Abstract
Density functional theory (DFT) studies have been performed on the unprecedented adsorption of glyphosate pesticide on modified pyridine-like nitrogen-doped graphene (PNG) for the purpose of water remediation. The interaction of glyphosate on the PNG sheet, as well as on Pt-Cu decorated PNG substrates, is investigated. The Pt4-nCun (n = 0–4) clusters, such as Pt4, Pt3Cu1, Pt2Cu2, Pt1Cu3, and Cu4, have been decorated on the PNG surface to increase the reactivity of the adsorbent toward glyphosate. The adsorption of glyphosate on the PNG surface is physisorption, indicated by the low adsorption energy and negligible charge transfer. The mixed metal (Pt-Cu) clusters play a significant role in enhancing the interactions between the adsorbate and adsorbent, leading to better results for the adsorption of glyphosate. Exothermic chemisorption is shown by all Pt4-nCun clusters decorated PNG substrates, and chemical bond formation takes place between the adsorbate and adsorbent. Various electronic properties, like electron density difference plots, give information about the adsorption behavior of glyphosate, and density of states (DOS) plots reveal that on decorating with the cluster, the substrates start exhibiting magnetic character.
Similar content being viewed by others
References
Aguilera-Granja F, Pis-Diez R (2016) Molecular adsorption of NO on free-standing and on graphene-supported Mo3W5 cluster: a density functional theory investigation. J Nanopart Res 18:121–112. https://doi.org/10.1007/s11051-016-3421-2
Andzelm J, King-Smith RD, Fitzgerald G (2001) Geometry optimization of solids using delocalized internal coordinates. Chem Phys Lett 335:321–326. https://doi.org/10.1016/S0009-2614(01)00030-6
Bai SH, Ogbourne SM (2016) Glyphosate: environmental contamination, toxicity and potential risks to human health via food contamination. Environ Sci Pollut R 23:18988–19001. https://doi.org/10.1007/s11356-016-7425-3
Baker J, Kessi A, Delley B (1996) The generation and use of delocalized internal coordinates in geometry optimization. J Chem Phys 105:192. https://doi.org/10.1063/1.471864
Benachour N, Sipahutar H, Moslemi S, Gasnier C, Travert C, Seralini GE (2007) Time-and dose-dependent effects of roundup on human embryonic and placental cells. Arch Environ Contam Toxicol 53:126–133. https://doi.org/10.1007/s00244-006-0154-8
Benbrook CM (2019) How did the US EPA and IARC reach diametrically opposed conclusions on the genotoxicity of glyphosate-based herbicides? Environ Sci Eur 31:2–16. https://doi.org/10.1186/s12302-018-0184-7
Bernareggi M, Chiarello GL, West G, Ratova M, Ferretti AM, Kelly P, Selli E (2019) Cu and Pt clusters deposition on TiO 2 powders by DC magnetron sputtering for photocatalytic hydrogen production. Catal Today 326:15–21. https://doi.org/10.1016/j.cattod.2018.07.011
Bolognesi C, Bonatti S, Degan P, Gallerani E, Peluso M, Rabboni R, Roggieri P, Abbondandolo A (1997) Genotoxic activity of glyphosate and its technical formulation roundup. J Agric Food Chem 45:1957–1962. https://doi.org/10.1021/jf9606518
Cox C (1995) Glyphosate, part 1: toxicology. Journal of Pesticide Reform 15:14–20
Cui H, Zhang X, Zhang J, Ali Mehmood M (2018) Interaction of CO and CH4 adsorption with Noble metal (Rh, Pd, and Pt)-decorated N3-CNTs: a first-principles study. ACS Omega 3:16892–16898. https://doi.org/10.1021/acsomega.8b02578
Delley B (1990) An all-electron numerical method for solving the local density functional for polyatomic molecules. J Chem Phys 92:508–517. https://doi.org/10.1063/1.458452
Delley B (1991) Analytic energy derivatives in the numerical local density-functional approach. J Chem Phys 94:7245–7250. https://doi.org/10.1063/1.460208
