Carboxylated carbon nanotubes-graphene oxide aerogels as ultralight and renewable high performance adsorbents for efficient adsorption of glyphosate
Hao Liu A , Xueying Wang A , Chaofan Ding A , Yuxue Dai A , Yuanling Sun A , Yanna Lin A , Weiyan Sun A , Xiaodong Zhu A , Rui Han A , Dandan Gao A and Chuannan Luo
A B
+ Author Affiliations
- Author Affiliations
A Key Laboratory of Interfacial Reaction and Sensing Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China.
B Corresponding author. Email: chm_yfl518@163.com
Environmental Chemistry 17(1) 6-16 https://doi.org/10.1071/EN19107
Submitted: 4 April 2019 Accepted: 16 July 2019 Published: 23 August 2019
Environmental context. Glyphosate is a highly effective and widely used organophosphorus pesticide, but its residues can harm the environment and human health. We report a carboxylated carbon nanotubes-graphene oxide aerogel that can efficiently remove glyphosate from water. This technology has great application prospects in dealing with water contaminated with glyphosate.
Abstract. Glyphosate, an organophosphorus pesticide, has received considerable attention in recent years owing to its carcinogenic potency. The technologies that remove glyphosate in the environment, especially in water, are important. In this work, we prepare a carboxylated carbon nanotubes-graphene oxide aerogel (cCNTs-GA) by the freeze-drying method for the adsorption of glyphosate. The prepared aerogel exhibits an ultra-low density (7.30 mg cm−3), good morphology and strong mechanical strength. Meanwhile, a NaOH solution (0.5 mol L−1) is selected as an eluent and the adsorption parameters for the adsorption of glyphosate are optimised. The properties of the adsorbents after multiple repetitions and the adsorption mechanism of the cCNTs-GA are also studied. The results show that the adsorbent can be recycled more than 20 times and maintains a good adsorption performance. The maximum adsorption capacity of glyphosate at pH 3 is calculated from the Langmuir isotherm model (546 mg g−1 at the temperature of 298 K), and the cCNTs-GA exhibits a high adsorption affinity and adsorption capacity for glyphosate, as determined by the partition coefficient (PC). The pseudo-second-order kinetic model fits well to the dynamic behaviour. The equilibrium adsorption process follows the Langmuir isotherm model and the adsorption process is mainly controlled by the intraparticle diffusion model. Furthermore, thermodynamic analysis indicates that the adsorption of glyphosate on the cCNTs-GA is exothermic and spontaneous. The adsorbent is used to remove glyphosate from waste water and the adsorption capacity of the cCNTs-GA for glyphosate is higher than other adsorbents, which indicates that the developed adsorbent has a great potential application in environmental pollution treatment.
Additional keywords: freeze drying method, water treatment.
References
Bai SH, Ogbourne SM (2016). Glyphosate: environmental contamination, toxicity and potential risks to human health via food contamination. Environmental Science and Pollution Research International 23, 18988–19001.| Glyphosate: environmental contamination, toxicity and potential risks to human health via food contaminationCrossref | GoogleScholarGoogle Scholar | 27541149PubMed |
Bora A, Mohan K, Pegu D, Gohain CB, Dolui SK (2017). A room temperature methanol vapor sensor based on highly conducting carboxylated multi-walled carbon nanotube/polyaniline nanotube composite. Sensors and Actuators. B, Chemical 253, 977–986.
| A room temperature methanol vapor sensor based on highly conducting carboxylated multi-walled carbon nanotube/polyaniline nanotube compositeCrossref | GoogleScholarGoogle Scholar |
Carneiro RTA, Taketa TB, Gomes Neto RJ, Oliveira JL, Campos EVR, de Moraes MA, da Silva CMG, Beppu MM, Fraceto LF (2015). Removal of glyphosate herbicide from water using biopolymer membranes. Journal of Environmental Management 151, 353–360.
