Porosity Development in Carbon Nanofibers by Physical and Chemical Activation

Abstract:

In this Work we Have Compared the Effects of Physical Activation with CO₂ and Chemical Activation with KOH on Porosity Development in Vapor Grown Carbon Nanofibers (CNFs). both Physical and Chemical Activations Result in Micro- and Mesoporosity Development in the Studied Cnfs. under this Work’s Conditions, Chemical Activation with KOH Was More Efficient than Physical Activation with CO₂ in Terms of Surface Area Increase Regarding the Fresh Material (7.5-Fold versus 4-Fold, Respectively, under the Optimal Conditions Found for each Type of Activation). Atomic Force Microscopy Indicated that, although the CNF Samples Retained their Fibrous Morphology upon both Physical and Chemical Activation, the Latter Treatment Brought about Noticeable Changes in their Nanometer-Scale Structure. Likewise, an Appreciable Decrease in Nanofiber Diameter Following both Types of Activation Was Noticed. However, such Diameter Reduction Could Not Account for the Increase in Specific Surface Area of the Activated Materials, which Has to Be Attributed to Porosity Development. X-Ray Diffraction Studies Showed that both Physical as Chemical Activation Take Place Mainly on the Disordered Skin of the Cnfs but in a Different Way. Thus, Physical Activation Removes the More Amorphous Areas from the CNF Skin by Gasification (which Increases their Structural Order), while upon Chemical Activation with KOH, the Carbon Material Is Oxidized to a Carbonate, and the Alkali Hydroxide Is Reduced to Metallic Potassium, which Becomes Intercalated between the Graphene Layers of the Carbon Material, Leading to a Certain Expansion of the Structure.

• Periodical: Journal of Nano Research (Volume 17)
• Pages: 211-227
• DOI: https://doi.org/10.4028/www.scientific.net/JNanoR.17.211
• Online since: February 2012
• Authors: F. Suárez-García, J.I. Paredes, M. Pérez-Mendoza, J. Nauroy, A. Martínez-Alonso, J.M.D. Tascón
• Keywords: Carbon Nanowires, Chemical Activation, Physical Activation, Porosity

References

[1] L.P. Biró, C.A. Bernardo, G.G. Tibbetts, P. Lambin (Eds. ), Carbon Filaments and Nanotubes: Common Origins, Differing Applications?, Kluwer, Dordrecht, (2001).

DOI: 10.1007/978-94-010-0777-1

[2] K.L. Klein, A.V. Melechko, T.E. McKnight, S.T. Retterer, P.D. Rack, J.D. Fowlkes, D.C. Joy, M.L. Simpson, Magnetic properties of Fe-Co catalysts used for carbon nanofiber synthesis, J. Appl. Phys. 103 (2008) 061301.

DOI: 10.1063/1.2840049

[3] G.G. Tibbetts, M.L. Lake, K.L. Strong, B.P. Rice, A review of the fabrication and properties of vapor-grown carbon nanofiber/polymer composites, Compos. Sci. Technol. 67 (2007) 1709-1718.

DOI: 10.1016/j.compscitech.2006.06.015

[4] M.H. Al-Saleh, U. Sundararaj, A review of vapor grown carbon nanofiber/polymer conductive composites, Carbon 47 (2009) 2-22.

DOI: 10.1016/j.carbon.2008.09.039

[5] S.E. Baker, K.Y. Tse, C.S. Lee, R.J. Hamers, Fabrication and characterization of vertically aligned carbon nanofiber electrodes for biosensing applications, Diamond Relat. Mater. 15 (2006), 433-439.

DOI: 10.1016/j.diamond.2005.08.019

[6] P.A. Tran, L. Zhang, T.J. Webster, Carbon nanofibers and carbon nanotubes in regenerative medicine, Adv. Drug Deliver. Rev. 61 (2009) 1097-1114.

DOI: 10.1016/j.addr.2009.07.010

[7] P. Serp, M. Corrias, P. Kalck, Carbon nanotubes and nanofibers in catalysis, Appl. Catal. AGen. 253 (2003) 337-358.

