Aggregation of Graphene Oxide in Natural Waters: Role of Solution Chemistry and Specific Interactions
Publication: Journal of Environmental Engineering
Volume 145, Issue 9
Abstract
In this paper, the impact of pH, ionic strength, and dissolved organic matter [humic acid (HA) and tannic acid (TA)] on graphene oxide (GO) stability was investigated. The results showed that the GO is negatively charged over a pH range from 2 to 11. pH did significantly affect GO stability at a level of 4 or higher, but the particles became unstable below pH 3 due to protonation of at the edge. Ionic strength (IS) and salt type had observable effects on stability as a result of electrical double layer compression and specific interactions. affects GO more noticeably than NaCl because of the binding ability of ions with carboxyl and hydroxyl functional groups. pH had negligible effects in the presence of 10 mM NaCl, but 1 mM decreased GO stability as pH increased owing to the adsorption of ions on the surface functional groups of GO and the consequent decrease of surface charge. The applicability of DLVO theory as a predictive tool was investigated by modeling GO sheets in two different geometries; three-dimensional spherelike particles and two-dimensional particles at different values of pH and IS. Overall, the specific interactions and chemical structure of adsorbed organics had a dominant role in GO stability.
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Acknowledgments
We acknowledge the support of Dr. Keith Goyne, School of Natural Resources, University of Missouri-Columbia, who provided access to the FTIR instrument. We also thank Dr. Eric Bohannan and Brian Porter, Materials Research Center, University of Missouri-Rolla, for their assistance collecting XRD, AFM, and XPS data.
References
Akhavan, O., E. Ghaderi, and A. Esfandiar. 2011. “Wrapping bacteria by graphene nanosheets for isolation from environment, reactivation by sonication, and inactivation by near-infrared irradiation.” J. Phys. Chem. B 115 (19): 6279–6288. https://doi.org/10.1021/jp200686k.
Archanjo, B. S., J. R. Araujo, A. M. Silva, R. B. Capaz, N. P. S. Falcão, A. Jorio, and C. A. Achete. 2014. “Chemical analysis and molecular models for calcium-oxygen–carbon Interactions in black carbon found in fertile Amazonian anthrosoils.” Environ. Sci. Technol. 48 (13): 7445–7452. https://doi.org/10.1021/es501046b.
Arvidsson, R., S. Molander, and B. A. Sandén. 2013. “Review of potential environmental and health risks of the nanomaterial graphene.” Hum. Ecol. Risk Assess. 19 (4): 873–887. https://doi.org/10.1080/10807039.2012.702039.
Chen, L., P. Hu, L. Zhang, S. Huang, L. Luo, and C. Huang. 2012. “Toxicity of graphene oxide and multi-walled carbon nanotubes against human cells and zebrafish.” Sci. China Chem. 55 (10): 2209–2216. https://doi.org/10.1007/s11426-012-4620-z.
Chowdhury, I., M. C. Duch, N. D. Mansukhani, M. C. Hersam, and D. Bouchard. 2013. “Colloidal properties and stability of graphene oxide nanomaterials in the aquatic environment.” Environ. Sci. Technol. 47 (12): 6288–6296. https://doi.org/10.1021/es400483k.
Chowdhury, I., N. D. Mansukhani, L. M. Guiney, M. C. Hersam, and D. Bouchard. 2015. “Aggregation and stability of reduced graphene oxide: Complex roles of divalent cations, pH, and natural organic matter.” Environ. Sci. Technol. 49 (18): 10886–10893. https://doi.org/10.1021/acs.est.5b01866.
Chu, K. H., Y. Huang, M. Yu, N. Her, J. R. V. Flora, C. M. Park, S. Kim, J. Cho, and Y. Yoon. 2016. “Evaluation of humic acid and tannic acid fouling in graphene oxide-coated ultrafiltration membranes.” ACS Appl. Mater. Interfaces 8 (34): 22270–22279. https://doi.org/10.1021/acsami.6b08020.
Cohen-Tanugi, D., and J. C. Grossman. 2012. “Water desalination across nanoporous graphene.” Nano Lett. 12 (7): 3602–3608. https://doi.org/10.1021/nl3012853.
Compton, O. C., and S. T. Nguyen. 2010. “Graphene oxide, highly reduced graphene oxide, and graphene: Versatile building blocks for carbon-based materials.” Small 6 (6): 711–723. https://doi.org/10.1002/smll.200901934.