| Removal of glyphosate herbicide from water using biopolymer membranesCrossref | GoogleScholarGoogle Scholar |
Cattani D, de Liz Oliveira Cavalli VL, Heinz Rieg CE, Domingues JT, Dal-Cim T, Tasca CI, Mena Barreto Silva FR, Zamoner A (2014). Mechanisms underlying the neurotoxicity induced by glyphosate-based herbicide in immature rat hippocampus: Involvement of glutamate excitotoxicity. Toxicology 320, 34–45.
| Mechanisms underlying the neurotoxicity induced by glyphosate-based herbicide in immature rat hippocampus: Involvement of glutamate excitotoxicityCrossref | GoogleScholarGoogle Scholar | 24636977PubMed |
Chen Z, Pierre D, He H, Tan S, Pham-Huy C, Hong H, Huang J (2011). Adsorption behavior of epirubicin hydrochloride on carboxylated carbon nanotubes. International Journal of Pharmaceutics 405, 153–161.
| Adsorption behavior of epirubicin hydrochloride on carboxylated carbon nanotubesCrossref | GoogleScholarGoogle Scholar | 21145959PubMed |
Connolly A, Jones K, Galea KS, Basinas I, Kenny L, McGowan P, Coggins M (2017). Exposure assessment using human biomonitoring for glyphosate and fluroxypyr users in amenity horticulture. International Journal of Hygiene and Environmental Health 220, 1064–1073.
| Exposure assessment using human biomonitoring for glyphosate and fluroxypyr users in amenity horticultureCrossref | GoogleScholarGoogle Scholar | 28668341PubMed |
Corrie AM, Williams DR (1976). Thermodynamic considerations in co-ordination. Part XXIV. Gibbs free-energy changes, enthalpies, and entropies of formation of complexes of glycinate, glycylglycinate, glycylglycylglycinate, cysteinate, and glutathionate with hydrogen and lead(II) ions and suggested aqueous structures. Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry 12, 1068–1072.
| Thermodynamic considerations in co-ordination. Part XXIV. Gibbs free-energy changes, enthalpies, and entropies of formation of complexes of glycinate, glycylglycinate, glycylglycylglycinate, cysteinate, and glutathionate with hydrogen and lead(II) ions and suggested aqueous structuresCrossref | GoogleScholarGoogle Scholar |
Dada AO, Olalekan AP, Olatunya AM, Dada O (2012). Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms studies of equilibrium sorption of Zn2+ onto phosphoric acid modified rice husk. IOSR Journal of Applied Chemistry 3, 38–45.
| Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms studies of equilibrium sorption of Zn2+ onto phosphoric acid modified rice huskCrossref | GoogleScholarGoogle Scholar |
Ding C, Wang X, Liu H, Li Y, Sun Y, Lin Y, Sun W, Zhu X, Dai Y, Luo C (2018). Glyphosate removal from water by functional three-dimensional graphene aerogels. Environmental Chemistry 15, 325–335.
| Glyphosate removal from water by functional three-dimensional graphene aerogelsCrossref | GoogleScholarGoogle Scholar |
Felton DE, Ederer M, Steffens T, Hartzell PL, Waynant KV (2018). UV-Vis Spectrophotometric Analysis and Quantification of Glyphosate for an Interdisciplinary Undergraduate Laboratory. Journal of Chemical Education 95, 136–140.
| UV-Vis Spectrophotometric Analysis and Quantification of Glyphosate for an Interdisciplinary Undergraduate LaboratoryCrossref | GoogleScholarGoogle Scholar |
Fu D, He Z, Su S, Xu B, Liu Y, Zhao Y (2017). Fabrication of α-FeOOH decorated graphene oxide-carbon nanotubes aerogel and its application in adsorption of arsenic species. Journal of Colloid and Interface Science 505, 105–114.
