The Structure and ferromagnetism of carbon nanofibers from polyacrylonitrile/ polyvinylpyrrolidone
Keywords:Electrospinning, Ferromagnetic carbon, Magnetic, Nanofiber, Polymer
Room-temperature ferromagnetism was successfully induced in carbon. Carbon nanofibers were fabricated using sequential electrospinning of polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP). The morphologies, crystal structures, chemical bonding states and magnetic properties were characterized over three different weight ratios which were 10:0, 7:3 and 6:4 of PAN/PVP. The carbon nanofibers obtained after pyrolysis of polymer fibers were placed inside a tube furnace using a three steps process: stabilization, carbonization, and activation at 800℃. XRD patterns indicated the amorphous structure of carbon. The average diameter of the carbon nanofibers was between 340 nm to 511 nm. Raman analysis was used to determine the carbon qualities in the samples by the numbers of sp3/sp2 hybridized atoms. The chemical analysis obtained XPS indicated that there were no magnetic contaminants. The PAN/PVP weight ratio of 6:4 showed ferromagnetic carbon nanofibers with the highest specific saturation magnetization as ~144.2 m-emu×g-1 at 300 K. This indicated that the mixing of sp2-sp3 carbon system had localized magnetic moments. This finding suggests an inexpensive method for preparing magnetic particles and human-friendly ways to produce magnetic material without metals. These results inspire us to further research on the potential of carbon materials, as a completely new class of magnetic devices.
J. M. D. Coey, "d0 Ferromagnetism," Solid State Sciences, vol. 7, no. 6, pp. 660-667, 2005.
A. Goldman and A. Goldman, "Applications and Functions of Ferromagnetic Materials," in Handbook of Ferromagnetic Materials, Kluwer Academic Publishing, 1999, pp. 1-15.
X. L. Wu, R. S. Wang, J. Cheng, G. H. Zhong, X. J. Chen, Y. Gao, and Z. B. Huang, "Room temperature ferromagnetism in naphthalene," Carbon, vol. 36, pp. 125-129, 2018.
P. Esquinazi and R. Höhne, "Magnetism in carbon structures," Journal of Magnetism and Magnetic Materials, vol. 290-291, pp. 20-27, 2005.
R. Caudillo, X. Gao, R. Escudero, M. José-Yacaman, and J. B. Goodenough, "Ferromagnetic behavior of carbon nanospheres encapsulating silver nanoparticles," Physical Review B: Condensed Matter and Materials Physics, vol. 74, no. 21, pp. 1-12, 2006.
Z. He, H. Xia, X. Zhou, X. Yang, Y. Song, and T. Wang, "Raman study of correlation between defects and ferromagnetism in graphite," Journal of Physics D: Applied Physics, vol. 44, no. 8, pp. 1-9, 2011.
J. Červenka, M. I. Katsnelson, and C. F. J. Flipse, "Room-temperature ferromagnetism in graphite driven by two-dimensional networks of point defects," Nature Physics, vol. 5, no. 11, pp. 840-844, 2009.
T. Saito, D. N. Hamane, S. Yoshii, and T. Nojima, "Ferromagnetic carbon materials prepared from polyacrylonitrile," Applied Physics Letters, vol. 98, no. 5, pp. 12-15, 2011.
H. Pardo, N. D. Khan, R. Faccio, F. M. A. Moreira, L. F. Werner, T. Makarova, and Á.W. Mombrú, "Raman characterization of bulk ferromagnetic nanostructured graphite," Physica B: Condensed Matter, vol. 407, no. 16, pp. 3206-3209, 2012.
S. S. Rao, S. N. Jammalamadaka, A. Stesmans, V. V. Moshchalkov, J. V Tol, D. V. Kosynkin, A. H. Duque, and J. M. Tour, "Ferro-magnetism in graphene nanoribbons: Split versus oxidative unzipped ribbons," Nano Letters, vol. 12, no. 3, pp. 1210-1217, 2012.
P. Esquinazi, D. Spemann, R. Höhne, A. Setzer, K. H. Han, and T. Butz, "Induced magnetic ordering by proton irradiation in graphite," Physical Review Letters, vol. 91, no. 22, pp. 8-11, 2003.
X. Yang, H. Xia, X. Qin, W. Li, Y. Dai, X. Liu, Y. Xia, S. Yan, and B. Wang, "Correlation between the vacancy defects and ferromagnetism in graphite," Carbon, vol. 47, no. 5, pp. 1399-1406, 2009.
S. Okada, K. Nakada, K. Kuwabara, K. Daigoku, and T. Kawai, "Ferromagnetic spin ordering on carbon nanotubes with topological line defects," Physical Review B: Condensed Matter and Materials Physics, vol. 74, no. 12, pp. 2-5, 2006.