Cote, L. J., J. Kim, V. C. Tung, J. Luo, F. Kim, and J. Huang. 2010. “Graphene oxide as surfactant sheets.” Pure Appl. Chem. 83 (1): 95–110. https://doi.org/10.1351/PAC-CON-10-10-25.
Crittenden, J. C., R. R. Trussell, D. W. Hand, K. J. Howe, and G. Tchobanoglous. 2005. Water treatment: Principles and design. 2nd ed. New York: Wiley.
Dimiev, A. M., L. B. Alemany, and J. M. Tour. 2013. “Graphene oxide. Origin of acidity, its instability in water, and a new dynamic structural model.” ACS Nano 7 (1): 576–588. https://doi.org/10.1021/nn3047378.
Dreyer, D. R., S. Park, C. W. Bielawski, and R. S. Ruoff. 2010. “The chemistry of graphene oxide.” Chem. Soc. Rev. 39 (1): 228–240. https://doi.org/10.1039/B917103G.
Elimelech, M., J. Gregory, X. Jia, and R. A. Williams. 1995. Particle deposition & aggregation. 1st ed. Boston: Butterworth-Heinemann.
Emara, M. M., N. A. Farid, A. M. Wasfi, M. M. Bahr, and H. M. Abd-Elbary. 1984. “Thermodynamics of ion association in aqueous solutions of calcium- and magnesium-substituted hydroxybenzoates using an ion-selective electrode technique.” J. Phys. Chem. 88 (15): 3345–3348. https://doi.org/10.1021/j150659a042.
Esfahani, M. R., V. L. Pallem, H. A. Stretz, and M. J. M. Wells. 2016. “Humic acid disaggregation with/of gold nanoparticles: Effects of nanoparticle size and pH.” Environ. Nanotechnol. Monit. Manage. 6 (Dec): 54–63. https://doi.org/10.1016/j.enmm.2016.06.007.
Esfahani, M. R., H. A. Stretz, and M. J. M. Wells. 2015. “Abiotic reversible self-assembly of fulvic and humic acid aggregates in low electrolytic conductivity solutions by dynamic light scattering and zeta potential investigation.” Sci. Total Environ. 537 (Dec): 81–92. https://doi.org/10.1016/j.scitotenv.2015.08.001.
Feriancikova, L., and S. Xu. 2012. “Deposition and remobilization of graphene oxide within saturated sand packs.” J. Hazard. Mater. 235–236 (Oct): 194–200. https://doi.org/10.1016/j.jhazmat.2012.07.041.
Gao, W., L. B. Alemany, L. Ci, and P. M. Ajayan. 2009. “New insights into the structure and reduction of graphite oxide.” Nat. Chem. 1 (5): 403–408. https://doi.org/10.1038/nchem.281.
Gao, W., M. Majumder, L. B. Alemany, T. N. Narayanan, M. A. Ibarra, B. K. Pradhan, and P. M. Ajayan. 2011. “Engineered graphite oxide materials for application in water purification.” ACS Appl. Mater. Interfaces 3 (6): 1821–1826. https://doi.org/10.1021/am200300u.
Gao, Y., X. Ren, X. Tan, T. Hayat, A. Alsaedi, and C. Chen. 2017. “Insights into key factors controlling GO stability in natural surface waters.” J. Hazard. Mater. 335 (Aug): 56–65. https://doi.org/10.1016/j.jhazmat.2017.04.027.
Gudarzi, M. M. 2016. “Colloidal stability of graphene oxide: Aggregation in two dimensions.” Langmuir 32 (20): 5058–5068. https://doi.org/10.1021/acs.langmuir.6b01012.
Hartono, T., S. Wang, Q. Ma, and Z. Zhu. 2009. “Layer structured graphite oxide as a novel adsorbent for humic acid removal from aqueous solution.” J. Colloid Interface Sci. 333 (1): 114–119. https://doi.org/10.1016/j.jcis.2009.02.005.
Hua, Z., Z. Tang, X. Bai, J. Zhang, L. Yu, and H. Cheng. 2015. “Aggregation and resuspension of graphene oxide in simulated natural surface aquatic environments.” Environ. Pollut. 205 (Oct): 161–169. https://doi.org/10.1016/j.envpol.2015.05.039.
Hummers, W. S., and R. E. Offeman. 1958. “Preparation of graphitic oxide.” J. Am. Chem. Soc. 80 (6): 1339. https://doi.org/10.1021/ja01539a017.