| Fabrication of α-FeOOH decorated graphene oxide-carbon nanotubes aerogel and its application in adsorption of arsenic speciesCrossref | GoogleScholarGoogle Scholar | 28577460PubMed |
Gao L, Wang Y, Yan T, Cui L, Hu L, Yan L, Wei Q, Du B (2015). A novel magnetic polysaccharide-graphene oxide composite for removal of cationic dyes from aqueous solution. New Journal of Chemistry 39, 2908–2916.
| A novel magnetic polysaccharide-graphene oxide composite for removal of cationic dyes from aqueous solutionCrossref | GoogleScholarGoogle Scholar |
Ge J, Shi L-A, Wang Y-C, Zhao H-Y, Yao H-B, Zhu Y-B, Zhang Y, Zhu H-W, Wu H-A, Yu S-H (2017). Joule-heated graphene-wrapped sponge enables fast clean-up of viscous crude-oil spill. Nature Nanotechnology 12, 434–440.
| Joule-heated graphene-wrapped sponge enables fast clean-up of viscous crude-oil spillCrossref | GoogleScholarGoogle Scholar | 28369045PubMed |
Guo L, Cao Y, Jin K, Han L, Li G, Liu J, Ma S (2018). Adsorption Characteristics of Glyphosate on Cross-Linked Amino-Starch. Journal of Chemical & Engineering Data 63, 422–428.
| Adsorption Characteristics of Glyphosate on Cross-Linked Amino-StarchCrossref | GoogleScholarGoogle Scholar |
Hall KR, Eagleton LC, Acrivos A, Vermeulen T (1966). Pore- and Solid-Diffusion Kinetics in Fixed-Bed Adsorption under Constant-Pattern Conditions. Industrial & Engineering Chemistry Fundamentals 5, 212–223.
| Pore- and Solid-Diffusion Kinetics in Fixed-Bed Adsorption under Constant-Pattern ConditionsCrossref | GoogleScholarGoogle Scholar |
He J, Shang H, Zhang X, Sun X (2018). Synthesis and application of ion imprinting polymer coated magnetic multi-walled carbon nanotubes for selective adsorption of nickel ion. Applied Surface Science 428, 110–117.
| Synthesis and application of ion imprinting polymer coated magnetic multi-walled carbon nanotubes for selective adsorption of nickel ionCrossref | GoogleScholarGoogle Scholar |
Ho YS, McKay G (1999). Pseudo-second order model for sorption processes. Process Biochemistry 34, 451–465.
| Pseudo-second order model for sorption processesCrossref | GoogleScholarGoogle Scholar |
Ho YS, McKay G (2000). The kinetics of sorption of divalent metal ions onto sphagnum moss peat. Water Research 34, 735–742.
| The kinetics of sorption of divalent metal ions onto sphagnum moss peatCrossref | GoogleScholarGoogle Scholar |
Hossaini H, Moussavi G, Farrokhi M (2014). The Investigation of the LED-Activated FeFNS-TiO2 Nanocatalyst for Photocatalytic Degradation and Mineralization of Organophosphate Pesticides in Water. Water Research 59, 130–144.
| The Investigation of the LED-Activated FeFNS-TiO2 Nanocatalyst for Photocatalytic Degradation and Mineralization of Organophosphate Pesticides in WaterCrossref | GoogleScholarGoogle Scholar | 24793111PubMed |
Hu YS, Zhao YQ, Sorohan B (2011). Removal of glyphosate from aqueous environment by adsorption using water industrial residual. Desalination 271, 150–156.
| Removal of glyphosate from aqueous environment by adsorption using water industrial residualCrossref | GoogleScholarGoogle Scholar |
Huang H, Chen P, Zhang X, Lu Y, Zhan W (2013). Edge-to-Edge Assembled Graphene Oxide Aerogels with Outstanding Mechanical Performance and Superhigh Chemical Activity. Small 9, 1397–1404.
