Skip to main content Accessibility help

Surface energetics of carbon nanotubes–based nanocomposites fabricated by microwave-assisted approach

  • Gengnan Li (a1), Shatila Sarwar (a2), Xianghui Zhang (a1), Chen Yang (a1), Xiaofeng Guo (a3), Xinyu Zhang (a2) and Di Wu (a4)...


Using ethanol adsorption calorimetry, the surface energetics of two carbon substrates and two products in microwave-assisted carbon nanotube (CNT) growth was studied. In this study, the ethanol adsorption enthalpies of the two graphene-based samples at 25 °C were measured successfully. Specifically, the near-zero differential enthalpies of ethanol adsorption are −75.7 kJ/mol for graphene and −63.4 kJ/mol for CNT-grafted graphene. Subsequently, the differential enthalpy curve of each sample becomes less exothermic until reaching a plateau, −55.8 kJ/mol for graphene and −49.7 kJ/mol for CNT-grafted graphene, suggesting favorable adsorbate–adsorbent binding. Moreover, the authors interpreted and discussed the partial molar entropy and chemical potential of adsorption as the ethanol surface coverage (loading) increases. Due to the low surface areas of carbon black–based samples, adsorption calorimetry could not be performed. This model study demonstrates that using adsorption calorimetry as a fundamental tool and ethanol as the molecular probe, the overall surface energetics of high–surface area carbon materials can be estimated.


Corresponding author

b)Address all correspondence to these authors. e-mail:


Hide All

These authors contributed equally to this work.