Z. Zanolli and J. C. Charlier, "Spin transport in carbon nanotubes with magnetic vacancy-defects," Physical Review B: Condensed Matter and Materials Physics, vol. 81, no. 16, 2010.
U. Weissker, S. Hampel, A. Leonhardt, and B. Büchner, "Carbon nanotubes filled with ferromagnetic materials," Materials (Basel), vol. 3, no. 8, pp. 4387-4427, 2010.
H. Ohldag, T. Tyliszczak, R. Höhne, D. Spemann, P. Esquinazi, M. Ungureanu, and T. Butz, "Π-Electron Ferromagnetism in Metal-Free Carbon Probed by Soft X-Ray Dichroism," Physical Review Letters, vol. 98, no. 18, 2007.
S. Talapatra, P. G. Ganesan, T. Kim, R. Vajtai, M. Huang, M. Shima, G. Ramanath, D. Srivastava, S. C. Deevi, and P. M. Ajayan, "Irradiation-induced magnetism in carbon nanostructures," Physical Review Letters, vol. 95, no. 9, 2005.
A. Komlev, E. Lähderanta, E. Shevchenko, and N. Vorob’ev-Desyatovskii, "Magnetism of purified amorphous carbon," EPJ Web of Conferences, vol. 185, pp. 8-11, 2018.
Y. W. Ma, Y. H. Lu, J. B. Yi, Y. P. Feng, T. S. Herng, X. Liu, D. Q. Gao, D. S. Xue, J. M. Xue, J. Y. Ouyang, and J. Ding, "Room temperature ferromagnetism in Teflon due to carbon dangling bonds," Nature Communications, vol. 3, 2012.
E. Lähderanta, A. V. Lashkul, K. G. Lisunov, D. A. Zherebtsov, D. M. Galimov, and A. N. Titkov, "Magnetic properties of carbon nanoparticles," IOP Conference Series: Materials Science and Engineering, vol. 38, no. 1, pp. 1-7, 2012.
G. Z. Magda, X. Jin, I. Hagymási, P. Vancsó, Z. Osváth, P. N. Incze, C. Hwang, L. P. Biró, and L. Tapasztó," Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons," Nature, vol. 514, no. 7524, pp. 608-611, 2014.
P. O. Lehtinen, A. S. Foster, A. Ayuela, A. Krasheninnikov, K. Nordlund, and R. M. Nieminen, "Magnetic Properties and Diffusion of Adatoms on a Graphene Sheet," Physical Review Letters, vol. 91, no. 1, pp.1-4, 2003.
Y. Zhang, S. Talapatra, S. Kar, R. Vajtai, S. K. Nayak, and P. M. Ajayan, "First-principles study of defect-induced magnetism in carbon," Physical Review Letters, vol. 99, no. 10, pp. 1-4, 2007.
O. V. Yazyev, and L. Helm, "Defect-induced magnetism in graphene," Physical Review B: Condensed Matter and Materials Physics, vol. 75, no. 12, pp. 1-5, 2007.
P. Esquinazi, A. Setzer, R. Hoehne, C. Semmelhack, Y. Kopelevich, D. Spemann, T. Butz, B. Kohlstrunk, and M. Loesche, "Ferromagnetism in oriented graphite samples," Physical Review B: Condensed Matter and Materials Physics, vol. 66, no. 2, pp. 1-10, 2002.
A. A. Ovchinnikov and V. N. Spector, "Organic ferromagnets. New results," Synthetic Metals, vol. 27, no. 3-4, pp. 615-624, 1988.
C. Liu, Y. Yang, Z. Ma, C. Zhou, D. Liu, X. Luo, X. Zhu, Y. Sun, and Z. Sheng, "Edge-Induced Room-Temperature Ferromagnetism in Carbon Nanosheets," The Journal of Physical Chemistry C, vol. 124, pp. 7396-7403, 2020.
J. J. P. Barragán, K. Gross, H. A. Calderón, P. Prieto, C. D. Giorgio, F. Bobba, and A. M. Cucolo, "Room-temperature ferromagnetism in oxidized-graphenic nanoplatelets induced by topographic defects," Journal of Magnetism and Magnetic Materials, vol. 524, pp. 664-674, 2021.
J. C. Ruiz-cornejo, "Synthesis and applications of carbon nanofibers: a review," Reviews in Chemical Engineering, vol. 36, no. 4, pp. 1-19, 2018.
S. Hao, V. L. J. Joly, S. Kaneko, and J. Takashiro, "Magnetic edge-states in nanographene, HNO3-doped nanographene and its residue compounds of nanographene-based nanoporous carbon," Physical Chemistry Chemical Physics, vol. 16, pp. 6273-6282, 2014.