Delley B (1995) In: Seminario JM, Politzer P (eds) DMol, a standard tool for density functional calculations: review and advances. Elsevier, New York, pp 221–254
Delley B (1996a) High order integration schemes on the unit sphere. J Comp Chem 17:1152–1155. https://doi.org/10.1002/(SICI)1096-987X(19960715)17:9<1152::AID-JCC7>3.0.CO;2-R
Delley B (1996b) Fast calculation of electrostatics in crystals and large molecules. J Phys Chem 100:6107–6110. https://doi.org/10.1021/jp952713n
Delley B (2000) From molecules to solids with the DMol3 approach. J Chem Phys 113:7756–7764. https://doi.org/10.1063/1.1316015
Delley B (2002) Hardness conserving semilocal pseudopotentials. Phys Rev B 66:155125/1–155125/9. https://doi.org/10.1103/PhysRevB.66.155125
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. Environ Chem 15:325–335. https://doi.org/10.1071/EN18087
Duke SO, Powles SB (2008) Glyphosate: a once-in-a-century herbicide. Pest Manag Sci 64:319–325. https://doi.org/10.1002/ps.1518
Gálvez-González LE, Juárez-Sánchez JO, Pacheco-Contreras R, Garzón IL, Paz-Borbón LO, Posada-Amarillas A (2018) CO2 adsorption on gas-phase Cu4-x Ptx (x= 0-4) clusters: a DFT study. Phys Chem Chem Phys 20:17071–17080. https://doi.org/10.1039/C8CP00818C
Gao JJ, Du P, Zhang QH, Shen X, Chiang FK, Wen YR, Lin X, Liu XJ, Qiu HJ (2019) Platinum single atoms/clusters stabilized in transition metal oxides for enhanced electrocatalysis. Electrochim Acta 297:155–162. https://doi.org/10.1016/j.electacta.2018.11.200
Gasnier C, Dumont C, Benachour N, Clair E, Chagnon MC, Seralini GE (2009) Glyphosate-based herbicides are toxic and endocrine disruptors in human cell lines. Toxicology 262:184–191. https://doi.org/10.1016/j.tox.2009.06.006
Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104. https://doi.org/10.1063/1.3382344
Guo L, Cao Y, Jin K, Han L, Li G, Liu J, Ma S (2018) Adsorption characteristics of glyphosate on cross-linked amino-starch. J Chem Eng Data 63:422-428. https://doi.org/10.1021/acs.jced.7b00842
Hirshfeld FL (1977) Bonded-atom fragments for describing molecular charge densities. Theor Chim Acta 44:129–138. https://doi.org/10.1007/BF00549096
Hohenberg P, Kohn W (1964) Inhomogeneous electron gas. Phys Rev B 136:864–871. https://doi.org/10.1103/PhysRev.136.B864
Hu YS, Zhao YQ, Sorohan B (2011) Removal of glyphosate from aqueous environment by adsorption using water industrial residual. Desalination 271:150–156. https://doi.org/10.1016/j.desal.2010.12.014
Jamison JP, Langlands JH, Lowry RC (1986) Ventilatory impairment from pre-harvest retted flax. Occup Environ Med 43:809–813. https://doi.org/10.1136/oem.43.12.809
Li Y, Zhao C, Wen Y, Wang Y, Yang Y (2018) Adsorption performance and mechanism of magnetic reduced graphene oxide in glyphosate contaminated water. Environ Sci Pollut Res 25:21036–21048. https://doi.org/10.1007/s11356-018-2282-x
Lin YF, Tian N, Xiao C, Sheng T, Li G, Zhang FY, Ye JY, Xu BB, Zhou ZY, Sun SG (2018) Effects of atom arrangement and thickness of Pt atomic layers on Pd nanocrystals for electrocatalysis. Electrochim Acta 271:519–525. https://doi.org/10.1016/j.electacta.2018.03.124
Liu LL, Chen CP, Zhao LS, Wang Y, Wang XC (2017) Metal-embedded nitrogen-doped graphene for H2O molecule dissociation. Carbon 115:773–780. https://doi.org/10.1016/j.carbon.2017.01.073
Mandeep, Sharma L, Kakkar R (2018) DFT study on the adsorption of p-nitrophenol over vacancy and Pt-doped graphene sheets. Comput Theor Chem 1142:88–96. https://doi.org/10.1016/j.comptc.2018.08.020
Mandeep, Sharma L, Kakkar R (2019) Adsorption of bromonitromethane over graphene-based substrates: a density functional theory analysis. ChemistrySelect. 4:4967–4974
