Professional Documents
Culture Documents
Bioinspired Fabrication of Magneto-Optic Hierarchical Architecture by Hydrothermal Process From Butterfly Wing
Bioinspired Fabrication of Magneto-Optic Hierarchical Architecture by Hydrothermal Process From Butterfly Wing
a r t i c l e i n f o a b s t r a c t
Article history: We developed a green solution to incorporate nano-Fe3O4 into the hierarchical architecture of a natural
Received 21 December 2010 butterfly wing, thus obtaining unique magneto-optic nanocomposites with otherwise unavailable
Received in revised form photonic features. Morphological characterization and Fourier Transform Infrared–Raman Spectroscope
8 March 2011
measurements indicate the assembly of Fe3O4 nanocrystallites. The magnetic and optical responses of
Available online 12 March 2011
Fe3O4/wing show a coupling effect between the biological structure and magnetic material. The
Keywords: saturation magnetization and coercivity values of the as-prepared magneto-optic architecture varied
Bioinspired with change of subtle structure. Such a combination of nano-Fe3O4 and natural butterfly wing might
Hydrothermal process create novel magneto-optic properties, and the relevant ideas could inspire the investigation of
Magnetite
magneto-optical devices.
Hierarchical architecture
Crown Copyright & 2011 Published by Elsevier B.V. All rights reserved.
0304-8853/$ - see front matter Crown Copyright & 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2011.03.015
W. Peng et al. / Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069 2065
advance on the up two method using ferrous sulfate heptahydrate 2.3. Sample characterization
as the only iron source and hydrogen peroxide as the oxidant. We
develop the one-step synthesis of hierarchical microstructures of The as-synthesized samples were examined by FTIR measure-
magnetite magnetic optical architecture from butterfly wing via ments using a Bruker EQUINOX 55 instrument. X-ray diffraction
Hydrothermal Method (HM). The as-synthesized sample exhibits (XRD) measurements were carried out with a Bruker-AXS X-ray
increase magnetic properties with the ultrafine structure. Since diffractometer system by applying CuKa radiation. The investiga-
hierarchy porous structure could participate in tuning nano-Fe3O4 tions of the morphologies and microstructures of the products were
magneto-optical properties, the combination of nano-Fe3O4 and carried out using a FESEM (FEI XL30). The FESEM was operated
wing scales would be promising and significant. This investiga- under 5.0 kV (Acc.V). Transmission electron micrographs (TEM),
tion may also provide helpful information for the synthesis of high-resolution transmission electron micrographs (HRTEM), and
other magnetic materials with peculiar structures. selected area electron diffraction (SAED) patterns were obtained on
a JEOL JEM-2100F instrument. Reflection spectra were measured on
a UV spectrometer (Cary 500) and an integrating sphere. The
2. Experimental magnetization measurements were performed using a Vibrating
Sample Magnetometer (VSM, Lakeshore 7407) at room temperature
2.1. Materials to investigate the magnetic properties.
Table 1
Procedure factor of different method synthesis magnetic butterfly wing.
AOM 8% NaOH ethanol solution 60 1C, 1 h 0.1 mol FeCl2 4H2O,0.1 mol citric acid monohydrate, 100 ml ethanol sintering under air
VRM 8% NaOH ethanol solution 60 1C, 1 h 2 mol/L Fe(NO3)3 9H2O ethylene glycol solution vacuum sintering
HM EDTA/DMF 110 1C, 6 h 0.009mol FeSO4 7H2O, 20 ml deionized water, 10 ml of PEG 20000 hydrothermal method
solution (50 gL-1), 10 ml of (2.5%) ammonia 0.27 ml H2O2
2066 W. Peng et al. / Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069
unit-cell parameter of 0.8396 nm and peaks at 2y ¼29.981, 35.399, standard card (JCPDS no. 19- 0629), The average grain sizes are
43.020, 56.979, and 62.579, can be assigned to (2 2 0), (3 1 1), (4 0 0), calculated to be around 26 nm, according to the Scherrer formula.
(5 1 1), and (4 4 0) planes of Fe3O4, which were identical with the The broadening of the reflection peak also indicates the formation of
the ultrafine nanoparticles. It is known that Fe3O4 can be oxidized to g-
Fe2O3, which can be further transformed into a-Fe2O3 at higher
temperature. The diffraction peaks at (1 1 3), (2 1 0), (2 1 3), and
(2 1 0) are the characteristic peaks of g-Fe2O3, and a-Fe2O3, respec-
tively [26]. Herein, No impurity peaks were detected, indicating the
high purity of main product.
The mechanism of Hydrothermal Method (HM) was studied by
Fourier Transform Infrared–Raman Spectroscope (FTIR) spectrum
in Fig. 2. The natural Butterfly wing presents characteristic bands of
protein and chitin. The absorption bands at 1652 and 1542 cm 1
corresponds to amide I mode (primarily CQO stretch) and amide II
(primarily NH in-plane bend plus CN stretch) [27], respectively. The
bands at 1157, 1114, 1074, and 1029 cm 1 should be assigned to
the vibrational motion of characteristic C–O bonds of chitin. The
band near 1726 cm 1 might be the COOH of glutamic and aspartic
acid residue and the O–H out-plane deformation vibration around
band 950 cm 1 confirm the existence of COOH groups [28]. As
Fig. 1. XRD patterns of the products synthesize through Vacuum Reduction depicted before, the natural wing is treated with EDTA/DMF
Method (a) and Hydrothermal method (b). activation medium to gain more COO– active sites, which is
confirmed by the FTIR results. In detail, OH stretch mode of the
COOH group around 3293 cm 1 (supporting information) decreases
sharply, along with the slight intensification of the 1407 cm 1 band
(COO– stretching) [29]. In the growth stage, the following mechan-
isms of the Fe3O4 nanoparticles embedded into the honeycomb
structure of wing scales were proposed to occur: Fe3O4 nuclei
(nanoparticles) were increasingly formed on the surface of the
substrates. The active sites of substrates (like COO–, O–H) bind
Fe3O4, which is verified by the FTIR results. In the spectrum the new
band at 579 cm 1 corresponded to vibrations of the Fe–O bonds in
the crystalline lattice of magnetite (Fe3O4) [30]. The enhancement
of O–H out-plane deformation vibration (OHyO) near 950 cm-1
indicated magnetite associate with hydrogen bonding of COOH. The
antisymmetric stretching vibration of COO– around 1543 cm 1 is
blueshifted as compared to the activated wing and original wing,
owing to the chelation between the COOH/COO– groups and
magnetite in the final product [31]. Hence, butterfly wings could
be activated by EDTA/DMF suspension to serve as reactive sites and
successive assembly of Fe3O4. Besides, the result of XRD agreed well
with that of the FTIR.
Fig. 2. FTIR spectrum of original wing, activated wing, and final product Fe3O4/ FESEM images in Fig. 3 show the well-organized hierarchical
wing fabricated using HM. cross-ribbing structure of the target product Fe3O4/wing
Fig. 3. FESEM images of natural wing (a,d), final product Fe3O4 architecture obtained by vacuum sintering (b,e), and hydrothermal method (c,d), respectively. (Forewing of
male Euploea mulciber butterflies was used.)
W. Peng et al. / Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069 2067
wavelength ranges with the increase in the materials’ reflective The magnetic properties of the Fe3O4/wing (Fig. 7(a)) synthesized
index, present results are quite reasonable. The reflection peak at using VRM and the quasi-honeycomb like magnetite (Fig. 7(b)),
410 nm implied that the HM synthesized magnetite architecture cross-ribbing magnetite (Fig. 7(c)), and Fe3O4 nanoparticles
(Fig. 4(c)) inherits the optical response of natural wing. Besides, we
attribute the slight enhancement reflection peak of Fe3O4 architec-
ture composite around 690 nm to the change of optical parameters
(refractive index and lattice distance). Relative to natural wing, the
lattice distance of the magneto-optic architecture with a coating
layer of nano-Fe3O4 was decreased, and the surface of the final
product is much rougher. The rougher surface can enhance scatter-
ing, which also explain the low reflectance of the magnetite
architecture.
Research shows that the patterns of magnetic materials are
essential to their magneto-optic properties. Herein, another type of
wing scales with different patterns is applied to mediate the
assembly of nano-Fe3O4. Fig. 6(d–f) present the quasi-honey comb
like magnetite architecture corresponding to the natural Papilio paris
butterfly wings (Fig. 6 (a–c)).The natural Papilio paris butterflies
show the well-organized quasi-honeycomb structure, the porous is
consisted from micrometer down to 300 nm. The direct evidence of
the formation of Fe3O4 nanoparticles coating on natural butterfly
wing is given in Fig. 6(d–f). It is apparent that Fe3O4 nanoparticle is
homogeneous coated on the subtle structure of Papilio paris butter- Fig. 7. Magnetization loops of Fe3O4/wing (a) synthesized using VRM, quasi-
flies and the porous of final product is slight smaller compared to the honeycomb like magnetite (b), cross-ribbing magnetite (c), and Fe3O4 nanoparticles
natural butterfly wing because of the coating layer. (d) prepared using HM.
