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Article
Facile Synthesis of Fe3O4/GCs Composites and
their Enhanced Microwave Absorption Properties
Xian Jian, Biao Wu, Yufeng Wei, Shixue Dou, Xiaolin Wang, Weidong He, and Nasir Mahmood
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b00388 • Publication Date (Web): 18 Feb 2016
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Facile Synthesis of Fe3O4/GCs Composites and their
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12 Enhanced Microwave Absorption Properties
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17 Xian Jian†,⊥,ζ,*, Biao Wu†,ζ, Yufeng Wei⊥,ζ, Shi Xue Dou⊥, Xiaolin Wang⊥, Weidong He†,*and
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19 Nasir Mahmood⊥,*
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22 †
23 School of Energy Science and Engineering, State key Laboratory of Electronic Thin Films and
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25 Integrated Devices, University of Electronic Science and Technology of China, Chengdu,
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611731, China.
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⊥
30 Institute for Superconducting and Electronic Materials, Australian Institute for Innovative
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Materials, University of Wollongong, North Wollongong, 2500, Australia.
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37 KEYWORDS: graphene capsules; catalytic chemical vapor deposition; Fe3O4; microwave
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absorption; hydrothermal.
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ABSTRACT: Graphene has good stability and adjustable dielectric properties along with
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46 tunable morphologies, hence can be used to design novel and high-performance functional
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48 materials. Here, we have reported a facile synthesis method of nanoscale Fe3O4/graphene
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capsules (GCs) composites using the combination of catalytic chemical vapor deposition
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53 (CCVD) and hydro-thermal process. The resulted composite has the advantage of unique
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55 morphology that offers better synergism among the Fe3O4 particles as well as particles and GCs.
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58 The microwave-absorbing characteristics of developed composites were investigated through
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experimentally measured electromagnetic properties and simulation studies based on the
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6 transmission line theory, explained on the basis of eddy current, natural and exchange
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8 resonance as well as dielectric relaxation processes. The composites bear minimum RL
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value of -32 dB at 8.76 GHz along with the absorption bandwidth range from 5.4 to 17
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13 GHz for RL lower than -10 dB. The better performance of the composite based on the
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15 reasonable impedance characteristic, existence of interfaces around the composites and the
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18 polarization of free carriers in 3D GCs that make the as-prepared composites capable of
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20 absorbing microwave more effectively. These results offer an effective way to design high-
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22 performance functional materials to facilitate the research in electromagnetic shielding and
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25 microwave absorption.
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29 1. INTRODUCTION
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31 Nowadays, with the rapid development of communication devices and extensive use of
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33 electronic devices, the electromagnetic interference (EMI) pollution has become a serious
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36 problem.1-3 To resolve the issues associated with the EMI pollution, considerable
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38 attention has been devoted to develop high-performance microwave absorption materials
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with low density, low thickness strong absorption over a broad frequency and high
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43 thermal stability. But the present development is not sufficient to overcome the issues
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45 raised by the growing usage of communication devices and further research is required to
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48 provide the healthy environment to the humankind. Generally, the microwave absorbing
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50 materials can be classified into two categories based on their microwave loss mechanism
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52 likewise dielectric loss and magnetic loss.1, 4, 5
The loss mechanism of dielectric loss
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55 materials such as carbon nanotubes (CNTs), carbon nanofibers (CNFs) and graphene is
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57 mainly based on the polarization. Although, the carbon-based materials possess the
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advantages of low density, superior mechanical and electronic properties and great
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6 thermal stability, but their microwave absorption capability is not good enough that limits
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8 their applications.6-9 For example, the graphene had a minimum RL value of −6.9 dB at
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7.0 GHz without any effective bandwidth that is higher than the required -10dB; however,
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13 the CNT arrays have a minimum RL value of −24.6 at 9.0 GHz with a bandwidth of 2.1
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15 from 8.2 to 10.3 GHz but its short bandwidth limits the applications.6, 10 Similarly, to
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18 realize the microwave loss of materials like Fe3O4, Fe and Co where the working
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20 mechanism is magnetic loss mainly depends on the magnetic properties of these
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22 materials. However, despite the high density of magmatic metal, most absorbers
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25 consisting of single component are incapable of producing high dielectric and magnetic
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27 loss simultaneously, thus limiting their applications.11, 12
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Thus, constructing composites with high dielectric and magnetic loss has attracted a lot of
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32 attention.13-17 Among them, the composites composed of magnetic nanoparticles and
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34 carbon materials have been the focus of major research due to many advantages such as
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37 low density, high thermal and chemical stability, tunable dielectric and magnetic
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39 properties, combination of both dielectric and magnetic loss mechanisms. Recently
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41 researchers have found that by combining the two different syntheses such as dielectric
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44 loss based materials with magnetic loss one can bring a rational design for high
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46 microwave absorption. Likewise, Che et al. reported that mutli-walled carbon nanotubes
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48 (MWCNT) containing Fe particles possessed improved microwave absorption ability than
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51 the individual components.18 Furthermore, it is found that the higher absorption capabilities
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53 of the carbon-metal composites are because of the polarization free carriers in carbon
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component and the charge transfer at metal/carbon interface.19 Though most of the
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research has been concentrated on developing one dimensional (1D) and 2D carbon
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6 materials like CNTs,20 CNFs21 and graphene,22 it is notable that 3D graphene capsules
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8 (GCs) will be more beneficial to enhanced the microwave absorption because of their
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special structure that resulted in an adjustable dielectric and magnetic property.
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13 Recently, yolk-shell C@C microsphere have been developed to observe the effect of such
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15 a structure on the microwave absorption and it is found that this structure brings an
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18 enhanced value, but the complicated synthesis process is one hurdle here.25 It is well-
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20 known that the electromagnetic absorption is based on the combination of enhanced performance
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22 and the effective absorption range (2-18 GHz), thus for practical applications, to reduce the
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25 effective RL value less than -10 dB with the relatively low frequency remains a challenge. Thus,
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27 a rational design for carbon/metal/oxide composites considering their morphology, structure and
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composition that can construct a strong synergism among the two components for better
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32 properties is highly required.
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34 Here, we have developed unique hybrid structure of Fe3O4/GCs via catalytic chemical
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37 vapor deposition (CCVD) and hydrothermal process as schematically shown in Figure 1.
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39 The resulted composite having sandwiched structure where Fe3O4 nanoparticles are
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41 attached both on inner and outer side of the carbon wall of GCs, which brings an
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44 exclusive 3D morphology for composite. Thus, carbon backbone provides multiple
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46 advantages such as it connects the particles and brings effective synergism among the
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48 different components of composite along with introducing an additional loss mechanism
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51 i.e. dielectric loss to the magnetic loss mechanism of magnetic component of the
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53 composite. Furthermore, this additional loss mechanism introduced by the GCs provides a
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reasonable impedance characteristic to the composite for improved microwave
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absorption. The resulted composite exhibited minimum RL value of -32 dB at 8.76 GHz
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6 as well as shows lower RL values than -10dB in the absorption bandwidth range from 5.4
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8 to 17 GHz. Further dielectric loss analysed by using Debye dielectric relaxation model
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and free electronic theory as well as magnetic loss analysis done by using eddy current
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13 effects, natural resonance and exchange resonance have proved that Fe3O4 particles and
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15 GCs have strong synergistic effect that brings aforementioned excellent results. Thus, we
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18 believed that as-synthesized hybrid structure is a potential candidate for the microwave
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20 shielding and will open an avenue for the development of functional materials.
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23 2. EXPERIMENTAL METHODS
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26 Synthesis of Graphene capsules: the GCs were synthesized by CCVD through catalytic
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29 decomposition of highly pure acetylene without any carrier gas using ZnO nanoparticles
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31 as catalysts as well as substrate to define the special capsule structure. To be precise, 200
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33 mg ZnO nanoparticles were dispersed on a quartz boat located inside a quartz tube and
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36 heated up to 700 °C under vacuum. As the temperature was stabilized for about 30 min,
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38 C2H2 was introduced into quartz tube for 30 min at a flow rate of 50 mL/min and then
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reaction system was cooled down to room temperature. After completion of reaction the
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43 products were collected from the quartz boat and washed with nitric acid for 24 h in order
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45 to remove the ZnO nanoparticles. Finally, the pure GCs were obtained after 5 times
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48 washing with copious amount of water and ethanol repeatedly and dried at 60 °C for 4
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50 hours in vacuum oven.
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52 Graphene capsules/Fe3O4 composites: the composite was prepared using 2.7 g of FeCl3·6H2O
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55 and 5 g sodium acetate (NaAc) by dissolving in 70 mL and 30 mL of ethylene glycol to
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57 form transparent solution, respectively. The GCs were immersed in the solution of FeCl3,
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followed by ultrasonication for 5 min. The GCs and Fe3+ are in molar radio of 1:5 (GF15),
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6 1:3 (GF13), 1:1(GF11), 3:1(GF31) and 5:1(GF51), respectively. Later on, the NaAc
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8 solution was dropped into the above suspension slowly with continues magnetic stirring.
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The mixture was then sealed in a Teflon-lined stainless steel autoclave and aged at 200 °C
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13 for 24 hours. After natural cooled down to room temperature, the as-synthesized products
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15 were centrifuged and washed with distilled water and absolute ethanol repeatedly for
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18 three times and finally dried in vacuum oven at 60 °C for 4 hours.
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20 Characterization: the morphological and structural features of pure GCs, Fe3O4 nanoparticles
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22 and their composites were characterized using a field emission scanning electron
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25 microscope (FE-SEM, Fei, Inspect-F) with an accelerating voltage of 20.0 kV,
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27 transmission electron microscopy (TEM, Fei-F200) at an accelerating voltage of 200 kV,
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and x-ray diffraction spectrometer (XRD, Panalytical X'Pert PRO diffractometer with Ni-
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32 filtered, the Netherlands). To evaluate the microwave absorption properties of original
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34 GCs and Fe3O4/GCs composites, their mixtures with paraffin were pressed into toroidal
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37 shaped samples of 7.0 mm outer diameter and 3.4 mm inner diameter, respectively. The
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39 electromagnetic parameters of the samples with 30 wt.% Fe3O4 or GC-related materials
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41 were measured at 2–18 GHz with an AV3618 network analyzer. The reflection losses R
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44 (dB) of the composites were calculated according to the transmission line theory, using
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46 the measured data of relative complex permeability and permittivity.
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33 Figure 1. The schematic presentation for the preparation route of GCs/Fe3O4 composites.
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36 3. RESULTS AND DISCUSSION
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39 The synthesis process of Fe3O4/GCs composites is depicted in Figure 1, where ZnO
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nanoparticles were used as structure defining substrate as well as catalyst to decompose
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44 the carbon source in order to prepare GCs. The nitric acid was used to completely remove
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46 the ZnO nanoparticles to obtained pure GCs as host for magnetic nanoparticles. The
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49 Fe3O4 nanoparticles were decorates on the inner and outer surfaces of GCs by utilizing
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51 the hydrothermal method.26 Thus, as-synthesized hybrid has a unique morphology as the
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53 nanoparticles of Fe3O4 are decorated both inner and outer side of the GCs wall that will provide
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56 the strong synergism among the nanoparticles as well as nanoparticles and GCs for better
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microwave absorption through dual loss mechanism e.g. dielectric loss and magnetic loss.
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6 Further the Fe3O4 nanoparticles are connected through the GCs backbone which will reduce the
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8 inter-particle resistance and bring a strong correlation among the particles. The structural
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features of both GCs and GCs/Fe3O4 composites were performed using XRD analysis. The
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13 XRD pattern of pristine GCs is of typical quasi-graphene structure, which shows two
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15 characteristics peaks around 26° and 41° according to the standard card No. 00-001-0640
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18 as shown in Figure 2. Moreover, no peaks were detected for ZnO which indicate the high
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20 purity of as-synthesized GCs after acid treatment. However, the addition of the Fe3O4
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22 nanoparticles to the GCs results in very strong and sharp diffraction peaks correspond to
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25 the Fe3O4 according to the standard card No. 01-075-0033, suggesting their high
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27 crystallinity. Interestingly, the diffraction peaks for graphene are not appeared in case of
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Fe3O4/GCs composites because of the highly strong and sharp reflection from of Fe3O4
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32 and slightly lower crystallinity of GCs.
