PEDOT coated Cu-BTC metal-organic frameworks decorated with Fe3O4 nanoparticles and their enhanced electromagnetic wave absorption

doi:10.1016/j.matchemphys.2020.123458

Materials Chemistry and Physics

Volume 253, 1 October 2020, 123458

https://doi.org/10.1016/j.matchemphys.2020.123458 Get rights and content

Highlights

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Cu₃(1,3,5-benzenetricarboxylate) (Cu-BTC) metal-organic frameworks decorated with Fe3O4 nanoparticles were synthesized.
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The PEDOT coated Fe₃O₄/Cu-BTC was successfully prepared.
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The sample with 45 wt% loading exhibits optimal R_L characteristics.
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RL_min of the sample is −18.3 dB with a broad effective bandwidth of 2 GHz at 5 mm.

Abstract

In this study, Cu₃(1,3,5-benzenetricarboxylate) (Cu-BTC) metal-organic frameworks decorated with Fe₃O₄ nanoparticles were synthesized via the hydrothermal process. Subsequently, the obtained Fe₃O₄/Cu-BTC was coated by poly(3,4-ethylenedioxythiophene) (PEDOT) via in situ chemical polymerization methods. The chemical, structural, and magnetic hysteresis analysis of particles were carried oud via scanning electron microscope (SEM), X-ray diffractometer (XRD), vibrating sample magnetometer (VSM), and fourier transform infrared spectroscopy (FTIR) machines. The characteristic peaks of C/F and P@C/F were obtained without any other impurities and extra peaks. The Fe₃O₄ decorated Cu-BTC displayed octahedral morphology with average particle size of 150–170 nm. As an electromagnetic wave absorber, the obtained Fe₃O₄ decorated Cu-BTC was mixed with 45% by weight of paraffin. For comparative studies, the PEDOT coated Fe₃O₄/Cu-BTC was also filled to the paraffin matrix. The higher real and imaginary part of permittivity values were obtained with introduction of conductive PEDOT shell. The electromagnetic wave absorption performance of composites was determined with permeability and permittivity values. The result exhibited that the strongest reflection loss was −18.3 dB at 17.5 GHz frequency with a thickness of 5 mm for PEDOT coated Fe₃O₄/Cu-BTC composite. It was proved that the conductive PEDOT coating on Fe₃O₄/Cu-BTC enhanced electromagnetic wave absorption capability of composite and the PEDOT coated Fe₃O₄/Cu-BTC can be considered as a good candidate for electromagnetic wave absorption applications.

Introduction

Recently the magnetic materials have been used in a wide range of applications such as antimicrobial, magnetic shields, catalysis, microwave application [[1], [2], [3], [4]]. On the other hand, dielectric materials have been studied in batteries, energy storage, molecular electronics, optics, and insulator applications [[5], [6], [7]]. The electromagnetic (EM) wave absorption capabilities of materials can be originated by these dielectric magnetic loss factors [8]. The EM wave absorbers can be classified as magnetic (such as ferrite, nickel, cobalt) and/or dielectric absorbers (such as graphene, carbon black, conductive polymers) based on their filler types [[9], [10], [11]]. Recently, some dielectric and magnetic nanoparticles coated with conductive polymers such as poly(3,4-ethylenedioxythiophene), polypyrrole, polyaniline have been prepared for EM wave absorption applications [12,13]. Many studies reported that the multiple interfacial phases occurred between nanoparticles and polymer shells enhanced dielectric and magnetic properties of particles/polymers systems [14,15]. For instance, the electrophysical and magnetic properties of polymer composites have been developed using multi-walled carbon nanotube (MWCNT) or graphite [16,17]. Among dielectric materials, the metal-organic frameworks (MOFs) have attracted a great deal of interest due to their porous structures for different applications such as adsorption separation, gas storage, luminescence, drug delivery, and catalysis. In the last decade, the large amount of MOF materials, which are coordinating cationic and anionic metal-oxygen frameworks with polymer linkers have been synthesized. However, the MOFs can provide new properties for EM wave absorption applications due to their well pore size distribution and tailorable structural properties [[18], [19], [20], [21]].

One of the most studied MOFs is Cu₃(1,3,5-benzenetricarboxylate) abbreviated as Cu-BTC that used for especially gas purification, separation, and storages. The Cu-BTC MOFs have been synthesized with various methods such as electrochemical, solvothermal, and electrospraying methods. Li et al. [22] prepared Cu-BTC functionalized with imidazole by ultrafast room temperature synthesis method for enhanced its steam stability. Ramasubbu et al. [23] synthesized novel TiO₂ aerogel-Cu-BTC MOFs via the sol-gel method and the chemical and structural properties of products were characterized with TEM, SEM, FT-IR, XRD, and BET. Hosseini et al. [24] have developed Cu-BTC metal-organic frameworks film as a new type of nanosensor by using an electrochemical method. Crawford et al. [25] have studied optimization and growth of Cu₃(1,3,5-benzenetricarboxylate) thin film on conductive Al-doped ZnO (AZO) templates. Yin et al. [26] have reported to NH₃ gas sensor based on Cu-BTC doped polypyrrole (PPy) coated graphene oxide (GO) composites. Grajciar et al. [27] have studied water absorption properties of Cu-BTC metal-organic frameworks (MOFs) theoretically.

