Abstract
The objective of this study was to investigate the chemisorption mechanisms of Cu(II) on alcohol functionalized carbon nanotubes (OH-CNT) compared to granulated activated carbon (F-400). Two different sizes of OH-CNT were used on both adsorption isotherm experiments and continuous-flow fixed-bed columns. The experiments were conducted as a function of adsorbent type with fixed bed height (5 cm), fixed flow rate (0.035 mL/min), and one initial Cu(II) concentration (10 mg/L) at pH 5.1 and room temperature. Isotherm curves follow Freundlich model with better adsorption capacity for OH-CNT (6.3 and 15.7 mg/g) compared to F-400 (6.0 mg/g). Breakthrough curves for all adsorbents were typical, while OH-CNT showed higher capacity to treat water per amount of adsorbent than F-400. After 5 days of desorption, there was very little Cu(II) leached from the OH-CNT column as compared to F-400 that slowly desorbed 85 % of Cu(II). These results indicated chemisorption process on OH-CNT with low residual release of Cu(II) from adsorbent after reaching saturation. A systematic correlation method using converted FTIR absorbance curves (first derivative analysis) of as-received and hybrid OH-CNT identified new peaks on the spectra for Cu(II) chemisorbed on CNT surface, showing that Cu(II) target acidic functional groups during adsorption.
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References
Ahamad, K. U., & Jawed, M. (2011). Breakthrough column studies for iron(II) removal from water by wooden charcoal and sand: a low cost approach. International Journal of Environmental Research, 5, 127–138.
Atkins, P. W. (2003). Molecules. Cambridge: Cambridge University Press.
Branche, C. M., P., S. & Geraci, C. (2009). Approaches to safe nanotechnology—managing the health and safety concerns associated with engineered nanomaterials. NIOSH.
Chen, J. P., & Lin, M. (2000). Equilibrium and kinetics of metal ion adsorption onto a commercial H-type granular activated carbon: experimental and modeling studies. Water Research, 35, 2385–2394.
Chen, W., Duan, L., & Zhu, D. (2007). Adsorption of polar and nonpolar organic chemicals to carbon nanotubes. Environmental Science and Technology, 41, 8295–8300.
Chen, C., Liang, B., Ogino, A., Wang, X., & Nagatsu, M. (2009). Oxygen functionalization of multiwall carbon nanotubes by microwave-excited surface-wave plasma treatment. Journal of Physical Chemistry C, 113, 7659–7665.
Cooney, D. O. (1999). Adsorption design for wastewater treatment. (pp. 165): CRC Press LLC.
Fischer, J. E. (2006). Carbon nanotubes: structure and properties. In Y. Gogotsi (Ed.), Nanotubes and nanofibers (p. 1). Boca Raton: Taylor and Francis Group.
Gao, Z., Bandosz, T. J., Zhao, A., Han, M., & Qiu, J. (2009). Investigation of factors affecting adsorption of transition metals on oxidized carbon nanotubes. Journal of Hazardous Materials, 167, 357–365.
Harris, D. (2010). Chapter 20—atomic spectroscopy. In W. H. f. a. Company (Ed.), Quantitative chemical analysis (pp. 482–494). New York: Clancy Marshall.
He, H., Klinowski, J., Forster, M., & Lerf, A. (1998). A new structural model for graphite oxide. Chemical and Physics Letters, 287, 53–56.
Inglezakis, V. J., & Grigoropoulou, H. (2004). Effects of operating conditions on the removal of heavy metals by zeolite in fixed bed reactors. Journal of Hazardous Materials, B112, 37–43.
Krause, N. (2003). Modern organocopper chemistry, Wiley-VCH.
Kuo, C. Y. (2009). Water purification of removal aqueous copper (II) by as-grown and modified multi-walled carbon nanotubes. Desalination, 249, 781–785.
Naseh, M. V., Khodadadi, A. A., Sahraei, O. A., Pourfayaz, F., & Sedghi, S. M. (2009). Functionalization of carbon nanotubes using nitric acid oxidation and DBD plasma. International Journal of Chemical and Biological Engineering, 2, 66–68.
Naseh, M. V., Khodadadi, A. A., Mortazavi, Y., Pourfayaz, F., Alizadeh, O., et al. (2010). Fast and clean functionalization of carbon nanotubes by dielectric barrier discharge plasma in air compared to acid treatment. Carbon, 48, 1369–1379.