| Edge-to-Edge Assembled Graphene Oxide Aerogels with Outstanding Mechanical Performance and Superhigh Chemical ActivityCrossref | GoogleScholarGoogle Scholar | 23512583PubMed |
Jiang X, Ouyang Z, Zhang Z, Yang C, Li X, Dang Z, Wu P (2018). Mechanism of glyphosate removal by biochar supported nano-zero-valent iron in aqueous solutions. Colloids and Surfaces. A, Physicochemical and Engineering Aspects 547, 64–72.
| Mechanism of glyphosate removal by biochar supported nano-zero-valent iron in aqueous solutionsCrossref | GoogleScholarGoogle Scholar |
Karthikraj R, Kannan K (2019). Widespread occurrence of glyphosate in urine from pet dogs and cats in New York State, USA. The Science of the Total Environment 659, 790–795.
| Widespread occurrence of glyphosate in urine from pet dogs and cats in New York State, USACrossref | GoogleScholarGoogle Scholar | 31096409PubMed |
Khenifi A, Derriche Z, Mousty C, Prévot V, Forano C (2010). Adsorption of Glyphosate and Glufosinate by Ni2AlNO3 layered double hydroxide. Applied Clay Science 47, 362–371.
| Adsorption of Glyphosate and Glufosinate by Ni2AlNO3 layered double hydroxideCrossref | GoogleScholarGoogle Scholar |
Kittle RP, McDermid KJ, Muehlstein L, Balazs GH (2018). Effects of glyphosate herbicide on the gastrointestinal microflora of Hawaiian green turtles (Chelonia mydas) Linnaeus. Marine Pollution Bulletin 127, 170–174.
| Effects of glyphosate herbicide on the gastrointestinal microflora of Hawaiian green turtles (Chelonia mydas) LinnaeusCrossref | GoogleScholarGoogle Scholar | 29475651PubMed |
Langmuir I (1918). The adsorption of gases on plane surfaces of glass mica and platinum. Journal of the American Chemical Society 40, 1361–1403.
| The adsorption of gases on plane surfaces of glass mica and platinumCrossref | GoogleScholarGoogle Scholar |
Liang Q, Luo H, Geng J, Chen J (2018). Facile one-pot preparation of nitrogen-doped ultra-light graphene oxide aerogel and its prominent adsorption performance of Cr(VI). Chemical Engineering Journal 338, 62–71.
| Facile one-pot preparation of nitrogen-doped ultra-light graphene oxide aerogel and its prominent adsorption performance of Cr(VI)Crossref | GoogleScholarGoogle Scholar |
Liu B, Dong L, Yu Q, Li X, Wu F, Tan Z, Luo S (2016). Thermodynamic Study on the Protonation Reactions of Glyphosate in Aqueous Solution: Potentiometry, Calorimetry and NMR spectroscopy. The Journal of Physical Chemistry B 120, 2132–2137.
| Thermodynamic Study on the Protonation Reactions of Glyphosate in Aqueous Solution: Potentiometry, Calorimetry and NMR spectroscopyCrossref | GoogleScholarGoogle Scholar | 26862689PubMed |
Liu Y, Liu X, Zhao Y, Dionysiou DD (2017). Aligned α-FeOOH nanorods anchored on a graphene oxide-carbon nanotubes aerogel can serve as an effective Fenton-like oxidation catalyst. Applied Catalysis B: Environmental 213, 74–86.
| Aligned α-FeOOH nanorods anchored on a graphene oxide-carbon nanotubes aerogel can serve as an effective Fenton-like oxidation catalystCrossref | GoogleScholarGoogle Scholar |
Mayakaduwa SS, Kumarathilaka P, Herath I, Ahmad M, Al-Wabel M, Ok YS, Usman A, Abduljabbar A, Vithanage M (2016). Equilibrium and kinetic mechanisms of woody biochar on aqueous glyphosate removal. Chemosphere 144, 2516–2521.
