Hybrid Plasma-Liquid Treatment of Carbon Nanotubes for Application in Direct Absorption Solar Thermal Collectors
Authors: McGlynn Ruairi , Brunet Paul , Hussein Hussein Sayed , Chakrabarti Supriya , Mariotti Davide 
Published: July 2021

Covalent functionalization of carbon nanotubes (CNTs) with oxygen-based or nitrogen-based functional groups is one of the most popular techniques to modify the surface energy and inherent properties of the CNTs.1 This functionalization generates interest for a broad range of applications including mechanically superior advanced composites,2 more sensitive gas sensors,3 enhanced energy storage materials4 or ultra-conductive fibers.5 As an alternative to the harsh chemicals used by traditional chemical functionalization, plasma-based surface treatments can be used with great efficacy and reduced reaction times, providing an array of application-specific benefits.
Awareness of the environmental pollution caused by fossil fuels and the ever-increasing demand for energy has driven research focussed on zero-carbon renewable energy sources. Conscious of this, direct absorption solar thermal collectors are gaining prominence, both for domestic heating and steam generation. CNTs have been investigated as an additive to take advantage of the near blackbody absorption and high thermal conductivity to improve system efficiency. Critical to the success of the additive nanoparticles is the stability in the fluid, however, due to their high surface energy CNTs tend to agglomerate which can limit the efficacy of their integration into real-world products.
In this work, macroscopic ribbon-like assemblies of carbon nanotubes are functionalized by plasma-induced non-equilibrium electrochemistry (PiNE) implemented through a simple direct current-based plasma-liquid system. This system utilizes the plasma-generated species in an electrolyte of 10 %vol ethanol in water, with or without a nitrogen precursor, for the oxygen and/or nitrogen functionalization of the carbon nanotube assembly. For this treatment, a ribbon-like piece of CNT was used as the anode and a helium plasma discharge triggered by applying 10 mA and 1 - 1.6 kV to act as the cathode. The plasma-generated species are then expected to migrate towards the CNTs and functionalize the sidewalls.
The oxygen content is shown to be increased by between 70 % and 300 % when the treatment solution of 10 %vol ethanol is used in the ribbon electrode configuration. When ethylenediamine is added as a nitrogen precursor, the atomic concentration of nitrogen reaches 23 %, with amine groups, pyrrolic groups and graphitic nitrogen observed in the x-ray photoelectron spectra. This nitrogen content is unmatched in quantity when compared to either a simple soaking procedure or an electrolysis process with a platinum foil replacing the plasma as the counter-electrode. This demonstrates that the plasma either directly or indirectly, through plasma-generated species, facilitates and enhances the availability of nitrogen from the ethylenediamine precursor. The potential plasma-induced chemical pathways which lead to the functionalization of the CNTs are also investigated and discussed.
In the application of a direct absorption solar collector system, it is found that the covalent functionalization provided by the plasma-liquid system enhances the stability of the CNT-ethylene glycol nanofluid, with the oxygen-functionalized samples producing the most stable nanofluids. This is explained through the lower value for contact angle measurements, suggesting greater hydrophobicity of the CNTs.
References
(1) Mallakpour, S.; Soltanian, S. Surface Functionalization of Carbon Nanotubes: Fabrication and Applications. RSC Adv.
2016, 6 (111), 109916–109935. https://doi.org/10.1039/c6ra24522f.
(2) Williams, J.; Broughton, W.; Koukoulas, T.; Rahatekar, S. S. Plasma Treatment as a Method for Functionalising and Improving Dispersion of Carbon Nanotubes in Epoxy Resins. J. Mater. Sci.
2013, 48 (3), 1005–1013. https://doi.org/10.1007/s10853-012-6830-3.
(3) Ham, S. W.; Hong, H. P.; Kim, J. H.; Min, S. J.; Min, N. K. Effect of Oxygen Plasma Treatment on Carbon Nanotube-Based Sensors. J. Nanosci. Nanotechnol.
2014, 14 (11), 8476–8481. https://doi.org/10.1166/jnn.2014.10007.
(4) Hulicova-Jurcakova, D.; Seredych, M.; Lu, G. Q.; Bandosz, T. J. Combined Effect of Nitrogen- and Oxygen-Containing Functional Groups of Microporous Activated Carbon on Its Electrochemical Performance in Supercapacitors. Adv. Funct. Mater.
2009, 19 (3), 438–447. https://doi.org/10.1002/adfm.200801236.
(5) Li, L.; Liu, E.; Shen, H.; Yang, Y.; Huang, Z.; Xiang, X.; Tian, Y. Charge Storage Performance of Doped Carbons Prepared from Polyaniline for Supercapacitors. J. Solid State Electrochem.
2011, 15 (1), 175–182. https://doi.org/10.1007/s10008-010-1087-8.

Figure 1