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55 Figure 2. The XRD patterns of GCs, Fe3O4 and Fe3O4/GCs composites (GF11, GF13 and
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The morphological and microstructures of the GCs and GCs/Fe3O4 composites were
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6 carried out using SEM, TEM and HRTEM studies as shown in Figure 3 and S1. From
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including rod, triangular prism and cubic based on the morphological diversity of ZnO
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13 nanoparticle used as substrate and catalysts. Thus, from these results it can be concluded
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15 that the morphology of the GCs can easily be tuned using the developed method, simply
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18 by selecting the required shape of catalyst nanoparticles which will define the
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20 morphology of the GCs. From the TEM images it is obvious that the GCs are completely
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22 hollow and the catalyst particles are completely removed by the acid treatment, which
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25 assures the high purity of the as-synthesized GCs for further use. It is found that the sizes
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27 of GCs are within the range of 200-500 nm with an average size of ~250 nm. To develop
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the functional materials, GCs were decorated with the Fe3O4 nanoparticles through
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32 hydrothermal reaction as shown in Figure 3c and S1. From Figure S1 it is clear that after
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34 decorating the nanoparticles the GCs maintain their original shape and 3D characteristics
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37 for the GCs/Fe3O4 composites. The high magnification FESEM studies have further revealed
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39 that Fe3O4 particles are closely attached to GCs surface (Figure S1(c)), that made the GC surface
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41 relatively rough. The rough surface along with the strong attachment of particle to GCs are
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44 witnessed that in-situ growth of Fe3O4 nanoparticles on GCs is an effective approach to develop
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46 better synergistic effect among the components, not by simple mixing of two components.
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48 Figure 3c shows the existence of the Fe3O4 nanoparticles on the surface of GCs,
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51 indicating that Fe3O4 nanoparticles have successfully grown on the outer and inner
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53 surfaces of GCs, additional some nanoparticles are also present in the core of the GCs. It
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can be speculated that some Fe3+ ion migrate to the inner part of the GCs to that were
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converted to Fe3O4 under high pressure and temperature. The as-prepared GCs/Fe3O4
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6 composites have a uniform grain diameter distribution of Fe3O4 nanoparticles with an
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8 average size of about 28 nm. Furthermore, from the High magnification TEM image it is
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clearly that GCs have uniform wall with thickness of about 10 nm. The composites with
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13 different ratios of GCs and Fe were prepared to adjust their microwave absorption ability.
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15 The microstructure of the composite was analyzed by evaluation both the walls of the
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18 GCs and crystal structure of the nanoparticles. The Figure 3d depicts the crystal structure
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20 of the Fe3O4 nanoparticles, the lattice spacing of 0.48 nm is found that corresponds to the
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22 plane (111) of Fe3O4 according to the standard card No. 01-075-0033.27 Similarly, the
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25 lattice spacing of 0.34 nm is observed for GCs walls that corresponds to (002) plane of
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27 graphite in accordance with the standard XRD card No. 00-001-0640, shown in Figure 3e.
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Furthermore, the corresponding fast Fourier transform (FFT) studies have further proved
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32 that the Fe3O4 nanoparticles have high crystallinity corresponding to the bright electron
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34 diffraction spots (Figure 3f). Beside this some diffused electron diffraction rings are
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37 found that might be corresponds to relatively low crystalline GCs in the composite
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39 structure. Thus, these results are well-matched with the XRD studies that Fe3O4
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41 nanoparticles have been decorated on the GCs inner and outer surface for better
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44 synergistic effects to improve the functionality of individual components.
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50 Figure 3. The TEM images of (a, b) GCs and (c) GCs/Fe3O4 composites of GF11. The HRTEM
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53 images of (d) Fe3O4 nanoparticles and (e) GCs walls. (f) FFT pattern for GF11 composites.
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In general, high-performance microwave absorption usually comes from efficient
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6 complementarities between complex permittivity and permeability of materials. Single-
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8 typed dielectric loss or magnetic loss in materials results in a weak electromagnetic
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impedance matching. GCs mainly possess the dielectric loss for microwave absorption,
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13 whereas Fe3O4 is a typical magnetic material. Then Fe3O4/GCs composites have the
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15 potential to exhibit excellent EM absorption properties. Most of the related literatures
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18 cover the wax loading in the range of 70%-90% and it found that the amount of wax used
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20 for measurement has great effect on the EM properties. Shibing Ni et al. reported the
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22 influence of wax loading and concluded that the complex permittivity and permeability of
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25 the composite of paraffin wax and Fe3O4 increased linearly with the increase in the volume
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27 fraction of Fe3O4.28 Interestingly, the calculated reflection loss in the wax/Fe3O4 composite
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reaches a maximum value of −21.2 dB with 70% volume fraction of wax. Thus, we have
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32 carried out the measurement for the EM property at the 70% mass percentage of GF
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34 composite, which is required for practical applications. To investigate the microwave
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37 absorption properties of composites, the real part and imaginary part of relative complex
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39 permittivity and permeability for the Fe3O4, pristine GCs and their composites in a
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41 frequency range of 2-18 GHz are measured, as shown in Figure 4. The dielectric loss of
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44 the original Fe3O4 is negligible and magnetic loss dominates the loss mechanisms. In
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46 addition, it can be found that two peaks appear at 9.3 GHz and 16.5 GHz for ε′′ and
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48 dielectric loss factor for GF11 therefore exhibits a significant similar fluctuation in the
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51 range of 2–18 GHz. From the dielectric curves, the GF11 has the stronger fluctuation than
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53 pure GCs, GF13, GF15. The resonance peak amplitudes of GF31 and GF51 become
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smaller than other composites; however, the peak also shifts when adjusting the ratio of
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GC to Fe3O4. It is found that the resonance peak is mainly raised from the pure GCs with
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6 hollow structure, therefore an obvious resonance peak resent in all the GCs-dominant
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8 composites and pure GCs. Thus, the resonance peak can be enhanced by adjusting ratio of
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GCs to Fe3O4. Thus, the resonance peaks are probably associated with the interfaces
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13 between Fe3O4 nanocrystal and hollow GCs, which is due to the displacement current lag
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15 caused by the interface.8, 29 The analysis based on the Debye theory30 and free electron
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18 theory31, two important factors are proposed to be accounting for dielectric loss. One
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20 factor is the combined loss of the dipole polarizations and interfacial polarizations. The
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22 former probably originates from defects in GCs materials, while the latter comes from the
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25 existence of the large amount of interfaces among Fe3O4 nanocrystals and the interfaces
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27 between Fe3O4 nanocrystals and GCs materials. The beautiful designing of the Fe3O4
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nanocrystals on inner and outer surfaces of GCs results in large number of interfaces that
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32 cause the interfacial polarization associated with relaxation could also give rise to
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34 dielectric loss.32-34 The second factor is the contribution of conductivity loss originating
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37 by the GCs, aaccording to the free electron theory ε′′ ≈ 1/2πε0ρf, where ρ is the electrical
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39 resistivity. Thus, the graphene layer of GCs greatly increased the conductivity of the
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24 Figure 4. Measured relative (a, b) complex permittivity, (d, e) complex permeability and (c)
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26 dielectric and (f) magnetic loss values of pure Fe3O4 nanoparticles, pristine GCs and Fe3O4/GCs
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29 composites.
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31 To investigate the microwave absorption property of these materials, the reflection loss
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33 (RL) were calculated according to the transmission line theory.35
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36 Z  Z μ /ε tanhj 
√μ ε  (1)
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" %"
39 RL  20log "#$ '"& (2)
40 #$ &

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42 where Zin is the input impedance of the absorber, Z0 is the impedance of free space, µr is
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44 the relative complex permeability, εr is the complex permittivity, f is the frequency of
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47 microwaves, d is the thickness of the absorber and c is the velocity of light. Figure 5a
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49 shows a comparison of calculated RL curves in the frequency range of 2-18 GHz for the
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51 composites, original GCs and Fe3O4 nanoparticles with a thickness of 3.5 mm. The
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54 minimum RL of the Fe3O4, GCs and the Fe3O4/GCs composites are about -5 dB, -19 dB
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56 and -32 dB, respectively. To investigate the RL performance of the products in detail,
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three-dimensional RL values of the products are shown in Figure 5b-d. The minimum RL
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6 of the GF11 composites is -32 dB with thickness of about 3.5 mm at 8.76 GHz and the
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8 absorption bandwidths with RL lower than -10 dB is from 5.4 to 17 GHz for an absorber
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thickness of 2.5-4 mm as shown in Figure 5d. Moreover, it can be seen that both
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13 minimum RL value and the absorption bandwidth have enhanced a lot compared with
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15 Fe3O4 and GCs, demonstrating that this novel Fe3O4/GCs composite structure improve the
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18 microwave absorption property of GCs through multiple advantages and mechanisms.
