Abstract
Synthesis, characterization and adsorption studies of polyaniline (PANI) and polyaniline/montmorillonite clay (PANI/MMT) nanocomposites have been carried out. In situ polymerization method was used to synthesize PANI/MMT nanocomposites using HCl as a catalyst and ammonium persulfate as an oxidizing agent. The molar ratio of monomer/oxidant was 1:1, and the polymerization was done at two different temperatures, i.e.,. 0° and 20 °C. Complete removal of Acid Green 25 (AG25) dye was achieved with PANI/MMT adsorbent. The kinetic adsorption data of AG25 dye were found to fit pseudo-second-order kinetic model. Since the removal of this dye takes place efficiently at a very fast rate, PANI/MMT nanocomposites will be excellent adsorbents in continuous adsorption systems.














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Koswojo R, Utomo RP, Ju YH, Ayucitra A, Soetaredjo FE, Sunarso J, Ismadji S (2010) Acid Green 25 removal from wastewater by organo-bentonite from Pacitan. Appl Clay Sci 48:81–86
Salahuddin NA, Ayad MM, Essa ME (2015) Modified chitosan for efficient dye adsorption in low acid media. Int J Mater Chem 5(3):54–63. https://doi.org/10.5923/j.ijmc.20150503.02
Ayad MM, El-Nasr AA (2012) Anionic dye (acid green 25) adsorption from water by using polyaniline nanotubes salt/silica composite. J Nanostructure Chem 3:3
Ansari R, Alaei S, Mohammad-khah A (2011) Application of polyaniline for removal of acid green 25 from aqueous solution. J Sci Ind Res 70(9):804–809
Khan MI, Ansari TM, Zafar S, Buzdar AR, Khan MA, Mumtaz F, Prapamonthon P, Akhtar M (2018) Acid Green-25 removal from wastewater by anion exchange membrane: adsorption kinetic and thermodynamic studies. Membr Water Treat 9(2):79–85
Lee SY, Shim HE, Yang JE, Choi YJ, Jeon J (2019) Continuous flow removal of anionic dyes in water by chitosan-functionalized iron oxide nanoparticles incorporated in a dextran gel column. Nanometer 9:1164. https://doi.org/10.3390/nano9081164
Kaykhaii M, Sasani M, Marghzari S (2018) Removal of Dyes from the environment by adsorption process. Chem Mater Eng 6(2):31–35. https://doi.org/10.13189/cme.2018.060201
Jain SN, Gogate PR (2018) Efficient removal of Acid Green 25 dye from wastewater using activated Prunus Dulcis as biosorbent: batch and column studies. J Environ Manag 210:226–238
Mahmoodi NM, Taghizadeh M, Taghizadeh A (2019) Activated carbon/metal-organic framework composite as a bio-based novel green adsorbent: preparation and mathematical pollutant removal modeling. J Mol Liq 277:310–322
Cottet L, Almeida CAP, Naidek N, Viante MF, Lopes MC, Debacher NA (2014) Adsorption characteristics of montmorillonite clay modified with iron oxide with respect to methylene blue in aqueous media. Appl Clay Sci 95:25–31
Yap PW, Priyaa V (2019) Removal of crystal violet and acid green 25 from water using kaolin. Mater Sci Eng 495:012052. https://doi.org/10.1088/1757-899X/495/1/012052
Unuabonah EI, Taubert A (2014) Clay–polymer nanocomposites (CPNs): Adsorbents of the future for water treatment. Appl Clay Sci 99:83–92
Olad A, Rashidzadeh A (2012) Poly(N-vinylpyrrolidone) modified polyaniline/Na+ -cloisite nanocomposite: synthesis and characterization. Fiber Polym 13:16–20
Mahanta D, Madras G, Radhakrishnan S, Patil S (2008) Adsorption of sulfonated dyes by polyaniline emeraldine salt and its kinetics. J Phys Chem 112:10153–10157
