Abstract
Rapid removal of toxic dye pollutants in water by conventional materials is ineffective and expensive that warrants the necessity for the architecture of hybrid nanofibrous membrane through layer by layer deposition using electrospinning method. In order to achieve this, here we demonstrated the electrospun fabrication of graphene/ferrocene intercalated polyacrylonitrile nanofibrous (GFPN) membrane through hydrothermal carbonization (HTC) method and studied its potential adsorption properties for the removal of environmental pollutants. An aqueous dispersion of graphene/ferrocene (1 mg/mL) stabilized by the polymeric backbone was prepared by the solvent homogenization method and electrospun to yield nanofibrous membrane and further characterized by several analytical and spectroscopic techniques. Raman and XPS investigations corroborated the intercalation of graphene/Fe decorated onto the nanofibrous network. Adsorption experiments found that the GFPN membrane achieved more than 90% removal of anionic Congo red (CR) dye within 30 min in the aqueous phase irrespective of the concentration and takes some additional time for attaining the equilibrium. The longevity and stability of the membrane was studied by conducting successive adsorption-desorption cycles for the regeneration of its adsorption properties. The de-coloration mechanism was comprehensively investigated through the mathematical approaches using the kinetic and intraparticle diffusion studies and confirmed with the experimental findings through IR and XPS spectroscopic techniques. In a nutshell, this work focuses on the fabrication of hybrid nanofibrous membrane and studied its adsorption properties through varying concentrations of dye (20 to 150 mg/L). Moreover, this work extensively explored the mechanism associated with the adsorption process and specifically emphasize the existence of combined phenomena during the process, i.e., anion-cation interactions, hydrogen bonding, and successive stages of intraparticle diffusion through the comparative elucidation of both theoretical and experimental approaches.
Similar content being viewed by others
References
Allen SJ, McKay G, Khader KYH (1989) Intraparticle diffusion of a basic dye during adsorption onto sphagnum peat. Environ Pollut 56:39–50. https://doi.org/10.1016/0269-7491(89)90120-6
Aunkor MTH, Mahbubul IM, Saidur R, Metselaar HSC (2016) The green reduction of graphene oxide. RSC Adv 6:27807–27828. https://doi.org/10.1039/C6RA03189G
Avinash MB, Subrahmanyam KS, Sundarayya Y, Govindaraju T (2010) Covalent modification and exfoliation of graphene oxide using ferrocene. Nanoscale 2:1762–1766. https://doi.org/10.1039/c0nr00024h
Bharath G, Veeramani V, Chen S-M et al (2015) Edge-carboxylated graphene anchoring magnetite-hydroxyapatite nanocomposite for an efficient 4-nitrophenol sensor. RSC Adv 5:13392–13401. https://doi.org/10.1039/C4RA16035E
Brennan LJ, Surolia PK, Rovelli L et al (2016) Electrophoretic separation and deposition of metal–graphene nanocomposites and their application as electrodes in solar cells. RSC Adv 6:64097–64109. https://doi.org/10.1039/C6RA12825D
Bulut E, Özacar M, Şengil IA (2008) Adsorption of malachite green onto bentonite: equilibrium and kinetic studies and process design. Microporous Mesoporous Mater 115:234–246. https://doi.org/10.1016/j.micromeso.2008.01.039
Chen X, Lai X, Hu J, Wan L (2015) An easy and novel approach to prepare Fe3O4 –reduced graphene oxide composite and its application for high-performance lithium-ion batteries. RSC Adv 5:62913–62920. https://doi.org/10.1039/C5RA07347B
Cui P, Lee J, Hwang E, Lee H (2011) One-pot reduction of graphene oxide at subzero temperatures. Chem Commun 47:12370–12372. https://doi.org/10.1039/c1cc15569e
De Faria AF, Perreault F, Shaulsky E et al (2015) Antimicrobial electrospun biopolymer nanofiber mats functionalized with graphene oxide-silver nanocomposites. ACS Appl Mater Interfaces 7:12751–12759. https://doi.org/10.1021/acsami.5b01639
Doǧan M, Özdemir Y, Alkan M (2007) Adsorption kinetics and mechanism of cationic methyl violet and methylene blue dyes onto sepiolite. Dyes Pigments 75:701–713. https://doi.org/10.1016/j.dyepig.2006.07.023
Dong Y, Li J, Shi L et al (2013) Graphene oxide–iron complex: synthesis, characterization and visible-light-driven photocatalysis. J Mater Chem A 1:644–650. https://doi.org/10.1039/C2TA00371F
Dong Y, Zhang X, Cheng X et al (2014) Highly selective NO2 sensor at room temperature based on nanocomposites of hierarchical nanosphere-like α-Fe 2 O 3 and reduced graphene oxide. RSC Adv 4:57493–57500. https://doi.org/10.1039/C4RA10136G
Dubinin MM (1967) Adsorption in micropores. J Colloid Interface Sci 23:487–499
Ewaldz E, Brettmann B (2019) Molecular interactions in electrospinning: from polymer mixtures to supramolecular assemblies. ACS Appl Polym Mater. https://doi.org/10.1021/acsapm.8b00073
Fang Z, Ito A, Stuart AC et al (2013) Soluble reduced graphene oxide sheets grafted with polypyridylruthenium-derivatized polystyrene brushes as light harvesting antenna for photovoltaic applications. ACS Nano 7:7992–8002. https://doi.org/10.1021/nn403079z
Feng ZQ, Wang T, Zhao B, Li J, Jin L (2015) Soft graphene nanofibers designed for the acceleration of nerve growth and development. Adv Mater 27:6462–6468. https://doi.org/10.1002/adma.201503319
Gao W (2015) The chemistry of graphene oxide. Graphene Oxide Reduct Recipes. Spectrosc Appl:61–95. https://doi.org/10.1007/978-3-319-15500-5_3
Gao Y, Hu G, Zhang W et al (2011) π–π interaction intercalation of layered carbon materials with metallocene. Dalton Trans 40:4542. https://doi.org/10.1039/c0dt01392g
Gao Q, Luo J, Wang X, Gao C, Ge M (2015) Novel hollow α-Fe2O3 nanofibers via electrospinning for dye adsorption. Nanoscale Res Lett 10:1–8. https://doi.org/10.1186/s11671-015-0874-7
Geim AK, Novoselov KS (2007) The rise of graphene. Nat Mater 6:183–191. https://doi.org/10.1038/nmat1849
Ghosh S, Ganesan K, Polaki SR et al (2014) Evolution and defect analysis of vertical graphene nanosheets. J Raman Spectrosc 45:642–649. https://doi.org/10.1002/jrs.4530
Hazra KS, Rafiee J, Rafiee MA et al (2011) Thinning of multilayer graphene to monolayer graphene in a plasma environment. Nanotechnology 22. https://doi.org/10.1088/0957-4484/22/2/025704
Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339. https://doi.org/10.1021/ja01539a017
Jana M, Saha S, Khanra P et al (2014) Bio-reduction of graphene oxide using drained water from soaked mung beans (Phaseolus aureus L.) and its application as energy storage electrode material. Mater Sci Eng B Solid State Mater Adv Technol 186:33–40. https://doi.org/10.1016/j.mseb.2014.03.004
Jin L, Wu D, Kuddannaya S, Zhang Y, Wang Z (2016) Fabrication, characterization, and biocompatibility of polymer cored reduced Graphene oxide nanofibers. ACS Appl Mater Interfaces 8:5170–5177. https://doi.org/10.1021/acsami.6b00243
Kellici S, Acord J, Ball J et al (2014) A single rapid route for the synthesis of reduced graphene oxide with antibacterial activities. RSC Adv 4:14858. https://doi.org/10.1039/c3ra47573e
Lee J, Hwang T-Y, Kang MK et al (2019) High-performance, cost-effective permanent nanomagnet: microstructural and magnetic properties of Fe-substituted SmCo nanofiber. Appl Surf Sci 471:273–276. https://doi.org/10.1016/j.apsusc.2018.11.217
Lin L, Liu Z (2016) Graphene synthesis: on-the-spot growth. Nat Mater 15:9–10. https://doi.org/10.1038/nmat4498
Liu C, Shen J, Yeung KWK, Tjong SC (2017) Development and antibacterial performance of novel polylactic acid-graphene oxide-silver nanoparticle hybrid nanocomposite mats prepared by electrospinning. ACS Biomater Sci Eng 3:471–486. https://doi.org/10.1021/acsbiomaterials.6b00766
Lv W, Zhang C, Li Z, Yang QH (2015) Self-assembled 3D graphene monolith from solution. J Phys Chem Lett 6:658–668. https://doi.org/10.1021/jz502655m
Mahto TK, Pandey SC, Chandra S et al (2015) Hydroxyapatite conjugated graphene oxide nanocomposite: a new sight for significant applications in adsorption. RSC Adv 5:96313–96322. https://doi.org/10.1039/c5ra16022g
Malwal D, Gopinath P (2015) Fabrication and characterization of poly (ethylene oxide) templated nickel oxide nanofibers for dye degradation. Environ Sci Nano 2:78–85. https://doi.org/10.1039/C4EN00107A
Mandal P, Chattopadhyay AP (2015) Excellent catalytic activity of magnetically recoverable Fe 3 O 4 –graphene oxide nanocomposites prepared by a simple method. Dalton Trans 44:11444–11456. https://doi.org/10.1039/C5DT01260K