Marc J, Mulner-Lorillon O, Bell R (2004) Glyphosate-based pesticides affect cell cycle regulation. Biol Cell 96:245–249. https://doi.org/10.1016/j.biolcel.2003.11.010
Marcinkowski MD, Darby MT, Liu J, Wimble JM, Lucci FR, Lee S, Michaelides A, Flytzani-Stephanopoulos M, Stamatakis M, Sykes EC (2018) Pt/cu single-atom alloys as coke-resistant catalysts for efficient C–H activation. Nat Chem 10:325–332. https://doi.org/10.1038/nchem.2915
Marin P, Bergamasco R, Módenes AN, Paraiso PR, Hamoudi S (2019) Synthesis and characterization of graphene oxide functionalized with MnFe2O4 and supported on activated carbon for glyphosate adsorption in fixed bed column. Process Saf Environ 123:59–71. https://doi.org/10.1016/j.psep.2018.12.027
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. https://doi.org/10.1016/j.chemosphere.2015.07.080
Mayer (1986) Bond orders and valences from ab initio wave functions. Int J Quantum Chem 29:477–483. https://doi.org/10.1002/qua.560290320
McComb BC, Curtis L, Chambers CL, Newton M, Bentson K (2008) Acute toxic hazard evaluations of glyphosate herbicide on terrestrial vertebrates of the Oregon coast range. Environ Sci Pollut R 15:266–272. https://doi.org/10.1065/espr2007.07.437
Monkhorst HJ, Pack JD (1976) Special points for Brillonin-zone integrations. Phys Rev B 13:5188–5192. https://doi.org/10.1103/PhysRevB.13.5188
Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA (2004) Electric field effect in atomically thin carbon films. Science 306:666–669. https://doi.org/10.1126/science.1102896
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys rev Lett 77:3865-3868. Erratum: (1997) Phys rev Lett 78: 1396. https://doi.org/10.1103/PhysRevLett.77.3865
Qiu HJ, Shen X, Wang JQ, Hirata A, Fujita T, Wang Y, Chen MW (2015) Aligned nanoporous Pt–cu bimetallic microwires with high catalytic activity toward methanol electrooxidation. ACS Catal 5:3779–3785. https://doi.org/10.1021/acscatal.5b00073
Rafique M, Mirjat NH, Soomro AM, Khokhar S, Shuai Y (2018) Manipulation of inherent characteristics of graphene through N and mg atom co-doping; a DFT study. Phys Let A 382:1108–1119. https://doi.org/10.1016/j.physleta.2018.02.027
Rangel E, Sansores E (2014) Theoretical study of hydrogen adsorption on nitrogen doped graphene decorated with palladium clusters. Int J Hydrog Energy 39:6558–6566. https://doi.org/10.1016/j.ijhydene.2014.02.062
Rapallo A, Rossi G, Ferrando R, Fortunelli A, Curley BC, Lloyd LD, Tarbuck GM, Johnston RL (2005) Global optimization of bimetallic cluster structures. I. Size-mismatched Ag–cu, Ag–Ni, and au–cu systems. The journal of chemical physics 122: 194308. https://doi.org/10.1063/1.1898223
Richard S, Moslemi S, Sipahutar H, Benachour N, Seralini G (2005) Differential effects of glyphosate and roundup on human placental cells and aromatase. Environ Health Perspect 113:716–720. https://doi.org/10.1289/ehp.7728
Roco MC (2004) Nanoscale science and engineering: unifying and transforming tools. AICHE J 50:890–897. https://doi.org/10.1002/aic.10087
Roco MC (2011) The long view of nanotechnology development: the National Nanotechnology Initiative at 10 years. J Nanopart Res 13:427–445. https://doi.org/10.1007/s11051-010-0192-z
Savvas D, Stefanou G (2018) Determination of random material properties of graphene sheets with different types of defects. Compos Part B: Eng 143:47–54. https://doi.org/10.1016/j.compositesb.2018.01.008
Sun M, Ren Q, Zhao Y, Chou JP, Yu J, Tang W (2017) Electronic and magnetic properties of 4d series transition metal substituted graphene: a first-principles study. Carbon 120:265–273. https://doi.org/10.1016/j.carbon.2017.04.060
Székács A, Darvas B (2012) Forty years with glyphosate. In: Hasaneen MN (ed) Herbicides-properties, synthesis and control of weeds. InTech, Croatia, pp 247–284