Souza FG, Sirelli L, Michel RC, Soares BG, Herbst MH (2006) In situ polymerization of aniline in the presence of carbon black. J Appl Polym Sci 102:535–541
Palaniappan S, John A (2008) Polyaniline materials by emulsion polymerization pathway. Prog Polym Sci 33:732–758
Baei MS, Babaee V, Pirouz F (2011) Preparation of polyaniline nanocomposites for removal of sulfate from wastewater. In: 2nd International conference on chemistry and chemical engineering vol 14, p 95
Chowdhury AN, Jesmeen SR, Hossain MM (2004) Removal of dyes from water by conducting polymeric adsorbent. Polym Adv Technol 15:633–638
Chen CH (2003) Thermal and morphological studies of chemically prepared emeraldine-base-form polyaniline powder. J Appl Polym Sci 89:2142–2148
Zahran M, Saleeb MM, Elhalawany N (2019) Electrical and dielectrical properties of some novel polyaniline nanocomposites. Egypt J Chem 62(11):1987–1994
Salem MA (2010) The role of polyaniline salts in the removal of direct blue 78 from aqueous solution: a kinetic study. React Funct Polym 70:707–714
Elsayed AH, Mohy Eldin MS, Elsyed AM, Abo Elazm AH, Younes EM, Motaweh HA (2011) Synthesis and properties of polyaniline/ferrites nanocomposites. Int J Electrochem Sci 6:206–221
Boddula R, Srinivasan P (2014) Emeraldine Base form of polyaniline nanofibers as new, economical, green, and efficient catalyst for synthesis of Z-Aldoximes. J Catal. https://doi.org/10.1155/2014/515428
Yeh JM, Liou SJ, Lai CY, Wu PC (2001) Enhancement of corrosion protection effect in polyaniline via the formation of polyaniline-clay nanocomposite Materials. Chem Mater 13:1131–1136
Stejskal J, Gilbert RG (2002) Polyaniline, preparation of a conducting polymer. Pure Appl Chem 74:857–867
Palaniappan S, John A, Amarnath CA, Rao VJ (2004) Mannich-type reaction in solvent free condition using reusable polyaniline catalyst. J Mol Catal A: Chem 218:47–53
Ramamurthy PC, Harrell WR, Gregory RV, Sadanadan B, Rao AM (2004) mechanical and electrical properties of solution-processed polyaniline multiwalled carbon nanotube composite films. J Electrochem Soc 151:502–506
Acevedo DF, Salavagione HJ, Miras MC, Barbero CA (2005) Synthesis, properties and aplications of functionalized polyanilines. J Braz Chem Soc. https://doi.org/10.1590/S010350532005000200020
Ansari R (2006) Application of polyaniline and its composites for adsorption/recovery of chromium (VI) from aqueous solutions. Acta Chim Slov 53(1):88–94
Chang KC, Jang GW, Peng CW, Lin CY, Shieh JC, Yeh JM, Yang JC, Li WT (2007) Comparatively electrochemical studies at different operational temperatures for the effect of nanoclay platelets on the anticorrosion efficiency of DBSA-doped polyaniline/Na+–MMT clay nanocomposite coatings. Electrochim Acta 52:5191–5200
Simoes FR, Bulhoes LOS, Pereira EC (2009) Synthesis and characterization of conducting composites of polyaniline and carbon black with high thermal stability. Polimeros 19:54–57
Babazadeh M (2009) Aqueous dispersions of DBSA-doped polyaniline: one-pot preparation, characterization, and properties study. J Appl Polym Sci 113:3980–3984
Chauhan NPS, Ameta R, Ameta R, Ameta SC (2011) Thermal and conducting behaviour of emeraldine base (EB) form of polyaniline (PANI). Indian J Chem Technol 18(2):118–122