K. S. Yang, D. D. Edie, D. Y. Lim, Y. M. Kim, and Y. O. Choi, "Preparation of carbon fiber web from electrostatic spinning of PMDA-ODA poly (amic acid) solution," Carbon, vol. 41, pp. 2039-2046, 2003.
G. H. An, B. R. Koo, and H. J. Ahn, "Activated mesoporous carbon nanofibers fabricated using water etching-assisted templating for high-performance electrochemical capacitors," Physical Chemistry Chemical Physics, vol. 18, no. 9, pp. 6587-6594, 2016.
M. Samadishadlou, M. Farshbaf, N. Annabi, T. Kavetskyy, R. Khalilov, S. Saghfi, A. Akbarzadeh, and S. Mousavi, "Magnetic carbon nanotubes: preparation, physical properties, and applications in biomedicine," Artificial Cells, Nanomedicine and Biotechnology, vol. 46, no. 7, pp. 1314-1330, 2018.
K. E. Albinali, M. M. Zagho, Y. Deng, and A. A Elzatahry, "A perspective on magnetic core – shell carriers for responsive and targeted drug delivery systems," International Journal of Nanomedicine, vol. 14, pp. 1707-1723, 2019.
T. L. Makarova, "Ferromagnetic Carbonaceous Compounds," in Carbon Based Magnetism, Elsevier, 2006, pp. 541-562.
D. Xiang, X. Liu, and X. Dong, "A facile synthetic method and electrochemical performances of nickel oxide/carbon fibers composites," Journal of Materials Science, vol. 52, no. 13, pp. 7709-7718, 2017.
X. Zhou, Y. Wang, C. Gong, B. Liu, and G. Wei, "Production, structural design, functional control, and broad applications of carbon nano fiber-based nanomaterials: A comprehensive review," Chemical Engineering Journal, vol. 402, pp. 126189, 2020.
H. Niu, J. Zhang, Z. Xie, X. Wang, and T. Lin, "Preparation, structure and supercapacitance of bonded carbon nanofiber electrode materials," Carbon, vol. 49, no. 7, pp. 2380-2388, 2011.
O. Pech, and S. Maensiri, "Electrochemical performances of electrospun carbon nanofibers, interconnected carbon nanofibers, and carbon-manganese oxide composite nanofibers," Journal of Alloys and Compounds, vol.781, pp. 541-552, 2019.
S. Ma, J. H. Xia, V. V. S. S. Srikanth, X. Sun, T. Staedler, X. Jiang, F. Yang, and Z. D. Zhang, "Magnetism of amorphous carbon nanofibers," Applied Physics Letters, vol. 95, pp. 1-4, 2009.
J. Lv, W. Gu, X. Cui, S. Dai, B. Zhang, and G. Ji, "Nanofiber network with adjustable nanostructure controlled by PVP content for an excellent microwave absorption," Scientific Reports, vol. 9, no. 1, pp. 2-11, 2019.
O. M. Mpukuta, K. Dincer, and M. O. Erdal, "Investigation of electrical conductivity of PAN nanofibers containing silica nanoparticles produced by electrospinning method," Materials Today: Proceedings, vol. 18, pp. 1927-1935, 2019.
G. Wanga, C. Panab, L. Wanga, Q. Donga, C. Yua, Z. Zhaoa, and J. Qiu, "Activated carbon nanofiber webs made by electro-spinning for capacitive deionization," Electrochimica Acta, vol. 69, pp. 65-70, 2012.
Z. Yue, K. R. Benak, J. Wang, C. L. Mangun, and J. Economy, "Elucidating the porous and chemical structures of ZnCl2-activated polyacrylonitrile on a fiberglass substrate," Journal of Materials Chemistry, vol. 15, no. 30, pp. 3142-3148, 2005.
L. Pérez-Álvarez, L. Ruiz-Rubio, I. Moreno, and J. L. Vilas-Vilela, "Characterization and optimization of the alkaline hydrolysis of polyacrylonitrile membranes," Polymers (Basel), vol.11, no. 11, pp.1-11, 2019.
B. Xu, S. Yue, Z. Sui, X. Zhang, S. Hou, G. Cao, and Y. Yang, "What is the choice for supercapacitors: Graphene or graphene oxide," Energy & Environmental Science, vol. 4, no. 8, pp. 2826-2830, 2011.
E. N. Attia, F. M. Hassan, M. Li, R. Batmaz, A. Elkamel, and Z. Chen, "Tailoring the chemistry of blend copolymers boosting the electrochemical performance of Si-based anodes for lithium ion batteries," Journal of Materials Chemistry A, vol. 5, no. 46, pp. 24159-24167, 2017.