Pyrzynska, K. (2011). Carbon nanotubes as sorbents in the analysis of pesticides. Chemosphere, 83, 1407–1413.
Rakov, E. G. (2006). Chemistry of carbon nanotubes. In Y. Gogotsi (Ed.), Nanotubes and nanofibers (p. 37). Boca Raton: Taylor and Francis Group.
Randtke, S. J. (1983). Evaluating GAC adsorptive capacity. AWWA, 75, 406.
Rao, G. P., Lu, C., & Su, F. (2007). Sorption of divalent metal ions from aqueous solution by carbon nanotubes: a review. Separation and Purification Technology, 58, 224–231.
Rosenzweig, S., Sorial, G. A., Sahle-Demessie, E., & Mack, J. (2013). Effect of acid and alcohol network forces within functionalized multiwall carbon nanotubes bundles on adsorption of copper (II) species. Chemosphere, 90, 395–402.
Schock, M. R., Darren, A. L. & Clement, J. A. (1995). Effect of pH, DIC, orthophosphate and sulfate on drinking water cuprosolvency. EPA/600/R-95/085, USEPA.
Sharma, Y. C., Srivastava, V., Singh, V. K., Kaul, S. N., & Weng, C. H. (2009). Nano-adsorbents for the removal of metallic pollutants from water and wastewater. Environmental Technology, 30, 583–609.
Sheng, G., Li, J., Shao, D., Hu, J., Chen, C., et al. (2010). Adsorption of copper (II) on multiwalled carbon nanotubes in the absence and presence of humic or fulvic acids. Journal of Hazardous Materials, 178, 333–340.
Shin, S., Jang, J., Yoon, S.-H., & Mochida, I. (1997). A study on the effect of heat treatment on functional groups of pitch based activated carbon fiber using FTIR. Carbon, 35, 1739–1743.
Tchobanoglous, G., Burton, F. & Stensel, H. D. (2003). Wastewater engineering: treatment and reuse. McGraw Hill.
Tumin, N. D., Chuah, A. L., Zawani, Z., & Rashid, S. A. (2008). Adsorption of copper from aqueous solution by Elaeis guineensis kernel activated carbon. Journal of Engineering Science and Technology, 3, 9.
Upadhyayula, V. K. K., Deng, S., Mitchell, M. C., & Smith, G. B. (2009). Application of carbon nanotube technology for removal of contaminants in drinking water: a review. Science of the Total Environment, 408, 1–13.
Wang, X., Chen, C., Hu, W., Ding, A., Xu, D., et al. (2005). Sorption of 243Am(III) to multiwall carbon nanotubes. Environmental Science and Technology, 39, 2856–2860.
Wu, C. H. (2007). Studies of the equilibrium and thermodynamics of the adsorption of Cu(II) onto as-produced and modified carbon nanotubes. Journal of Colloid and Interface Science, 311, 338–346.
Acknowledgments
The authors want to thank Stephen Harmon and Christina Bennett-Stamper for their work on SEM/EDS and Debby Roose for running the analysis in the ICP-AES. We also would like to acknowledge Dr. James Mack and Teresa Cook for the use of the department ball milling equipment. Special thanks to Liang Yan for the BET analysis. This study was supported by EPA project number S-10591-QP-1-0.
Conflict of Interest
The U.S. Environmental Protection Agency, through its Office of Research and Development, funded and managed, or partially funded and collaborated in, the research described herein. It has been subjected to the Agency’s administrative review and has been approved for external publication. Any opinions expressed in this paper are those of the authors and do not necessarily reflect the views of the Agency; therefore, no official endorsement should be inferred. Any mention of the trade names or commercial products does not constitute endorsement or recommendation for use.
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Zeta potential curves, ICP-AES results, SEM/EDS images, and tables of characteristic IR absorption frequencies can be found in the SI.
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Rosenzweig, S., Sorial, G.A., Sahle-Demessie, E. et al. Study of Cu(II) Chemisorption Mechanisms on Modified Carbon Nanotubes Based on Isotherms, Column Experiments, and FTIR First Derivative Analysis. Water Air Soil Pollut 226, 215 (2015). https://doi.org/10.1007/s11270-015-2482-7
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DOI: https://doi.org/10.1007/s11270-015-2482-7