Jastrzębska, A. M., and A. R. Olszyna. 2015. “The ecotoxicity of graphene family materials: Current status, knowledge gaps and future needs.” J. Nanopart. Res. 17 (1): 40. https://doi.org/10.1007/s11051-014-2817-0.
Jiang, Y., R. Raliya, J. D. Fortner, and P. Biswas. 2016. “Graphene oxides in water: Correlating morphology and surface chemistry with aggregation behavior.” Environ. Sci. Technol. 50 (13): 6964–6973. https://doi.org/10.1021/acs.est.6b00810.
Lanphere, J. D., C. J. Luth, and S. L. Walker. 2013. “Effects of solution chemistry on the transport of graphene oxide in saturated porous media.” Environ. Sci. Technol. 47 (9): 4255–4261. https://doi.org/10.1021/es400138c.
Li, D., M. B. Muller, S. Gilje, R. B. Kaner, and G. G. Wallace. 2008. “Processable aqueous dispersions of graphene nanosheets.” Nat. Nanotechnol. 3 (2): 101–105. https://doi.org/10.1038/nnano.2007.451.
Liang, L.-J., T. Wu, Y. Kang, and Q. Wang. 2013. “Dispersion of graphene sheets in aqueous solution by oligodeoxynucleotides.” Chemphyschem 14 (8): 1626–1632. https://doi.org/10.1002/cphc.201201084.
Lin, D., and B. Xing. 2008. “Tannic acid adsorption and its role for stabilizing carbon nanotube suspensions.” Environ. Sci. Technol. 42 (16): 5917–5923. https://doi.org/10.1021/es800329c.
Liu, S., T. H. Zeng, M. Hofmann, E. Burcombe, J. Wei, R. Jiang, J. Kong, and Y. Chen. 2011. “Antibacterial activity of graphite, graphite oxide, graphene oxide, and reduced graphene oxide: Membrane and oxidative Stress.” ACS Nano 5 (9): 6971–6980. https://doi.org/10.1021/nn202451x.
Lotya, M., P. J. King, U. Khan, S. De, and J. N. Coleman. 2010. “High-concentration, surfactant-stabilized graphene dispersions.” ACS Nano 4 (6): 3155–3162. https://doi.org/10.1021/nn1005304.
Luo, J., L. J. Cote, V. C. Tung, A. T. L. Tan, P. E. Goins, J. Wu, and J. Huang. 2010. “Graphene oxide nanocolloids.” J. Am. Chem. Soc. 132 (50): 17667–17669. https://doi.org/10.1021/ja1078943.
Novoselov, K. S., V. I. Falko, L. Colombo, P. R. Gellert, M. G. Schwab, and K. Kim. 2012. “A roadmap for graphene.” Nature 490 (7419): 192–200. https://doi.org/10.1038/nature11458.
Ouatmane, A., M. Hafidi, M. El Gharous, and J. C. Revel. 1999. “Complexation of calcium ions by humic and fulvic acids.” Analusis 27 (5): 428–431. https://doi.org/10.1051/analusis:1999270428.
Papageorgiou, D. G., I. A. Kinloch, and R. J. Young. 2015. “Graphene/elastomer nanocomposites.” Carbon 95 (Dec): 460–484. https://doi.org/10.1016/j.carbon.2015.08.055.
Park, S., K.-S. Lee, G. Bozoklu, W. Cai, S. T. Nguyen, and R. S. Ruoff. 2008. “Graphene oxide papers modified by divalent ions—Enhancing mechanical properties via chemical cross-linking.” ACS Nano 2 (3): 572–578. https://doi.org/10.1021/nn700349a.
Pelley, A. J., and N. Tufenkji. 2008. “Effect of particle size and natural organic matter on the migration of nano- and microscale latex particles in saturated porous media.” J. Colloid Interface Sci. 321 (1): 74–83. https://doi.org/10.1016/j.jcis.2008.01.046.
Qi, Y., T. Xia, Y. Li, L. Duan, and W. Chen. 2016. “Colloidal stability of reduced graphene oxide materials prepared using different reducing agents.” Environ. Sci. Nano 3 (5): 1062–1071. https://doi.org/10.1039/C6EN00174B.
Randviir, E. P., D. A. C. Brownson, and C. E. Banks. 2014. “A decade of graphene research: Production, applications and outlook.” Mater. Today 17 (9): 426–432. https://doi.org/10.1016/j.mattod.2014.06.001.