| Equilibrium and kinetic mechanisms of woody biochar on aqueous glyphosate removalCrossref | GoogleScholarGoogle Scholar | 26340852PubMed |
Mesnage R, Defarge N, Spiroux De Vendômois J, Séralini GE (2015). Potential toxic effects of glyphosate and its commercial formulations below regulatory limits. Food and Chemical Toxicology 84, 133–153.
| Potential toxic effects of glyphosate and its commercial formulations below regulatory limitsCrossref | GoogleScholarGoogle Scholar | 26282372PubMed |
Mi X, Huang G, Xie W, Wang W, Liu Y, Gao J (2012). Preparation of graphene oxide aerogel and its adsorption for Cu2+ ions. Carbon 50, 4856–4864.
| Preparation of graphene oxide aerogel and its adsorption for Cu2+ ionsCrossref | GoogleScholarGoogle Scholar |
Na CJ, Yoo MJ, Tsang DCW, Kim HW, Kim KH (2019). High-performance materials for effective sorptive removal of formaldehyde in air. Journal of Hazardous Materials 366, 452–465.
| High-performance materials for effective sorptive removal of formaldehyde in airCrossref | GoogleScholarGoogle Scholar | 30562657PubMed |
Peng G, Zhang M, Deng S, Shan D, He Q, Yu G (2018). Adsorption and catalytic oxidation of pharmaceuticals by nitrogen-doped reduced graphene oxide/Fe3O4 nanocomposite. Chemical Engineering Journal 341, 361–370.
| Adsorption and catalytic oxidation of pharmaceuticals by nitrogen-doped reduced graphene oxide/Fe3O4 nanocompositeCrossref | GoogleScholarGoogle Scholar |
Rivoira L, Appendini M, Fiorilli S, Onida B, Del Bubba M, Bruzzoniti MC (2016). Functionalized iron oxide/SBA-15 sorbent: investigation of adsorption performance towards glyphosate herbicide. Environmental Science and Pollution Research International 23, 21682–21691.
| Functionalized iron oxide/SBA-15 sorbent: investigation of adsorption performance towards glyphosate herbicideCrossref | GoogleScholarGoogle Scholar | 27522203PubMed |
Samet Y, Agengui L, Abdelhédi R (2010). Electrochemical Degradation of Chlorpyrifos Pesticide in Aqueous Solutions by Anodic Oxidation at Boron-Doped Diamond Electrodes. Chemical Engineering Journal 161, 167–172.
| Electrochemical Degradation of Chlorpyrifos Pesticide in Aqueous Solutions by Anodic Oxidation at Boron-Doped Diamond ElectrodesCrossref | GoogleScholarGoogle Scholar |
Sheindorf C, Rebhun M, Sheintuch M (1981). A Freundlich-type multicomponent isotherm. Journal of Colloid and Interface Science 79, 136–142.
| A Freundlich-type multicomponent isothermCrossref | GoogleScholarGoogle Scholar |
Szulejko JE, Kim KH, Parise J (2019). Seeking the most powerful and practical real-world sorbents for gaseous benzene as a representative volatile organic compound based on performance metrics. Separation and Purification Technology 212, 980–985.
| Seeking the most powerful and practical real-world sorbents for gaseous benzene as a representative volatile organic compound based on performance metricsCrossref | GoogleScholarGoogle Scholar |
Van Stempvoort DR, Spoelstra J, Senger ND, Brown SJ, Post R, Struger J (2016). Glyphosate residues in rural groundwater, Nottawasaga River Watershed, Ontario, Canada. Pest Management Science 72, 1862–1872.
| Glyphosate residues in rural groundwater, Nottawasaga River Watershed, Ontario, CanadaCrossref | GoogleScholarGoogle Scholar | 26732707PubMed |
Vikrant K, Kim KH (2019). Nanomaterials for the adsorptive treatment of Hg(II) ions from water. Chemical Engineering Journal 358, 264–282.
