038/35104634
[5]	Q.W. Lai, M. Paskevicius, and D.A. Sheppard, et al., Hydrogen storage materials for mobile and stationary applications: Current state of the art, ChemSusChem, 8(2015), No. 17, p. 2789. doi: 10.1002/cssc.201500231
[6]	S.K. Jeon, O.H. Kwon, H.S. Jang, K.S. Ryu, and S.H. Nahm, Effect of high pressure hydrogen on the mechanical characteristics of single carbon fiber, Appl. Surf. Sci., 432(2018), p. 176. doi: 10.1016/j.apsusc.2017.07.005
[7]	A. Hammad and I. Dincer, Analysis and assessment of an advanced hydrogen liquefaction system, Int. J. Hydrogen Energy, 43(2018), No. 2, p. 1139. doi: 10.1016/j.ijhydene.2017.10.158
[8]	Y. Li, Y. Tao, and Q. Huo, Effect of stoichiometry and Cu-substitution on the phase structure and hydrogen storage properties of Ml–Mg–Ni-based alloys, Int. J. Miner. Metall. Mater., 22(2015), No. 1, p. 86. doi: 10.1007/s12613-015-1047-5
[9]	J.O. Abe, A.P.I. Popoola, E. Ajenifuja, and O.M. Popoola, Hydrogen energy, economy and storage: Review and recommendation, Int. J. Hydrogen Energy, 44(2019), No. 29, p. 15072. doi: 10.1016/j.ijhydene.2019.04.068
[10]	Y. Kojima, Hydrogen storage materials for hydrogen and energy carriers, Int. J. Hydrogen Energy, 44(2019), No. 33, p. 18179. doi: 10.1016/j.ijhydene.2019.05.119
[11]	G.Z. Kang and H. Li, Review on cyclic plasticity of magnesium alloys: Experiments and constitutive models, Int. J. Miner. Metall. Mater., 28(2021), No. 4, p. 567. doi: 10.1007/s12613-020-2216-8
[12]	Y. Wang and Y.J. Wang, Recent advances in additive-enhanced magnesium hydride for hydrogen storage, Prog. Nat. Sci. Mater. Int., 27(2017), No. 1, p. 41. doi: 10.1016/j.pnsc.2016.12.016
[13]	F.Y. Cheng, Z.L. Tao, J. Liang, and J. Chen, Efficient hydrogen storage with the combination of lightweight Mg/MgH₂ and nanostructures, Chem. Commun., 48(2012), No. 59, art. No. 7334. doi: 10.1039/c2cc30740e
[14]	L.X. Hu and E.D. Wang, Hydrogen generation via hydrolysis of nanocrystalline MgH₂ and MgH₂-based composites, Trans. Nonferrous Met. Soc. China, 15(2005), No. 5, p. 965.
[15]	L.S. Xie, J.S. Li, T.B. Zhang, and H.C. Kou, Role of milling time and Ni content on dehydrogenation behavior of MgH₂/Ni composite, Trans. Nonferrous Met. Soc. China, 27(2017), No. 3, p. 569. doi: 10.1016/S1003-6326(17)60063-3
[16]	Y.H. Sun, T.Y. Ma, and K.F. Aguey-Zinsou, Magnesium supported on nickel nanobelts for hydrogen storage: Coupling nanosizing and catalysis, ACS Appl. Nano Mater., 1(2018), No. 3, p. 1272. doi: 10.1021/acsanm.8b00033
[17]	Q.Y. Zhang, Y.K. Huang, and L. Xu, et al., Highly dispersed MgH₂ nanoparticle–graphene nanosheet composites for hydrogen storage, ACS Appl. Nano Mater., 2(2019), No. 6, p. 3828. doi: 10.1021/acsanm.9b00694
[18]	C.Q. Zhou, Y.Y. Peng, and Q.G. Zhang, Growth kinetics of MgH₂ nanocrystallites prepared by ball milling, J. Mater. Sci. Technol., 50(2020), p. 178. doi: 10.1016/j.jmst.2020.01.063
[19]	Y.H. Zhang, D.L. Zhao, and B.W. Li, et al., Hydrogen storage behaviours of nanocrystalline and amorphous Mg₂₀Ni_10–xCo_x(x=0–4) alloys prepared by melt spinning, Trans. Nonferrous Met. Soc. China, 20(2010), No. 3, p. 405. doi: 10.1016/S1003-6326(09)60154-0
[20]	J.Z. Song, Z.Y. Zhao, X. Zhao, R.D. Fu, and S.M. Han, Hydrogen storage properties of MgH₂ co-catalyzed by LaH₃ and NbH, Int. J. Miner. Metall. Mater., 24(2017), No. 10, p. 1183. doi: 10.1007/s12613-017-1509-z