Fig. 6. FESEM images of natural wing (a–c) and final product Fe3O4/wing (d–f) obtained using a typical procedure as described in the experimental section. (Forewing of
male Papilio paris butterflies was used.)
W. Peng et al. / Journal of Magnetism and Magnetic Materials 323 (2011) 2064–2069 2069
Table 2
Magnetic characteristics of samples with different morphologies.
(Fig. 7(d)) synthesized using HM measured at room temperature are Shanghai University School and Materials Science and Engineering
illustrated in Fig. 7. The hysteresis loop of samples shows a ferro- for Magnetization loops measurement, Qin Hong from State Key Lab
magnetic behavior with saturation magnetization of 7.794, 19.313, of Metal Matrix Composites for XRD measurement, and SJTU
30.939, and 71.955 emu/g and coercivity of 117.18, 121.26, 118.58, Instrument Analysis Center for FESEM and FTIR measurements.
and 94.532 Oe, respectively. The saturation magnetization of Fe3O4/
wing is much lower than Fe3O4 nanoparticles, while the Ms of the
Fe3O4 nanoparticles were consistent with the reported values [34] Appendix A. Supporting information
(Table 2). Although the source of low saturation magnetization is
not clear, the chitin scaffold in the samples and specific structures Supplementary data associated with this article can be found
preventing Fe3O4 nucleus from magnetizing in directions other than in the online version at doi:10.1016/j.jmmm.2011.03.015.
along their easy magnetic axes [35], might be two major reasons.
Besides the coercivity of sample c is much higher than sample b
in Fig. 7, this may be due to shape anisotropy and different stress of References
cross-ribbing structure and quasi-honeycomb like structure [36].
[1] K. Autumn, Y.A. Liang, S.T. Hsieh, W. Zesch, W.P. Chan, T.W. Kenny, R. Fearing,
R.J. Full, Nature 405 (2000) 681–685.
[2] H. Lee, B.P. Lee, P.B. Messersmith, Nature 448 (2007) 338–341.
4. Conclusions
[3] R. Blossey, Nat. Mater. 2 (2003) 301–306.
[4] S.A. Jewell, et al., N. J. Phys. 9 (2007) 99.
In summary, nano-Fe3O4 was incorporated into butterfly [5] X. Zhang, F. Shi, J. Niu, Y. Jiang, Z. Wang, J. Mater. Chem. 18 (2008) 621–633.
wings successfully by a simple, cheap and harmless hydrothermal [6] X. Feng, L. Jiang, Adv. Mater. 18 (2006) 3063–3078.
[7] A.R. Parker, H.E. Townley, Nat. Nano 2 (2007) 347–353.
method using ferrous sulfate heptahydrate as the only iron source [8] Z. Wang, Di Zhang, Tongxiang Fan, Jian Ding, Qixin Guo, Hiroshi Ogawa,
and hydrogen peroxide as the oxidant. Natural butterfly wings Nanotechnology 17 (2006) 840.
could be activated via an EDTA/DMF treatment to get more COO– [9] Huang WangWang, Z.L. Wang, Nano Lett., 6 (2006) 2325–2331.
[10] G. Cook, P.L. Timms, C. Göltner-Spickermann, Angew. Chem. Int. Ed. 42 (2003)
active sites on their structure surfaces, and then serve as the 557–559.
nucleation sites of Fe3O4. As-prepared nano-Fe3O4 are spinel [11] J. Silver, R.W.T.G. Ireland, G.R. Fern, J. Mod. Opt. 52 (2005) 999–1007.
structure with average diameter of 26 nm and homogeneous [12] Z. Wang, et al., Nanotechnology 17 (2006) 840.