This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to



Hide All
1.Liu, K., Sun, Y., Lin, X., Zhou, R., Wang, J., Fan, S., and Jiang, K.: Scratch-resistant, highly conductive, and high-strength carbon nanotube-based composite yarns. ACS Nano 4, 5827 (2010).
2.Kang, I., Heung, Y.Y., Kim, J.H., Lee, J.W., Gollapudi, R., Subramaniam, S., Narasimhadevara, S., Hurd, D., Kirikera, G.R., Shanov, V., Schulz, M.J., Shi, D., Boerio, J., Mall, S., and Ruggles-Wren, M.: Introduction to carbon nanotube and nanofiber smart materials. Composites, Part B 37, 382 (2006).
3.Han, B., Yu, X., and Ou, J.: Multifunctional and smart carbon nanotube reinforced cement-based materials. Nanotechnol. Civ. Infrastruct., 1 (2011).
4.Martin, C.R., Che, G., Lakshmi, B.B., and Fisher, E.R.: Carbon nanotube membranes for electrochemical energy storage and production. Nature 393, 346 (1998).
5.Li, J., Lu, Y., Ye, Q., Cinke, M., Han, J., and Meyyappan, M.: Carbon nanotube sensors for gas and organic vapor detection. Nano Lett. 3, 929 (2003).
6.McEuen, P.L., Fuhrer, M.S., and Park, H.: Single-walled carbon nanotube electronics. IEEE Trans. Nanotechnol. 1, 78 (2002).
7.Journet, C., Maser, W.K., Bernier, P., Loiseau, A., de la Chapelle, M.L., Lefrant, S., Deniard, P., Lee, R., and Fischer, J.E.: Large-scale production of single-walled carbon nanotubes by the electric-arc technique. Nature 388, 756 (1997).
8.Scott, C.D., Arepalli, S., Nikolaev, P., and Smalley, R.E.: Growth mechanisms for single-wall carbon nanotubes in a laser-ablation process. Appl. Phys. A: Mater. Sci. Process. 72, 573 (2001).
9.Nikolaev, P., Bronikowski, M.J., Bradley, R.K., Rohmund, F., Colbert, D.T., Smith, K.A., and Smalley, R.E.: Gas-phase catalytic growth of single-walled carbon nanotubes from carbon monoxide. Chem. Phys. Lett. 313, 91 (1999).
10.Cassell, A.M., Raymakers, J.A., Kong, J., and Dai, H.: Large scale CVD synthesis of single-walled carbon nanotubes. J. Phys. Chem. B 103, 6484 (1999).
11.Baddour, C.E. and Briens, C.: Carbon nanotube synthesis: A review. Int. J. Chem. React. Eng. 3, 120 (2005).
12.Premkumar, T., Mezzenga, R., and Geckeler, K.E.: Carbon nanotubes in the liquid phase: Addressing the issue of dispersion. Small 8, 1299 (2012).
13.Fraczek-Szczypta, A., Bogun, M., and Blazewicz, S.: Carbon fibers modified with carbon nanotubes. J. Mater. Sci. 44, 4721 (2009).
14.Thostenson, E.T., Li, W.Z., Wang, D.Z., Ren, Z.F., and Chou, T.W.: Carbon nanotube/carbon fiber hybrid multiscale composites. J. Appl. Phys. 91, 6034 (2002).
15.Zhang, X. and Liu, Z.: Recent advances in microwave initiated synthesis of nanocarbon materials. Nanoscale 4, 707 (2012).
16.Liu, Z., Wang, J.L., Kushvaha, V., Poyraz, S., Tippur, H., Park, S., Kim, M., Liu, Y., Bar, J., Chen, H., and Zhang, X.Y.: Poptube approach for ultrafast carbon nanotube growth. Chem. Commun. 47, 9912 (2011).
17.Liu, Z., Zhang, L., Wang, R.G., Poyraz, S., Cook, J., Bozack, M.J., Das, S., Zhang, X.Y., and Hu, L.B.: Ultrafast microwave nano-manufacturing of fullerene-like metal chalcogenides. Sci. Rep. 6, 18 (2016).
18.Liu, Z., Chen, L., Zhang, L., Poyraz, S., Guo, Z.H., Zhang, X.Y., and Zhu, J.H.: Ultrafast Cr(VI) removal from polluted water by microwave synthesized iron oxide submicron wires. Chem. Commun. 50, 8036 (2014).
19.Liu, Y., Zhang, X., Poyraz, S., Zhang, C., and Xin, J.H.: One-step synthesis of multifunctional zinc-iron-oxide hybrid carbon nanowires by chemical fusion for supercapacitors and interfacial water marbles. ChemNanoMat 4, 546556 (2018).
20.Liu, Y., Zhang, X., and Xin, J.H.: Microwave fabrication of hierarchical carbon nanotube/carbon fiber nanocomposite. In Fiber Society’s Spring 2015 Conference, in Conjunction with the 2015 International Conference on Advanced Fibers and Polymer Materials: Functional Fibers and Textiles—Program (2015).
21.Liu, Z., Zhang, L., Poyraz, S., Smith, J., Kushvaha, V., Tippur, H., and Zhang, X.Y.: An ultrafast microwave approach towards multicomponent and multi-dimensional nanomaterials. RSC Adv. 4, 9308 (2014).
22.Poyraz, S., Flogel, M., Liu, Z., and Zhang, X.Y.: Microwave energy assisted carbonization of nanostructured conducting polymers for their potential use in energy storage applications. Pure Appl. Chem. 89, 173 (2017).
23.Poyraz, S., Cook, J., Liu, Z., Zhang, L., Nautiyal, A., Hohmann, B., Klamt, S., and Zhang, X.: Microwave energy-based manufacturing of hollow carbon nanospheres decorated with carbon nanotubes or metal oxide nanowires. J. Mater. Sci. 53, 1217812189 (2018).
24.Poyraz, S., Liu, Z., Liu, Y., and Zhang, X.: Devulcanization of scrap ground tire rubber and successive carbon nanotube growth by microwave irradiation. Curr. Org. Chem. 17, 22432248 (2013).
25.Poyraz, S., Zhang, L., Schroder, A., and Zhang, X.: Ultrafast microwave welding/reinforcing approach at the interface of thermoplastic materials. ACS Appl. Mater. Interfaces 7, 2246922477 (2015).
26.Wu, D., Guo, X., Sun, H., and Navrotsky, A.: Thermodynamics of methane adsorption on copper HKUST-1 at low pressure. J. Phys. Chem. Lett. 6, 2439 (2015).
27.Wu, D., McDonald, T.M., Quan, Z., Ushakov, S.V., Zhang, P., Long, J.R., and Navrotsky, A.: Thermodynamic complexity of carbon capture in alkylamine-functionalized metal–organic frameworks. J. Mater. Chem. A 3, 4248 (2015).
28.Wu, D., Guo, X., Sun, H., and Navrotsky, A.: Interplay of confinement and surface energetics in the interaction of water with a metal–organic framework. J. Phys. Chem. C 120, 7562 (2016).
29.Wu, D., Gassensmith, J.J., Gouveîa, D., Ushakov, S., Stoddart, J.F., and Navrotsky, A.: Direct calorimetric measurement of enthalpy of adsorption of carbon dioxide on CD-MOF-2, a green metal–organic framework. J. Am. Chem. Soc. 135, 6790 (2013).
30.Wu, D., Guo, X., Sun, H., and Navrotsky, A.: Energy landscape of water and ethanol on silica surfaces. J. Phys. Chem. C 119, 15428 (2015).
31.Wu, D. and Navrotsky, A.: Probing the energetics of organic-nanoparticle interactions of ethanol on calcite. Proc. Natl. Acad. Sci. U. S. A. 112, 5314 (2015).
32.Navrotsky, A., Ma, C., Lilova, K., and Birkner, N.: Nanophase transition metal oxides show large thermodynamically driven shifts in oxidation–reduction equilibria. Science 330, 199 (2010).
33.Navrotsky, A., Mazeina, L., and Majzlan, J.: Science 319, 1635 (2008).
34.Ushakov, S.V. and Navrotsky, A.: Direct measurements of water adsorption enthalpy on hafnia and zirconia. Appl. Phys. Lett. 87, 1 (2005).
35.Li, G., Sun, H., Xu, H., Guo, X., and Wu, D.: Probing the energetics of molecule-material interactions at interfaces and in nanopores. J. Phys. Chem. C 121, 2614126154 (2017).
36.Qiu, D., Fu, L., Zhan, C., Lu, J., and Wu, D.: Seeding iron trifluoride nanoparticles on reduced graphite oxide for lithium-ion batteries with enhanced loading and stability. ACS Appl. Mater. Interfaces, 2950529510 (2018).



Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed