Construction of binary assembled MOF-derived nanocages with dual-band microwave absorbing properties

doi:10.1016/j.jmst.2021.11.013

Abstract

Abstract:

It is challenging to prepare a binary assembled metal-organic framework (MOF) by anisotropic epitaxial growth method. Besides, nanocages (NCs) with hollow structures are often constructed to improve microwave absorbing abilities. Herein, we combine the selective epitaxial growth and hollow engineering technologies to fabricate hybrid MOF-derived NCs. Benefiting from the unique nanocage/porous structure, complementary magnetic/dielectric components and suitable impedance matching characteristics, the optimized absorber (CoNi/TiO₂@PC-NCs) exhibits unique microwave absorbing properties. It is worth noting that the minimum reflection loss (RL_min) of the absorber reaches -65.3 dB, and the overall effective absorption bandwidth (EAB, RL < -10 dB) covers 15.1 GHz (2.9-18 GHz). The maximum EAB under a single thickness covers 4.4 GHz, displaying skipping dual-band coverages at both high and low frequencies. This work might provide a novel perspective for the synthesis of assembled MOF-derived absorbers.

Key words: Epitaxial growth, MOF, Nanocage, Porous structure, Microwave absorption

Fei Wu, Lingyun Wan, Ting Wang, Muhammad Rizwan Tariq, Tariq Shah, Pei Liu, Qiuyu Zhang, Baoliang Zhang. Construction of binary assembled MOF-derived nanocages with dual-band microwave absorbing properties[J]. J. Mater. Sci. Technol., 2022, 117: 36-48.

Figures/Tables 12

Fig. 1. Synthetic strategy of CoNi/TiO2@PC-NCs.

Fig. 2. SEM images of MZ (a-c), TEM images of MZ (d), corresponding HAADF-STEM graph and EDS-mappings of MZ (e), side TEM image of MZ (f).

Fig. 3. SEM images of MZ-NCs (a-c), TEM images of MZ-NCs (d), corresponding HAADF-STEM graph and EDS-mappings of MZ-NCs (e), side TEM image of MZ-NCs (f).

Fig. 4. SEM images of MZ-NCs@PDA (a, b) and CoNi/TiO2@PC-NCs (c), TEM images of CoNi/TiO2@PC-NCs (d-f), corresponding HAADF-STEM graph, EDS-mappings and SAED pattern of CoNi/TiO2@PC-NCs (g), side TEM image of CoNi/TiO2@PC-NCs (h).

Fig. 5. XRD patterns (a), Raman spectra (b, c), XPS spectra (d), TGA curves (e), and room-temperature hysteresis loops (f) of typical absorbers.

Table 1. Key parameters of samples.

Absorber	I_D/I_G	M_s(emu/g)	H_c(Oe)	S_BET(m²/g)	V_BJH(cm³/g)	D_BJH(nm)
TiO₂@C-NDs	0.98	-	-	6.04	0.02	44.35
CoNi/TiO₂@C-NCs	-	65.83	176.50	12.20	0.03	15.56
CoNi/TiO₂@PC-NCs	0.95	57.52	264.71	51.67	0.12	11.71

Fig. 6. Nitrogen absorption/desorption isotherm curves (a), and corresponding pore size distribution plots (b) of TiO2@C-NDs, CoNi/TiO2@C-NCs, and CoNi/TiO2@PC-NCs.

Fig. 7. 3D curves as well as 2D plots of TiO2@C-NDs (a, b), CoNi/TiO2@C-NCs (c, d), CoNi/TiO2@PC-NCs under filler loadings of 50% (e, f), 55% (g, h), and 60% (i, j).

Fig. 8. Plots of simulated and experimental tm, RL values of matching thicknesses under 1/4 condition as well as |Zin/Z0| values for CoNi/TiO2@PC-NCs at the thickness of 1.5-5.0 mm.

Fig. 9. Electromagnetic parameters of samples in the frequency range of 2-18 GHz: ε′ (a), ε″ (b) and tanδε (c); μ′ (d), μ″ (e) and tanδμ (f).

Fig. 10. Cole-Cole circles of TiO2@C-NDs (a), CoNi/TiO2@C-NCs (b), CoNi/TiO2@PC-NCs (c), and C0 curves of all samples (d).

Fig. 11. Diagram of microwave absorption mechanisms.

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