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20 Firstly, it is generally known that to obtain an effective microwave, efficient
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22 complementarities between the relative permittivity and permeability should be
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25 satisfied.36 The loss mechanism of Fe3O4/GCs nanoparticles consists of both magnetic
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27 and dielectric loss and its impedance characteristic has been significantly tuned compared
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with GCs and Fe3O4. Secondly, interfaces around the nanoparticles and the polarization of
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32 free carriers in graphene result an enhancement in the microwave absorption property of
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34 the composites.19 The charge transfer between GCs and Fe3O4 also occurs with little
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37 hindrance. Therefore, the interfacial polarization and associated relaxation should
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39 contribute to the enhanced EM absorption properties. Conventionally the relaxation
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41 process, which can be described by a Cole–Cole semicircle37, has an important influence
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34 Figure 5. (a) The microwave RL curves of pure Fe3O4, GCs and GF11 (GC:Fe=1:1) composite
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36 in the frequency range of 2-18 GHz. The simulated curves for electromagnetic wave loss of (b)
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Fe3O4, (c) pristine GCs and (d) GF11 composite.
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41 According to the Debye dipolar relaxation30, 38, 39, the relative complex permittivity (εr)
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43 can be expressed by the following equation:
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45 , %,
46 ε  ε( ) iε((  ε+ ) /'012
- .
(3)
&
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51 where τ0, εs, and ε∞ are the relaxation time, the static dielectric constant, and the dielectric
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53 constant at infinite frequency, respectively. From Eq. (3), it can be deduced as given
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3 , %,
4 ε(  ε+ ) - . 3 (4)
/'12  &
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6 12& ,- %,. 
7 ε((  /'12& 3
(5)
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10 According to Eqs. (4) and (5), the relationship between ε' and ε" can be further deduced,
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,- ',.  ,- %,. 
12 ε( −  ) ε((     (6)
13  
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15 Thus, the plot of ε' versus ε" is a single semicircle, which is usually defined as a Cole–
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17 Cole semicircle and each semicircle corresponds to one Debye relaxation process. Plots of
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20 ε" versus ε' for Fe3O4, GCs, and their composites are shown in Figure 6, where both large
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22 and small Cole–Cole semicircles were found. For Fe3O4, a relatively large smooth
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24 semicircle accompanied by a tiny semicircle is found in Figure 6a and this large
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27 semicircle becomes more irregular and small semicircles appear for the GF15 and GF13
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29 samples as shown in Figure 6b and 6c, respectively. Interestingly, four small semicircles
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and a whole circle consisting of two large semicircles are found for GF11 sample as
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34 presented in Figure 6d, which consequently indicate the existence of several dielectric
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36 relaxation processes. However, only small semicircles are found for GF31 and GF51
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samples as shown in Figure 6e and f. Similarly, the middle-scale semicircle and small
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41 ones exists for the pure GCs sample, which may suggest that the dielectric relaxation
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43 processes happen in three discontinues way, shown in Figure 6g.15 The mechanisms of the
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46 permittivity dispersion can be interpreted in terms of the Debye dielectric relaxation
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48 model (Cole–Cole model). For the individual component of pure Fe3O4 and GCs, there is
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50 single or discontinuous Debye relaxation processes, while for the Fe3O4/GCs composite
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53 several continuous Debye relaxation processes. The Debye relaxation processes can be
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55 enhanced by adjusting the molar ratio of Fe3O4 to GCs. The existence of interfaces in this
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heterogeneous composite gives rise to the interfacial polarization or the Maxwell–Wagner
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effect.40 It becomes easy to happen in the 3D GCs with relatively high conductivity due to
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6 the accumulation of charges at the interfaces and the formation of large dipoles on Fe3O4
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53 Figure 6. Typical Cole–Cole semicircles (ε" versus ε') for (a) Fe3O4, (b) GF15, (c) GF13,
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(d) GF11, (e) GF31, (f) GF15 and (g) GCs in the frequency range of 2–18 GHz.