Musico YLF, Santos CM, Dalida MLP, Rodrigues DF (2014) Surface modification of membrane filters using graphene and graphene oxide-based nanomaterials for bacterial inactivation and removal. ACS Sustain Chem Eng 2:1559–1565. https://doi.org/10.1021/sc500044p
Park S, Ruoff RS (2009) Chemical methods for the production of graphenes. Nat Nanotechnol 4:217–224. https://doi.org/10.1038/nnano.2009.58
Park CM, Wang D, Han J et al (2019) Evaluation of the colloidal stability and adsorption performance of reduced graphene oxide–elemental silver/magnetite nanohybrids for selected toxic heavy metals in aqueous solutions. Appl Surf Sci 471:8–17. https://doi.org/10.1016/j.apsusc.2018.11.240
Raj Kumar S, Gopinath P (2016) Dual applications of silver nanoparticles incorporated functionalized MWCNTs grafted surface modified PAN nanofibrous membrane for water purification. RSC Adv 6:109241–109252. https://doi.org/10.1039/C6RA22735J
Sadasivam RK, Mohiyuddin S, Packirisamy G (2017) Electrospun polyacrylonitrile (PAN) templated 2D nanofibrous mats: a platform toward practical applications for dye removal and bacterial disinfection. ACS Omega 2:6556–6569. https://doi.org/10.1021/acsomega.7b01101
Shandilya M, Rai R, Singh J (2016) Review: Hydrothermal technology for smart materials. Adv Appl Ceram 115:354–376. https://doi.org/10.1080/17436753.2016.1157131
Si Y, Ren T, Ding B et al (2012) Synthesis of mesoporous magnetic Fe 3O 4@carbon nanofibers utilizing in situ polymerized polybenzoxazine for water purification. J Mater Chem 22:4619–4622. https://doi.org/10.1039/c2jm00036a
Song WL, Song K, Fan LZ (2015) A versatile strategy toward binary three-dimensional architectures based on engineering graphene aerogels with porous carbon fabrics for supercapacitors. ACS Appl Mater Interfaces 7:4257–4264. https://doi.org/10.1021/am508624x
Steenackers M, Gigler AM, Zhang N, Deubel F, Seifert M, Hess LH, Lim CH, Loh KP, Garrido JA, Jordan R, Stutzmann M, Sharp ID (2011) Polymer brushes on graphene. J Am Chem Soc 133:10490–10498. https://doi.org/10.1021/ja201052q
Su B, Button TW, Ponton CB (2004) Control of the particle size and morphology of hydrothermally synthesised lead zirconate titanate powders. J Mater Sci 39:6439–6447. https://doi.org/10.1023/B:JMSC.0000044881.35754.ea
Sykam N, Jayram ND, Mohan Rao G (2019) Exfoliation of graphite as flexible SERS substrate with high dye adsorption capacity for Rhodamine 6G. Appl Surf Sci 471:375–386. https://doi.org/10.1016/j.apsusc.2018.11.082
Vinoth R, Karthik P, Muthamizhchelvan C et al (2016) Carrier separation and charge transport characteristics of reduced graphene oxide supported visible-light active photocatalysts. Phys Chem Chem Phys 18:5179–5191. https://doi.org/10.1039/C5CP08041J
Wang Q, Yang X, Yu L, Yang H (2011) Magnetic and luminescent properties of Fe / Fe 3 O 4 @ Y 2 O 3 : Eu nanocomposites. J Alloys Compd 509:9098–9104. https://doi.org/10.1016/j.jallcom.2011.06.058
Wang MC, Chun S, Han RS, Ashraf A, Kang P, Nam S (2015) Heterogeneous, three-dimensional texturing of graphene. Nano Lett 15:1829–1835. https://doi.org/10.1021/nl504612y
Wu XL, Shi Y, Zhong S et al (2016) Facile synthesis of Fe3O4-graphene@mesoporous SiO2nanocomposites for efficient removal of methylene blue. Appl Surf Sci 378:80–86. https://doi.org/10.1016/j.apsusc.2016.03.226
Acknowledgements
S.R.K. is thankful to Mr. Venkatesan Research scholar of Department of Civil Engineering for assistance in ANSYS and MHRD, Government of India, for fellowship. Chemistry department and Institute Instrumentation Centre, Indian Institute of Technology Roorkee, are acknowledged for the various analytical facilities provided.
Funding
This study is financially supported by the Science & Engineering Research Board (SERB), Project number: IMP/2019/000286, Government of India.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no competing interests.
Additional information
Responsible editor: Tito Roberto Cadaval Jr
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(DOC 1075 kb)
Rights and permissions
About this article
Cite this article
Sadasivam, R., Packirisamy, G. Facile architecture of highly effective nanofibrous membrane adsorbent via electrospun followed by hydrothermal carbonization for potential application in dye removal from water. Environ Sci Pollut Res 27, 11905–11918 (2020). https://doi.org/10.1007/s11356-019-07555-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-019-07555-z