[21]	Y.H. Zhang, T. Yang, and W.G. Bu, et al., Effect of Nd content on electrochemical performances of nanocrystalline and amorphous (Mg₂₄Ni₁₀Cu₂)_100−xNd_x (x=0−20) alloys prepared by melt spinning, Trans. Nonferrous Met. Soc. China, 23(2013), No. 12, p. 3668. doi: 10.1016/S1003-6326(13)62915-5
[22]	Y.H. Zhang, L.W. Li, and D.C. Feng, et al., Hydrogen storage behavior of nanocrystalline and amorphous La–Mg–Ni-based LaMg12-type alloys synthesized by mechanical milling, Trans. Nonferrous Met. Soc. China, 27(2017), No. 3, p. 551. doi: 10.1016/S1003-6326(17)60061-X
[23]	V. Knotek and D. Vojtěch, Electrochemical hydriding performance of Mg–TM–Mm (TM=transition metals, Mm=mischmetal) alloys for hydrogen storage, Trans. Nonferrous Met. Soc. China, 23(2013), No. 7, p. 2047. doi: 10.1016/S1003-6326(13)62695-3
[24]	X. Zhao, S.M. Han, Y. Li, X.C. Chen, and D.D. Ke, Effect of CeH_2.29 on the microstructures and hydrogen properties of LiBH₄–Mg₂NiH₄ composites, Int. J. Miner. Metall. Mater., 22(2015), No. 4, p. 423. doi: 10.1007/s12613-015-1089-8
[25]	C.C. Xu, X.Z. Xiao, and J. Shao, et al., Effects of Ti-based additives on Mg₂FeH₆ dehydrogenation properties, Trans. Nonferrous Met. Soc. China, 26(2016), No. 3, p. 791. doi: 10.1016/S1003-6326(16)64169-9
[26]	F.M. Nyahuma, L.T. Zhang, and M.C. Song, et al., Significantly improved hydrogen storage behaviors of MgH₂ with Nb nanocatalyst, Int. J. Miner. Metall. Mater., 2021, DOI: 10.1007/s12613-021-2303-5
[27]	Z. Zhang, J.H. Zhang, and J. Wang, et al., Toward the development of Mg alloys with simultaneously improved strength and ductility by refining grain size via the deformation process, Int. J. Miner. Metall. Mater., 28(2021), No. 1, p. 30. doi: 10.1007/s12613-020-2190-1
[28]	F.A.H. Yap, N.N. Sulaiman, and M. Ismail, Understanding the dehydrogenation properties of MgH₂ catalysed by Na₃AlF₆, Int. J. Hydrogen Energy, 44(2019), No. 58, p. 30583. doi: 10.1016/j.ijhydene.2018.02.073
[29]	Q.Y. Zhang, Y.K. Huang, and T.C. Ma, et al., Facile synthesis of small MgH₂ nanoparticles confined in different carbon materials for hydrogen storage, J. Alloys Compd., 825(2020), art. No. 153953. doi: 10.1016/j.jallcom.2020.153953
[30]	Y.H. Jia, S.M. Han, and W. Zhang, et al., Hydrogen absorption and desorption kinetics of MgH₂ catalyzed by MoS₂ and MoO₂, Int. J. Hydrogen Energy, 38(2013), No. 5, p. 2352. doi: 10.1016/j.ijhydene.2012.12.018
[31]	G.H. Majzoobi and K. Rahmani, Mechanical characterization of Mg–B₄C nanocomposite fabricated at different strain rates, Int. J. Miner. Metall. Mater., 27(2020), No. 2, p. 252. doi: 10.1007/s12613-019-1902-x
[32]	U. Ulmer, D. Oertel, and T. Diemant, et al., Performance improvement of V–Fe–Cr–Ti solid state hydrogen storage materials in impure hydrogen gas, ACS Appl. Mater. Interfaces, 10(2018), No. 2, p. 1662. doi: 10.1021/acsami.7b13541
[33]	X. Zhang, Z.H. Ren, and Y.H. Lu, et al., Facile synthesis and superior catalytic activity of nano-TiN@N–C for hydrogen storage in NaAlH₄, ACS Appl. Mater. Interfaces, 10(2018), No. 18, p. 15767. doi: 10.1021/acsami.8b04011
[34]	B. Yang, J.X. Zou, and T.P. Huang, et al., Enhanced hydrogenation and hydrolysis properties of core-shell structured Mg–MO_x (M = Al, Ti and Fe) nanocomposites prepared by arc plasma method, Chem. Eng. J., 371(2019), p. 233. doi: 10.1016/j.cej.2019.04.046