Tarone RE (2018) On the International Agency for Research on Cancer classification of glyphosate as a probable human carcinogen. Eur J Cancer Prev 27:82–87. https://doi.org/10.1097/CEJ.0000000000000289
Temple WA, Smith NA (1992) Glyphosate herbicide poisoning experience in New Zealand. N Z Med J 105:173–174
Tyagi J, Kakkar R (2013) Surface affinity of graphene for health, energy and environmental safety applications. Adv Mater Lett 4:721–736. https://doi.org/10.5185/amlett.2013.3438
Veiga F, Zapata JM, Marcos MF, Alvarez E (2001) Dynamics of glyphosate and aminomethylphosphonic acid in a forest soil in Galicia, north-west Spain. Sci Total Environ 271:135–144. https://doi.org/10.1016/S0048-9697(00)00839-1
Waiman CV, Avena MJ, Garrido M, Band BF, Zanini GP (2012) A simple and rapid spectrophotometric method to quantify the herbicide glyphosate in aqueous media. Application to adsorption isotherms on soils and goethite. Geoderma 170:154–158. https://doi.org/10.1016/j.geoderma.2011.11.027
Walsh L, McCormick C, Martin C, Stocco D (2000) Roundup inhibits steroidogenesis by disrupting steroidogenic acute regulatory (StAR) protein expression. Environ Health Perspect 108:769–776. https://doi.org/10.1289/ehp.00108769
Xu D, Tian Y, Zhao J, Wang X (2015) High stability and reactivity of defective graphene-supported FenPt13-n (n= 1, 2, and 3) nanoparticles for oxygen reduction reaction: a theoretical study. J Nanopart Res 17:25–12. https://doi.org/10.1007/s11051-014-2834-z
Yang Q, Wang J, Zhang W, Liu F, Yue X, Liu Y, Yang M, Li Z, Wang J (2017) Interface engineering of metal organic framework on graphene oxide with enhanced adsorption capacity for organophosphorus pesticide. Chem Eng J 313:19–26. https://doi.org/10.1016/j.cej.2016.12.041
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. Ecotox Environ Safe 155:1–8. https://doi.org/10.1016/j.ecoenv.2018.02.043
Zhao C, Wu H (2017) Density functional investigation of mercury and arsenic adsorption on nitrogen doped graphene decorated with palladium clusters: a promising heavy metal sensing material in farmland. Appl Surf Sci 399:55–66. https://doi.org/10.1016/j.apsusc.2016.12.084
Zhao C, Wu H (2018) A first-principles study on the interaction of biogas with noble metal (Rh, Pt, Pd) decorated nitrogen doped graphene as a gas sensor: a DFT study. Appl Surf Sci 435:1199–1212. https://doi.org/10.1016/j.apsusc.2017.11.146
Zhao J, Liu C, Ma J (2017) A light-driven modulation of electric conductance through the adsorption of azobenzene onto silicon-doped- and pyridine-like N3-vacancy graphene. Nanoscale 9:19017–19025. https://doi.org/10.1039/C7NR07382H
Zhou Q, Yong Y, Ju W, Su X, Li X, Wang C, Fu Z (2018) DFT study of the adsorption of 2, 3, 7, 8-tetrachlorodibenzofuran (TCDF) on vacancy-defected graphene doped with Mn and Fe. Curr Appl Phys 18:61–67. https://doi.org/10.1016/j.cap.2017.10.011
Funding
Mandeep acknowledges Council of Scientific and Industrial Research (CSIR), New Delhi, India, for providing financial assistance in form of Senior Research Fellowship (SRF) (CSIR Award No. 09/045(1341)/2014-EMR-I). Archa Gulati acknowledges University Grants Commission (UGC), New Delhi, India, for providing financial assistance in form of Junior Research Fellowship (JRF) (UGC-Ref. No. 111/(CSIR-UGC NET DEC. 2016)).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Mandeep, Gulati, A. & Kakkar, R. DFT study of adsorption of glyphosate pesticide on Pt-Cu decorated pyridine-like nitrogen-doped graphene. J Nanopart Res 22, 17 (2020). https://doi.org/10.1007/s11051-019-4730-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-019-4730-z