D. R. Baer, K. Artyushkova, H. Cohen, C. D. Easton, M. Engelhard, T. R. Gengenbach, G. Greczynski, P. Mack, D. J. Morgan, and A. Roberts, "XPS guide: Charge neutralization and binding energy referencing for insulating samples XPS guide: Charge neutralization and binding energy referencing for insulating samples," Journal of Vacuum Science and Technology A, vol. 38, no. 3, pp. 1-19, 2020.
V. Ţucureanu, A. Matei, and A. M. Avram, "FTIR Spectroscopy for Carbon Family Study," Critical Reviews in Analytical Chemistry, vol. 46, no. 6, pp. 502-520, 2016.
A. C. Obreja, D. Cristea, R. Gavrila, V. Schiopu, A. Dinescu, M. Danila, and F. Comanescu, "Isocyanate functionalized graphene/P3HT based nanocomposites," Applied Surface Science, vol. 276, pp. 458-467, 2013.
C. Liu, and K. Lafdi, "Fabrication and characterization of carbon nanofibers from polyacrylonitrile/pitch blends," Journal of Applied Polymer Science, vol. 134, no. 42, pp. 1-7, 2017.
N. B. A. Mansor, J. P. Tessonnier, A. Rinaldi, S. Reiche, and M. G. Kutty, "Chemically modified multi-walled carbon nanotubes (MWCNTs) with anchored acidic groups," Sains Malaysiana, vol. 41, no. 5, pp. 603-609, 2012.
V. A. E. Barrios, J. R. R. Méndez, N. V. P. Aguilar, G. A. Espinosa, and J. L. D. Rodríguez, "FTIR - An Essential Characterization Technique for Polymeric Materials," in Infrared Spectroscopy - Materials Science, Engineering and Technology, ed Greece, 2012, pp. 195-210.
M. R. Johan, S. H. Meriam Suhaimy, and Y. Yusof, "Physico-chemical studies of cuprous oxide (Cu2O) nanoparticles coated on amorphous carbon nanotubes (α-CNTs)," Applied Surface Science, vol. 289, pp. 450-454, 2014.
J. Coates, "Interpretation of Infrared Spectra, A Practical Approach," in Encyclopedia of Analytical Chemistry, John Wiley & Sons, 2006, pp.1-23.
F. E. C Othman, N. Yusof, J. Jaafar, A. F. Ismail, H. Hasbullah, N. Abdullah, and M. S. Ismail, "Preparation and characterization of Polyacrylonitrile/ Manganese Dioxides- based Carbon Nanofibers via electrospinning process," IOP Conference Series: Earth and Environmental Science, vol. 36, no. 1, pp. 012006, 2016.
J. Yan, Q. Wang, T. Wei, and Z. Fan, "Recent advances in design
and fabrication of electrochemical supercapacitors with high energy densities," Advanced Energy Materials, vol. 4, no. 4, pp. 1-43, 2014.
A. Sadezky, H. Muckenhuber, H. Grothe, R. Niessner, and U. Pöschl, "Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information," Carbon, vol. 43, no. 8, pp. 1731-1742, 2005.
M. A. Pimenta, G. Dresselhaus, M. S. Dresselhaus, L. G. Cançado, A. Jorio, and R. Saito, "Studying disorder in graphite-based systems by Raman spectroscopy," Physical Chemistry Chemical Physics, vol. 9, no. 11, pp. 1276-1291, 2007.
R. N. Bhowmik, "Ferromagnetism in lead graphite-pencils and magnetic composite with CoFe2O4 particles," Composites Part B: Engineering, vol. 43, no. 2, pp. 503-509, 2012.
D. Lee and J. Seo, "Magnetic frustration of graphite oxide," Scientific Reports, vol. 7, pp. 2-7, 2017.
P. O. Lehtinen, A. S. Foster, Y. Ma, A. V. Krasheninnikov, and R. M. Nieminen, "Irradiation-induced magnetism in graphite: A density functional study," Physical Review Letters, vol. 93, no. 18, pp. 1-4, 2004.
A. Sinha, A. Ali, and A. D. Thakur, "Ferromagnetism in graphene oxide," Materials Today: Proceedings, vol. 46, no. 14, pp. 6230-6233, 2021.
T. Ishii, Y. Kaburagi, A. Yoshida, Y. Hishiyama, H. Oka, N. Setoyama, J. Ozaki, and T. Kyotani, "Analyses of trace amounts of edge sites in natural graphite, synthetic graphite and high-temperature treated coke for the understanding of their carbon molecular structures," Carbon, vol. 125, pp. 146-155, 2017.
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