[8] F.U. Naab, M. Dhoubhadek, J.R. Gilbert, M.C. Gilbert, L.K. Savage, O.W. Holland, J.L. Duggan, F.D. McDaniel, Direct measurement of hydrogen adsorption in carbon nanotubes/nanofibers by elastic recoil detection, Phys. Lett. A 356 (2006) 152-155.

DOI: 10.1016/j.physleta.2006.03.031

[9] G. Andrade-Espinosa, E. Muñoz-Sandoval, M. Terrones, M. Endo, H. Terrones, J.R. RangelMendez, Acid modified bamboo-type carbon nanotubes and cup-stacked-type carbon nanofibres as adsorbent materials: Cadmium removal from aqueous solution, J. Chem. Technol. Biot. 84 (2009).

DOI: 10.1002/jctb.2073

[10] K.P. De Jong, J.W. Geus, Carbon Nanofibers: Catalytic Synthesis and Applications, Catal. Rev. 42 (2000) 481-510.

[11] F. Schüth, K.S.W. Sing, J. Weitkamp (Eds. ), Handbook of Porous Solids, Wiley-VCH, Weinheim, (2002).

[12] S. -H. Yoon, S. Lim, Y. Song, Y. Ota, W. Qiao, A. Tanaka, I. Mochida, KOH activation of carbon nanofibers, Carbon 42 (2004) 1723-1729.

DOI: 10.1016/j.carbon.2004.03.006

[13] C. Merino, P. Soto, E. Vilaplana-Ortego, J.M. Gómez de Salazar, F. Pico, J.M. Rojo, Carbon nanofibres and activated carbon nanofibres as electrodes in supercapacitors, Carbon 43 (2005) 551-557.

DOI: 10.1016/j.carbon.2004.10.018

[14] J.M. Blackman, J.W. Patrick, A. Arenillas, W. Shi, C.E. Snape, Activation of carbon nanofibres for hydrogen storage, Carbon 44 (2006) 1376-1385.

DOI: 10.1016/j.carbon.2005.11.015

[15] F. Suárez-García, J. Nauroy, A. Martínez-Alonso, J.M.D. Tascón, Thermogravimetric studies on the activation of nanometric carbon fibers, J. Therm. Anal. Calorim. 79 (2005) 525-528.

DOI: 10.1007/s10973-005-0573-1

[16] D. Cazorla-Amorós, J. Alcañiz-Monge, A. Linares-Solano, Characterization of activated carbon fibers by CO2 adsorption, Langmuir 12 (1996) 2820-2824.

DOI: 10.1021/la960022s

[17] D. Cazorla-Amorós, J. Alcañiz-Monge, M.A. Casa-Lillo, A. Linares-Solano, CO2 as an adsorptive to characterize carbon molecular sieves and activated carbons, Langmuir 14 (1998) 4589-4596.

DOI: 10.1021/la980198p

[18] A. Cuesta, P. Dhamelincourt, J. Laureyns, A. Martínez-Alonso, J.M.D. Tascón, Effect of various treatments on carbon fiber surfaces studied by Raman microprobe spectrometry, Appl. Spectroscopy 52 (1998) 356-360.

DOI: 10.1366/0003702981943815

[19] J.I. Paredes, A. Martínez-Alonso, J.M.D. Tascón, Detecting surface oxygen groups on carbon nanofibers by phase contrast imaging in tapping mode AFM, Langmuir 19 (2003) 7665-7668.

DOI: 10.1021/la020880q

[20] J.I. Paredes, A. Martínez-Alonso, J.M.D. Tascón, Surface characterization of submicron vapor grown carbon fibers by scanning tunneling microscopy, Carbon 39 (2001) 1575-1587.

DOI: 10.1016/s0008-6223(00)00286-4

[21] D.W. McKee, Mechanisms of the alkali metal catalysed gasification of carbon, Fuel 62 (1983) 170-175.

DOI: 10.1016/0016-2361(83)90192-8

[22] C.L. Spiro, D.W. McKee, P.G. Kosky, D.J. Lamby, Catalytic CO2-gasification of graphite versus coal char, Fuel 62 (1983) 180-184.

DOI: 10.1016/0016-2361(83)90194-1

[23] F. Kapteijn, J.A. Moulijn, Kinetics of the potassium carbonate-catalysed CO2 gasification of activated carbon, Fuel 62 (1983) 221-225.

