Preparation and hydrogen storage properties of MgH2-trimesic acid-TM MOF (TM=Co, Fe) composites

doi:10.1016/j.jmst.2019.05.049

Abstract

Abstract:

Two kinds of metal-organic frameworks (MOFs) based on Co (II) and Fe (II) as metal ions and trimasic acid (TMA) as organic linker were synthesized. They were used to prepare corresponding MgH₂-TM MOF (TM = Co, Fe) composites via ball-milling. X-ray diffraction analyses show the formation of Mg₂Co and α-Fe phases in MgH₂-TM MOF composites after decomposition. Both of the well dispersed Mg₂Co and α-Fe nanoparticles exhibit considerable catalytic efficiency in accelerating the sorption kinetics of MgH₂. The dehydrogenated MgH₂-Fe MOF composite shows faster hydriding kinetics than the pure MgH₂ and MgH₂-Co MOF. Meanwhile, the apparent dehydrogenation activation energy (E_d) of the MgH₂-Co MOF and MgH₂-Fe MOF composites are 151.3 ± 9.4 and 142.3 ± 6.5 kJ/mol H₂, both of which are lower than that of pure MgH₂ (181.4 ± 9.2 kJ/mol H₂). The improvement on the sorption kinetics of the MgH₂-TM MOF powders is mainly attributed to the catalytic effects of nano-sized Mg₂Co and α-Fe formed on the surface of Mg/MgH₂ particles.

Key words: TMA-TM MOFs, Mg hydride, Catalytic effects, Kinetic property

Zhewen Ma, Jianxin Zou, Darvaish Khan, Wen Zhu, Chuanzhu Hu, Xiaoqin Zeng, Wenjiang Ding. Preparation and hydrogen storage properties of MgH₂-trimesic acid-TM MOF (TM=Co, Fe) composites[J]. J. Mater. Sci. Technol., 2019, 35(10): 2132-2143.

Figures/Tables 12

Fig. 1. Schematic diagram of synthesized TMA-TM MOFs (TM = Co, Fe).

Fig. 2. SEM images of pure MgH2 (a), TMA-Co MOF (b) and TMA-Fe MOF (c).

Table 1 Pore structural parameters of TMA-TM MOFs (TM = Co, Fe) using N2 adsorption isotherms.

Samples	BET surface area (m²/g)	BJH pore size (nm)	Pore volume (cm³/g)
TMA-Co MOF	507.97	5.90	0.2339
TMA-Fe MOF	1015.49	3.02	0.5317

Fig. 3. FT-IR spectra of TMA (a), TMA-Co MOF (b) and TMA-Fe MOF (c) synthesized in DI water.

Fig. 4. TG and DSC curves of TMA-Co MOF (a) and TMA-Fe MOF (b) at the heating rate of 5 K/min.

Fig. 5. XRD patterns of TMA-Co MOF (a), TMA-Fe MOF (b), pure MgH2 and MgH2-TM MOF (TM = Co, Fe) composites at various states: as milled (c, d, e), re-hydrogenated at 623 K for 2 h (f, g, h), and dehydrogenated at 673 K for 2 h (i, j), respectively.

Fig. 6. SEM micrographs of the as milled (A), hydrogenated (H) and dehydrogenated (O) pure MgH2 powders, the as milled (B), (E), hydrogenated (C), (F) and dehydrogenated (D), (G) MgH2-TM MOF (TM = Co, Fe) composites, respectively. The corresponding EDS mappings showing distributions of Co (I-K), Fe (L-N) and O (P-U) (As milled: after ball-milling; Ab: absorption; De: desorption).

Fig. 7. Typical bright field TEM micrographs of the hydrogenated MgH2-Co MOF (a) and MgH2-Fe MOF (e) samples, the corresponding SAED patterns (b), (f), the dark field micrographs (c), (g) contributed by Mg2Co (442) and α-Fe (211) diffraction rings and the HRTEM images (d), (h), respectively.

Fig. 8. PC isotherms and the van’t Hoff plots of pure MgH2 (a, b), the MgH2-Co MOF (c, d) and the MgH2-Fe MOF (e, f) composites tested at 589, 623 and 648 K.

Table 2 PCT parameters of pure MgH2 and the MgH2-TM MOF (TM = Co and Fe) composite samples obtained at different temperatures.

Samples	Temperature (K)	Maximum H-absorption (wt%)	Reversible H₂ sorption capacity (wt%)	Absorption plateaus (MPa)	Desorption plateaus (MPa)
Pure Mg	598	6.51	3.63	0.46	0.26
	623	6.66	5.44	0.84	0.53
	648	6.91	6.05	1.29	0.97
MgH₂-Co MOF composite	598	5.08	4.62	0.39	0.28
	623	5.14	4.89	0.72	0.55
	648	5.19	5.04	1.36	1.02
MgH₂-Fe MOF composite	598	5.19	4.31	0.40	0.26
	623	5.30	4.64	0.73	0.49
	648	5.37	5.04	1.23	0.94

Fig. 9. Hydrogen absorption profiles and the corresponding lnk-1000/T plots of pure MgH2 (a, b), the MgH2-Co MOF (c, d) and the MgH2-Fe MOF (e, f) composites measured at 448, 473, 498, 523, 548 and 573 K under 3 MPa H2 pressure for 3 h.

Fig. 10. DSC profiles and the corresponding ln(β/Tp2)–1000/Tp plots for pure MgH2 (a, b), the MgH2-Co MOF (c, d) and the MgH2-Fe MOF (e, f) composites at different heating rates.

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Preparation and hydrogen storage properties of MgH₂-trimesic acid-TM MOF (TM=Co, Fe) composites

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