[13] H.S. Fang Song, Jie Han, Di Zhang, Zhixin Chen, Nanotechnology 20 (2009)
coated on the natural wings. The saturated magnetization values 495502.
and coercivity values changes with the structures affection, owing [14] J. Han, H. Su, D. Zhang, J. Chen, Z. Chen, J. Mater. Chem. 19 (2009) 8741–8746.
to the corresponding shape anisotropy and stress. The obtained [15] Q.A. Pankhurst, J.C.S.K. Jones, J. Dobson, J. Phys. D: Appl. Phys. 36 (2003)
R167.
nano-Fe3O4/wings inherit the optical response of natural wing [16] H. Zeng, J. Li, J.P. Liu, Z.L. Wang, S. Sun, Nature 420 (2002) 395–398.
though the reflectance intensity was a little lower. The new [17] M. Inoue, K.i. Arai, T. Fujii, M. Abe, J. Appl. Phys. 83 (1998) 6768–6770.
steamed bread reflection peak must be the affection of the change [18] A. Fedyanin, T. Yoshida, K. Nishimura, G. Marowsky, M. Inoue, O. Aktsipetrov,
JETP Lett. 76 (2002) 527–531.
of optical parameters (refractive index and lattice distance).
[19] M.H. Kryder, J. Appl. Phys. 57 (1985) 3913–3918.
Moreover, corresponding optical properties are supposed to be [20] H. Kato, T. Matsushita, A. Takayama, M. Egawa, K. Nishimura, M. Inoue, Magn.
tunable by the nano-Fe3O4/wing assembly patterns and it may be IEEE Trans. 38 (2002) 3246–3248.
useful for applications as magnetic recording media since Fe3O4 [21] P. Vukusic, J.R. Sambles, Nature 424 (2003) 852–855.
[22] N.J. Tang, W. Zhong, H.Y. Jiang, X.L. Wu, W. Liu, Y.W. Du, J. Magn. Magn.
itself has many functional usages, these composites can be served Mater. 282 (2004) 92–95.
as building blocks to construct micro- and nanoscale devices, such [23] M.T. Chang, L.J. Chou, C.H. Hsieh, Y.L. Chueh, Z.L. Wang, Y. Murakami,
as magneto-optic spatial light modulator and optical waveguide D. Shindo, Adv. Mater. 19 (2007) 2290–2294.
[24] J. Xu, H. Yang, W. Fu, K. Du, Y. Sui, J. Chen, Y. Zeng, M. Li, G. Zou, J. Magn.
isolator. Also, for some of the beautiful iridescent butterfly wings Magn. Mater. 309 (2007) 307–311.
are photonic crystal materials, the method presented here could [25] J. Wan, X. Chen, Z. Wang, X. Yang, Y. Qian, J. Cryst. Growth 276 (2005)
be used for potential applications in magneto-photonic crystals. 571–576.
[26] S. Sun, H. Zeng, D.B. Robinson, S. Raoux, P.M. Rice, S.X. Wang, G. Li, J. Am.
The magneto-optical property of the sample is still under inves- Chem. Soc. 126 (2003) 273–279.
tigation. Since the method of incorporated nanoparticles into [27] Y. Iridag, M. Kazanci, J. Appl. Polym. Sci. 100 (2006) 4260–4264.
natural hierarchical structure could inspire the investigation of [28] J.S. Church, G.L. Corino, A.L. Woodhead, Biopolymers 42 (1997) 7–17.
[29] P.K. Sengupta, S. Krimm, Biopolymers 24 (1985) 1479–1491.
materials coupling with special structure. A related research is [30] M. Ma, Y. Zhang, W. Yu, H.-y. Shen, H.-q. Zhang, N. Gu, Colloids Surf. A:
currently on the way which should brighten new valuable Physicochem. Eng. Aspects 212 (2003) 219–226.
applications in magnetic recording field. [31] P.C. Morais, S.W. da Silva, M.A. Godoy Soler, N. Buske, Biomol. Eng. 17 (2001)
41–49.
[32] J.G. Yu Chen, Shenmin Zhu, Fan Tongxiang, Di Zhang, Qixin Guo2, Appl. Phys.
Lett. 94 (2009) 053901.
Acknowledgements [33] K. Kertész, Z. Bálint, Z. Vértesy, G.I. Márk, V. Lousse, J.P. Vigneron, M. Rassart,
L.P. Biró, Phys. Rev. E 74 (2006) 021922.
This work was financially supported by Natural Science Funding [34] J. Sun, S. Zhou, P. Hou, Y. Yang, J. Weng, X. Li, M. Li, J. Biomed. Mater. Res. Part
A 80A (2007) 333–341.
of Shanghai (08ZR1410200) and Fundings (07DJ14001, 50671065, [35] J. Wang, Q. Chen, C. Zeng, B. Hou, Adv. Mater. 16 (2004) 137–140.
50772067, and 2009DF52410).The authors thank Qin Bai from [36] H.-U. Worm, Geophys. J. Int. 133 (1998) 201–206.