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The magnetic loss is another important factor that contributes to EM wave attenuation
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6 in Fe3O4/GCs composites. It is reported that magnetic loss mainly comes from eddy
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8 current effect, natural and exchange resonance in the microwave frequency band.15 The
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eddy current loss can be expressed by the equation of µ”=2πµ0(µ’)2σd2f/3, where µ0 is the
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13 permeability of vacuum, d is the thickness and σ is the electrical conductivity of the
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15 composite, thus existence of the GCs will bring higher eddy current loss because of their
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18 high conductivity and might contribute positively to magnetic loss. The values of µ”(µ’)–
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2 –1
20 f should be constant in case if the magnetic loss only originates from the eddy current
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22 loss. However, in present case the values of µ”(µ’)–2f–1 are not constant which suggest that
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25 the magnetic loss does not only originate from eddy current loss. Furthermore, the natural
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27 resonance can be another source of the magnetic loss and can be described by the natural-
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resonance equation as follows:
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32 2π67  89: (7)
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34 9:  4|=/ |/39? @A (8)
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37 where r is the gyromagnetic ratio, Ha is the anisotropic energy, |K1| is the anisotropic
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39 coefficient and Ms is saturation magnetization. As shown in Figure 7, the plots of µ”(µ’)–
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41 2 –1
f vs. frequency for the GCs, Fe3O4 and their composites differ from each other. For
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44 pure Fe3O4, the value of µ”(µ’)–2f–1 keeps constant at 8-12.8 GHz originating from the
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46 eddy current loss only as it drops and then recovers at the range of 12.8-17.2 GHz due to
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the natural response might be contributed by the small size effect. In contrast, the GCs
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51 exhibit the natural resonance in the low frequency range of 2-8 GHz and remained
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53 constant over the left range up to 18 GHz. It is worth noting that by combining the eddy
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natural resonance mainly, composite comes up with mixed mechanism comprising both
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6 eddy current loss and natural resonance phenomenon for magnetic loss in the composites.
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8 Thus, the natural resonance can be tuned by changing particle size and anisotropic energy
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according to the natural-resonance equation for the Fe3O4/GCs composites. On one hand,
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13 the smaller size of Fe3O4 gives rise to the increase in anisotropic energy of composite due
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15 to the surface anisotropic field by the reduced size effect.40 On other hand, as the Ms value
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18 of the Fe3O4/GCs composites should be lower than that of the pure Fe3O4, therefore, the
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20 composite will come up with higher anisotropic energy than the pure Fe3O4. Thus, it is
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22 well-known that the higher anisotropic energy is very helpful for the improved
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25 microwave absorption properties.40 Furthermore, the exchange resonance can also be found
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27 in ~4.9 GHz and 6.5 GHz for GCs-based samples GF31 and GF51. The natural response
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peaks shifts to the 16.3GHz for the Fe3O4-based samples such as GF13 and GF15. Some
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32 fluctuations happen for the GF11 sample in 11-17 GHz, which may be caused from the
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34 exchange resonance between GCs and Fe3O4 nanocrystals. Interestingly, the negative
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37 imaginary permeability of some samples such as GF11 is found between 2 and 18 GHz, which
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39 indicates that magnetic energy is radiated from these samples due to the motion of charges
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41 among the 3D hollow GCs. As the motion of charges in an electromagnetic field produce an
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44 alternating electric field and induces a magnetic field according to the Maxwell equations .37
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46 Furthermore, a series of experiments were conducted to investigate the effect of molar
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48 ratio of Fe3O4 and GCs on the microwave absorption property of the composites, since a
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51 high percentage of Fe3O4 or GCs would lead to relatively poor microwave absorption
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53 because of the imbalance between the dielectric and magnetic loss. Figure 8 shows the
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reflection loss of GF51, GF31, GF13 and GF15, having the minimum values of -27dB, -
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31 dB, -16 dB and -12 dB, respectively. It can be seen that with the increasing percentage
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6 of Fe3O4, the microwave absorption behaviors of GF51 and GF31 perform better than
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8 GF13 and GF15. Importantly, when the molar radio of Fe and GCs is of 1:1, the
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microwave absorption property is best among all the samples, which is due to a suitable
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13 EM behavior. Therefore, by decorating the GCs with Fe3O4, the Fe3O4/GCs composite of
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15 GF11 and GF31 shows reduced imaginary permittivity and increased imaginary
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18 permeability compared to pristine GCs, which helps to improve the level of impedance
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20 matching. Thus, the loss in eddy current in the range of 8-12 GHz is observed for all the
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22 samples due to their unique structural features, further small size and 3D hollow structure
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25 contributes a lot in the enhancement of magnetic loss in the forms of natural and exchange
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27 resonance as well as the magnetic loss can be tuned by adjusting the molar ratio of
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constituents for composite, which proves our composite a versatile material for
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32 microwave absorption.