[35]	X. Zhang, Y.F. Liu, K. Wang, M.X. Gao, and H.G. Pan, Remarkably improved hydrogen storage properties of nanocrystalline TiO₂-modified NaAlH₄ and evolution of Ti-containing species during dehydrogenation/hydrogenation, Nano Res., 8(2015), No. 2, p. 533. doi: 10.1007/s12274-014-0667-9
[36]	X.Y. Ma, J.Q. Li, and C.H. An, et al., Ultrathin Co(Ni)-doped MoS₂ nanosheets as catalytic promoters enabling efficient solar hydrogen production, Nano Res., 9(2016), No. 8, p. 2284. doi: 10.1007/s12274-016-1115-9
[37]	S.R. Naqvi, T. Hussain, W. Luo, and R. Ahuja, Metallized siligraphene nanosheets (SiC₇) as high capacity hydrogen storage materials, Nano Res., 11(2018), No. 7, p. 3802. doi: 10.1007/s12274-017-1954-z
[38]	Z.Y. Lu, H.J. Yu, and X. Lu, et al., Two-dimensional vanadium nanosheets as a remarkably effective catalyst for hydrogen storage in MgH₂, Rare Met., 40(2021), No. 11, p. 3195. doi: 10.1007/s12598-021-01764-7
[39]	L. Xie, Y. Liu, and X.Z. Zhang, et al., Catalytic effect of Ni nanoparticles on the desorption kinetics of MgH₂ nanoparticles, J. Alloys Compd., 482(2009), No. 1-2, p. 388. doi: 10.1016/j.jallcom.2009.04.028
[40]	W.C. Huang, J. Yuan, and J.G. Zhang, et al., Improving dehydrogenation properties of Mg/Nb composite films via tuning Nb distributions, Rare Met., 36(2017), No. 7, p. 574. doi: 10.1007/s12598-017-0913-x
[41]	Y. Wang, Q.Y. Zhang, Y.J. Wang, L.F. Jiao, and H.T. Yuan, Catalytic effects of different Ti-based materials on dehydrogenation performances of MgH₂, J. Alloys Compd., 645(2015), p. S509. doi: 10.1016/j.jallcom.2014.12.071
[42]	A. Bassetti, E. Bonetti, and L. Pasquini, et al., Hydrogen desorption from ball milled MgH₂ catalyzed with Fe, Eur. Phys. J. B, 43(2005), No. 1, p. 19. doi: 10.1140/epjb/e2005-00023-9
[43]	L.T. Zhang, L. Ji, and Z.D. Yao, et al., Facile synthesized Fe nanosheets as superior active catalyst for hydrogen storage in MgH₂, Int. J. Hydrogen Energy, 44(2019), No. 39, p. 21955. doi: 10.1016/j.ijhydene.2019.06.065
[44]	G.L. Xia, Y.B. Tan, and X.W. Chen, et al., Monodisperse magnesium hydride nanoparticles uniformly self-assembled on graphene, Adv. Mater., 27(2015), No. 39, p. 5981. doi: 10.1002/adma.201502005
[45]	L. Ji, L.T. Zhang, X.L. Yang, X.Q. Zhu, and L.X. Chen, The remarkably improved hydrogen storage performance of MgH₂ by the synergetic effect of an FeNi/rGO nanocomposite, Dalton Trans., 49(2020), No. 13, p. 4146. doi: 10.1039/D0DT00230E
[46]	J.Q. Liu, M.B. Zheng, X.Q. Shi, H.B. Zeng, and H. Xia, Amorphous FeOOH quantum dots assembled mesoporous film anchored on graphene nanosheets with superior electrochemical performance for supercapacitors, Adv. Funct. Mater., 26(2016), No. 6, p. 919. doi: 10.1002/adfm.201504019
[47]	R.V. Muraleedharan, On Johnson-Mehl-Avrami equation, J. Therm. Anal., 37(1991), No. 11-12, p. 2729. doi: 10.1007/BF01912817
[48]	E. Xu, H. Li, X.M. You, C. Bu, L.F. Zhang, Q. Wang, and Z.G. Zhao, Influence of micro-amount O₂ or N₂ on the hydrogenation/dehydrogenation kinetics of hydrogen-storage material MgH₂, Int. J. Hydrogen Energy, 42(2017), No. 12, p. 8057. doi: 10.1016/j.ijhydene.2016.12.102
[49]	G. Liu, Y.J. Wang, and C.C. Xu, et al., Excellent catalytic effects of highly crumpled graphene nanosheets on hydrogenation/dehydrogenation of magnesium hydride, Nanoscale, 5(2013), No. 3, p. 1074. doi: 10.1039/C2NR33347C