Rao, C. N. R., A. K. Sood, K. S. Subrahmanyam, and A. Govindaraj. 2009. “Graphene: The new two-dimensional nanomaterial.” Angew. Chem. Int. Ed. 48 (42): 7752–7777. https://doi.org/10.1002/anie.200901678.
Ruan, G., Z. Sun, Z. Peng, and J. M. Tour. 2011. “Growth of graphene from food, insects, and waste.” ACS Nano 5 (9): 7601–7607. https://doi.org/10.1021/nn202625c.
Saleh, N. B., L. D. Pfefferle, and M. Elimelech. 2010. “Influence of biomacromolecules and humic Acid on the aggregation kinetics of single-walled carbon nanotubes.” Environ. Sci. Technol. 44 (7): 2412–2418. https://doi.org/10.1021/es903059t.
Sposito, G. 1984. The surface chemistry of soils. 1st ed. New York: Clarendon Press.
Stumm, W. 1992. Chemistry of the solid-water interface: Processes at the mineral-water and particle-water interface in natural systems. New York: Wiley.
Suárez-Iglesias, O., S. Collado, P. Oulego, and M. Díaz. 2017. “Graphene-family nanomaterials in wastewater treatment plants.” Chem. Eng. J. 313 (Apr): 121–135. https://doi.org/10.1016/j.cej.2016.12.022.
Tang, H., Y. Zhao, X. Yang, D. Liu, P. Shao, Z. Zhu, S. Shan, F. Cui, and B. Xing. 2017. “New insight into the aggregation of graphene oxide using molecular dynamics simulations and extended Derjaguin-Landau–Verwey-Overbeek theory.” Environ. Sci. Technol. 51 (17): 9674–9682. https://doi.org/10.1021/acs.est.7b01668.
Terracciano, A., J. Zhang, C. Christodoulatos, F. Wu, and X. Meng. 2017. “Adsorption of on single layer graphene oxide.” J. Environ. Sci. 57 (Jul): 8–14. https://doi.org/10.1016/j.jes.2017.01.008.
Verwey, E. J. W. 1947. “Theory of the stability of lyophobic colloids.” J. Phys. Colloid Chem. 51 (3): 631–636. https://doi.org/10.1021/j150453a001.
Wu, L., L. Liu, B. Gao, R. Muñoz-Carpena, M. Zhang, H. Chen, Z. Zhou, and H. Wang. 2013. “Aggregation kinetics of graphene oxides in aqueous solutions: Experiments, mechanisms, and modeling.” Langmuir 29 (49): 15174–15181. https://doi.org/10.1021/la404134x.
Yang, K., B. Chen, X. Zhu, and B. Xing. 2016. “Aggregation, adsorption, and morphological transformation of graphene oxide in aqueous solutions containing different metal cations.” Environ. Sci. Technol. 50 (20): 11066–11075. https://doi.org/10.1021/acs.est.6b04235.
Ye, N., Z. Wang, S. Wang, H. Fang, and D. Wang. 2018. “Aqueous aggregation and stability of graphene nanoplatelets, graphene oxide, and reduced graphene oxide in simulated natural environmental conditions: Complex roles of surface and solution chemistry.” Environ. Sci. Pollut. Res. 25 (11): 10956–10965. https://doi.org/10.1007/s11356-018-1326-6.
Yoon, K. Y., S. J. An, Y. Chen, J. H. Lee, S. L. Bryant, R. S. Ruoff, C. Huh, and K. P. Johnston. 2013. “Graphene oxide nanoplatelet dispersions in concentrated NaCl and stabilization of oil/water emulsions.” J. Colloid Interface Sci. 403 (Aug): 1–6. https://doi.org/10.1016/j.jcis.2013.03.012.
Zhao, J., F. Liu, Z. Wang, X. Cao, and B. Xing. 2015. “Heteroaggregation of graphene oxide with minerals in aqueous phase.” Environ. Sci. Technol. 49 (5): 2849–2857. https://doi.org/10.1021/es505605w.
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Published In
Journal of Environmental Engineering
Volume 145 • Issue 9 • September 2019
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©2019 American Society of Civil Engineers.
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Received: Dec 16, 2017
Accepted: Jan 17, 2019
Published online: Jun 26, 2019
Published in print: Sep 1, 2019
Discussion open until: Nov 26, 2019
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