| Nanomaterials for the adsorptive treatment of Hg(II) ions from waterCrossref | GoogleScholarGoogle Scholar |
Wan W, Zhang R, Li W, Liu H, Lin Y, Li L, Zhou Y (2016). Graphene-carbon nanotube aerogel as an ultra-light, compressible and recyclable highly efficient absorbent for oil and dyes. Environmental Science. Nano 3, 107–113.
| Graphene-carbon nanotube aerogel as an ultra-light, compressible and recyclable highly efficient absorbent for oil and dyesCrossref | GoogleScholarGoogle Scholar |
Wang F, Wang Y, Zhan W, Yu S, Zhong W, Sui G, Yang X (2017). Facile synthesis of ultra-light graphene aerogels with super absorption capability for organic solvents and strain-sensitive electrical conductivity. Chemical Engineering Journal 320, 539–548.
| Facile synthesis of ultra-light graphene aerogels with super absorption capability for organic solvents and strain-sensitive electrical conductivityCrossref | GoogleScholarGoogle Scholar |
Wei W, Du J, Li J, Yan M, Zhu Q, Jin X, Zhu X, Hu Z, Tang Y, Lu Y (2013). Construction of Robust Enzyme Nanocapsules for Effective Organophosphate Decontamination, Detoxification, and Protection. Advanced Materials 25, 2212–2218.
| Construction of Robust Enzyme Nanocapsules for Effective Organophosphate Decontamination, Detoxification, and ProtectionCrossref | GoogleScholarGoogle Scholar | 23436305PubMed |
Xiong Y, Cui X, Zhang P, Wang Y, Lou Z, Shan W (2017). Improving Re(VII) Adsorption on Diisobutylamine-Functionalized Graphene Oxide. ACS Sustainable Chemistry & Engineering 5, 1010–1018.
| Improving Re(VII) Adsorption on Diisobutylamine-Functionalized Graphene OxideCrossref | GoogleScholarGoogle Scholar |
Zavareh S, Farrokhzad Z, Darvishi F (2018). Modification of zeolite 4A for use as an adsorbent for glyphosate and as an antibacterial agent for water. Ecotoxicology and Environmental Safety 155, 1–8.
| Modification of zeolite 4A for use as an adsorbent for glyphosate and as an antibacterial agent for waterCrossref | GoogleScholarGoogle Scholar | 29486406PubMed |
Zhan W, Yu S, Gao L, Wang F, Fu X, Sui G, Yang X (2018). Bioinspired Assembly of Carbon Nanotube into Graphene Aerogel with “Cabbagelike” Hierarchical Porous Structure for Highly Efficient Organic Pollutants Cleanup. ACS Applied Materials & Interfaces 10, 1093–1103.
| Bioinspired Assembly of Carbon Nanotube into Graphene Aerogel with “Cabbagelike” Hierarchical Porous Structure for Highly Efficient Organic Pollutants CleanupCrossref | GoogleScholarGoogle Scholar |
Zhou C, Jia D, Liu M, Liu X, Li C (2017). Removal of Glyphosate from Aqueous Solution Using Nanosized Copper Hydroxide Modified Resin: Equilibrium Isotherms and Kinetics. Journal of Chemical & Engineering Data 62, 3585–3592.
| Removal of Glyphosate from Aqueous Solution Using Nanosized Copper Hydroxide Modified Resin: Equilibrium Isotherms and KineticsCrossref | GoogleScholarGoogle Scholar |
Zhu X, Li B, Yang J, Li Y, Zhao W, Shi J, Gu J (2015). Effective Adsorption and Enhanced Removal of Organophosphorus Pesticides from Aqueous Solution by Zr-Based MOFs of UiO-67. ACS Applied Materials & Interfaces 7, 223–231.
| Effective Adsorption and Enhanced Removal of Organophosphorus Pesticides from Aqueous Solution by Zr-Based MOFs of UiO-67Crossref | GoogleScholarGoogle Scholar |