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Figure 7. Plots of µ’’(µ’)–2f–1 vs. frequency for the samples of Fe3O4, GF15, GF13, GF11,
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58 GF31, GF51 and GCs.
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32 Figure 8. 3D representations of RL for (a) GF51, (b) GF31, (c) GF13 and (d) GF15 composites
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35 in the frequency range of 2-18 GHz.
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38 CONCLUSIONS
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41 In summary, we have developed a novel Fe3O4/GCs composite with enhanced
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microwave absorption property using a combination of CCVD and facile hydrothermal
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46 method. The introduction of Fe3O4 nanoparticles around GCs not only significantly
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48 improve magnetic loss in form of eddy current effects, natural and exchange resonance
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51 for developed composite, but also produces the consequent dielectric relaxation
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53 processes, leading to a rational impedance characteristic compared with pure GCs and
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55 Fe3O4. Moreover, the microwave absorption property of the composites could be tuned by
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58 varying the percentage of Fe3O4 loadings. Better RL of -32 dB, broad effective bandwidth
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5.4 to 17 GHz for RL lower than -10 dB, low density and good chemical stability of
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6 Fe3O4/GCs composites make it to be a promising candidate as a microwave absorber. Due
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8 to their better electrical, chemical and mechanical properties these materials can also be
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applied to other fields such as photocatalysis and energy storage devices as well as
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13 developed methods open up an avenue to develop new functional materials.
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15 ASSOCIATED CONTENT
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19 Supporting Information. The SEM images, complex permittivity and permeability of pure
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21 Fe3O4 and Fe3O4/GCs composites. This material is available free of charge via the Internet at
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23 http://pubs.acs.org.
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25
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27 AUTHOR INFORMATION
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29
30 Corresponding Author
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32 * Xian Jian (jianxian@uestc.edu.cn)
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34
35 * Weidong He (weidong.he@uestc.edu.cn)
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37 * Nasir Mahmood (nasirm38@gmail.com )
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39
40 Author Contributions
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43 Xian Jian, Biao Wu, Yufeng Wei and Weidong He designed the experiment and carried out
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45 synthesis of materials and performed all the characteristic and properties, they also wrote the
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47
48
manuscript. Xiaolin Wang and Nasir Mahmood provided guidance in experiment and in writing
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50 manuscript. All the authors discussed the results. ζThese authors contributed equally.
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52
ACKNOWLEDGMENT
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55 This work was financially supported by the National Natural Science Foundation of
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58 China (Grant No. 51402040), the Open Foundation of State Key Laboratory of Electronic
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Thin Films and Integrated Devices (KFJJ201411), China Postdoctoral Science
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6 Foundation (2015M582539) and the National Hi-Tech Research and Development
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8 Program (863 Program) of China (No. 2015AA034202).
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51 38. Wen, B.; Cao, M.S.; Hou, Z.L.; Song, W.L.; Zhang, L.; Lu, M.M.; Jin, H.B.; Fang, X.Y.;
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53 Wang, W.Z.; Yuan, J. Temperature Dependent Microwave Attenuation Behavior for Carbon-
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39. Chen, Y.H.; Huang, Z.H.; Lu, M.M.; Cao, W.Q.; Yuan, J.; Zhang, D.Q.; Cao, M.S. 3D
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6 Fe3O4 Nanocrystals Decorating Carbon Nanotubes to Tune Electromagnetic Properties and
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8 Enhance Microwave Absorption Capacity. J. Mater. Chem. A 2015, 3, 12621-12625.
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40. Zong, M.; Huang, Y.; Zhao, Y.; Sun, X.; Qu, C.; Luo, D.; Zheng, J. Facile Preparation,
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13 High Microwave Absorption and Microwave Absorbing Mechanism of RGO-Fe3O4 composites.
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15 RSC Adv. 2013, 3, 23638-23648.
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