Today, magnetic oxide production has received much attention due to the unique combinations of spin, charge and orbital orders. Among the magnetic oxides, many studies have focused on perovskite-like oxides and Fe based oxides. Magnetite (Fe₃O₄) nanoparticles were used in a wide range of applications such as biomedical, magnetic resonance imaging, drug delivery, and electromagnetic wave applications due to unique properties such as high surface area, super magnetic properties, and nanoscale sizes [[28], [29], [30], [31]].

Recently, many metal-organic frameworks materials have been studied as EM wave absorbers due to their high surface areas and porous structure. In addition, novel structural designs were performed to enhanced EM wave absorption performance of metal-organic frameworks. However, Cu-BTC MOFs have not been studied for EM wave absorption applications yet. In this study, poly(3,4 ethylenedioxythiophene) (PEDOT) coated Cu-BTC metal-organic frameworks decorated with Fe₃O₄ nanoparticles were synthesized via the hydrothermal process and subsequent in situ chemical polymerization. Then the PEDOT coated Fe₃O₄/Cu-BTC and uncoated Fe₃O₄/Cu-BTC were dispersed in the paraffin matrix to determine their EM wave absorption performances. The electromagnetic wave absorption properties of Fe₃O₄ decorated Cu-BTC MOFs were first studied in this paper. It was seen that the PEDOT coated Fe₃O₄/Cu-BTC presented a minimum reflection loss value of −18.3 dB at 17.5 GHz frequency with 5 mm thickness. However, the uncoated Fe₃O₄/Cu-BTC did not display sufficient EM wave absorption capability.

Section snippets

Preparation of Cu-BTC MOF

All chemicals and materials were obtained from Sigma-Aldrich. In a typical synthesis, copper (II) nitrate trihydrate (Cu(NO₃)₂·3H₂O) and trimesic acid (H₃BTC) were dissolved in dimethyl sulfoxide and stirred for 3 h at ambient temperature. The solution was kept at room temperature for 24 h in the sealed vial without stirring. The Cu-BTC precipitate was completely separated by centrifugation and then washed with ethanol three times. The final product is dried at 70 °C for 24 h in vacuum oven.

Synthesis of Cu-BTC/Fe₃O₄ composite powder

Results and discussion

The XRD patterns of C/F and P@C/F were observed in Fig. 1. It was seen that the obtained peak at 26.0° is attributed to the existence of PEDOT [20]. The 2θ = 30.2°, 35.7°, 37.4°, 43.1°, 53°, 57.2°, and 62.7° corresponded to the (220), (311), (222), (400), 422), (511), and (440) lattice planes of Fe₃O₄ [32,33]. The characteristic peaks of Cu-BTC appeared at 2θ = 6.7°, 10°, 12.5°, 13.7°, 17°, 19.1°, and 20.3° corresponded to the (200), (220), (222), (400), (511), (440), and (442) lattice planes

Conclusion

In this study, PEDOT coated C/F metal-organic frameworks decorated with Fe₃O₄ nanoparticles were successfully synthesized via the hydrothermal process and subsequent in situ chemical polymerization and the characterizations of obtained particles have been investigated by using SEM, XRD, FT-IR, VSM, and VNA analyses. The Ms values of particles decreased while Hc increased with a coating of PEDOT on the C/F surface. The $ε^{'}$ and $ε^{''}$ values were significantly enhanced by coating C/F with conductive

CRediT authorship contribution statement

Haichun Niu: Methodology. Peixue Liu: Methodology. Fuzhen Qin: Investigation. XiaoLing Liu: Methodology. Yuksel Akinay: Writing - review & editing.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was supported by the Shandong Provincial Key Research and Development Program 2019GGX105001 and the Shandong Provincial Education Department Science and Technology Projects J18KB164 and J18KB155.

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PEDOT coated Cu-BTC metal-organic frameworks decorated with Fe3O4 nanoparticles and their enhanced electromagnetic wave absorption

Highlights

Abstract

Introduction

Section snippets

Preparation of Cu-BTC MOF

Synthesis of Cu-BTC/Fe3O4 composite powder

Results and discussion

Conclusion

CRediT authorship contribution statement

Declaration of competing interest

Acknowledgements

Ceram. Int.

J. Magn. Magn Mater.

J. Alloys Compd.

Mater. Chem. Phys.

Compos. Sci. Technol.

Chem. Eng. J.

Mater. Lett.

Sensor. Actuator. B Chem.

Mater. Res. Bull.

J. Alloys Compd.

Ceram. Int.

Mater. Res. Bull.

Compos. Sci. Technol.

J. Solid State Chem.

Polymer

Mater. Res. Bull.

J. Alloys Compd.

Surf. Coating. Technol.

Ceram. Int.

Vacuum

Synth. Met.

J. Alloys Compd.

J. Alloys Compd.

Multifunctionality of lanthanum-strontium manganite nanopowder

Phys. Chem. Chem. Phys.

Spintronic oxides grown by laser-MBE

J. Phys. D Appl. Phys.

PEDOT coated Cu-BTC metal-organic frameworks decorated with Fe₃O₄ nanoparticles and their enhanced electromagnetic wave absorption

Synthesis of Cu-BTC/Fe₃O₄ composite powder