DOI: 10.1016/0016-2361(83)90203-x

[24] J. Laine, A. Calafat, Factors affecting the preparation of activated carbons from coconut shell catalized by potassium, Carbon 29 (1991) 949-953.

DOI: 10.1016/0008-6223(91)90173-g

[25] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquerol et al., Reporting physisorption data for gas solid systems with special reference to the determination of surface-area and porosity (recommendations 1984), Pure Appl. Chem. 57 (1985).

DOI: 10.1515/iupac.57.0007

[26] F. Rouquerol, J. Rouquerol, K. Sing, Adsorpion by powders and porous solids. Principles, methodology and applications, Academic Press, San Diego, (1999).

DOI: 10.1002/vipr.19990110317

[27] J. Garrido, A. Linares-Solano, J.M. Martín-Martínez, M. Molina-Sabio, F. RodríguezReinoso, R. Torregrosa, Use of N2 vs CO2 in the characterization of activated carbons, Langmuir 3 (1987) 76-81.

DOI: 10.1021/la00073a013

[28] J.P. Olivier, Improving the models used for calculating the size distribution of micropore volume of activated carbons from adsorption data, Carbon 36 (1998) 1469-1472.

DOI: 10.1016/s0008-6223(98)00139-0

[29] Ph. Serp, J.L. Figueiredo, P. Bertrand, J.P. Issi, Surface treatments of vapor-grown carbon fibers produced on a substrate, Carbon 36 (1998) 1791-1799.

DOI: 10.1016/s0008-6223(98)00149-3

[30] A. Ahmadpour, D.D. Do, The preparation of activated carbon from macadamia nutshell by chemical activation, Carbon 35 (1997) 1723-1732.

DOI: 10.1016/s0008-6223(97)00127-9

[31] H. Teng, S. -C. Wang, Preparation of porous carbons from phenol-formaldehyde resins with chemical and physical activation, Carbon 38 (2000) 817-824.

DOI: 10.1016/s0008-6223(99)00160-8

[32] Y. Zou, B. -X. Han, High-surface-area activated carbon from Chinese coal, Energy Fuels 15 (2001) 1383-1386.

DOI: 10.1021/ef0002851

[33] I. Martín-Gullón, R. Andrews, M. Jagtoyen, F. Derbyshire, PAN-based activated carbon fiber composites for sulfur dioxide conversion: Influence of fiber activation method, Fuel 80 (2001) 969-977.

DOI: 10.1016/s0016-2361(00)00186-1

[34] A.C. Lua, T. Yang, Effect of activation temperature on the textural and chemical properties of potassium hydroxide activated carbon prepared from pistachio-nut shell, J. Colloid Interface Sci. 274 (2004) 594-601.

DOI: 10.1016/j.jcis.2003.10.001

[35] A. Linares-Solano, D. Lozano-Castelló, M.A. Lillo-Ródenas, D. Cazorla-Amorós, Carbon activation by alkaline hydroxides: preparation and reactions, porosity and performance, Chem. Phys. Carbon 30 (2007) 1-62.

DOI: 10.1201/9781420042993.ch1

[36] M.J. Illán-Gomez, A. García-García, C. Salinas-Martínez de Lecea, A. Linares-Solano, Activated carbons from Spanish coals. 2. Chemical activation Energy Fuels 10 (1996) 11081114.

DOI: 10.1021/ef950195+

[37] A. Ahmadpour, D.D. Do, The preparation of active carbons from coal by chemical and physical activation, Carbon 34 (1996) 471-479.

DOI: 10.1016/0008-6223(95)00204-9

[38] D. Lozano-Castelló, M.A. Lillo-Ródenas, D. Cazorla-Amorós, A. Linares-Solano, Preparation of activated carbons from Spanish anthracite I. Activation by KOH, Carbon 39 (2001) 741749.

DOI: 10.1016/s0008-6223(00)00185-8

[39] M.A. Lillo-Ródenas, D. Lozano-Castelló, D. Cazorla-Amorós, A. Linares-Solano, Preparation of activated carbons from Spanish anthracite: II. Activation by NaOH, Carbon 39 (2001) 751759.

DOI: 10.1016/s0008-6223(00)00185-8