Pande S, Swaruparani H, Bedre MD, Bhat R, Deshpande R, Venkataraman A (2012) Synthesis, characterization and studies of PANI–MMT nanocompoisites. Nanosci Nanotechnol 2:90–98
Kavitha B, Siva Kumar K, Narsimlu N (2013) Synthesis and characterization of polyaniline nano-fibers. Indian J Pure Ap Phy 51(3):207–209
Wasu MB, Raut AR (2014) Synthesis and characterization of polyaniline based conducting polymers. J Chem Cheml Sci 4(2):90–97
Sharma D, Kaith BS, Rajput J (2014) Single step in situ synthesis and optical properties of polyaniline/ZnO nanocomposites. Sci World J. https://doi.org/10.1155/2014/904513
Sangamesha MA, Pushpalatha K, Shekar GL (2014) Synthesis and characterization of conducting polyaniline/copper selenide nanocomposites. Indian J Adv Chem Sci 2(3):223–227
Najim TS, Salim AJ (2017) Polyaniline nanofibers and nanocomposites: Preparation, characterization, and application for Cr(VI) and phosphate ions removal from aqueous solution. Arab J Chem 10:S3459–S3467. https://doi.org/10.1016/j.arabjc.2014.02.008
Bavio MA, Acosta GG, Kessler T (2014) Polyaniline and polyaniline-carbon black nanostructures as electrochemical capacitor electrode materials. Int J Hydrog Energy 39:8582–8589
Kim BH, Jung JH, Hong SH, Joo J (2002) Nanocomposite of polyaniline and Na+-montmorillonite clay. Macromolecules 35:1419–1423
Nascimento GM, Constantino VRL, Landers R, Temperini MLA (2004) Aniline polymerization into montmorillonite clay: a spectroscopic investigation of the intercalated conducting polymer. Macromolecules 37:9373–9385
Nascimento GM, Constantino VRL, Landers R, Temperini MLA (2006) Spectroscopic characterization of polyaniline formed in the presence of montmorillonite clay. Polymer 47:6131–6139
Binitha NN, Sugunan S (2008) Polyaniline/pillared montmorillonite clay composite nanofibers. J Appl Polym Sci 107:3367–3372
Kalaivasan N, Shafi SS (2010) Synthesis of various polyaniline / clay nanocomposites derived from aniline and substituted aniline derivatives by mechanochemical intercalation method. E-J Chem 7(4):1477–1483
Narayanan BN, Koodathil R, Gangadharan T, Yaakob Z, Saidu FK, Chandralayam S (2010) Preparation and characterization of exfoliated polyaniline/montmorillonite nanocomposites. Mater Sci Eng B 168:242–244
Srivastava N, Singh Y, Singh RA (2011) Preparation of intercalated polyaniline/clay nanocomposite and its exfoliation exhibiting dendritic structure. Bull Mater Sci 34:635–638
Binitha N, Suraja V, Yaakob Z, Sugunan S (2011) Synthesis of polyaniline-montmorillonite nanocomposites using H2O2 as the oxidant. Sains Malays 40(3):215–219
Kazim S, Ahmad S, Pfleger J, Plestil J, Joshi YM (2011) Polyaniline–sodium montmorillonite clay nanocomposites: effect of clay concentration on thermal, structural, and electrical properties. J Mater Sci 47:420–428
Baldissera AF, Souza JF, Ferreira CA (2013) Synthesis of polyaniline/clay conducting nanocomposites. Synth Met 183:69–72
Deng S, Guang Li G (2013) structural features and microwave absorbing properties of polyaniline-montmorillonite composites prepared by in-situ. J Fiber Bioeng Informat 6(1):33–40
Abd El-Ghaffar MA, Youssef AM, Abd El-Hakim AA (2015) Polyaniline nanocomposites via in situ emulsion polymerization based on montmorillonite: preparation and characterization. Arab J Chem 8(6):771–779. https://doi.org/10.1016/j.arabjc.2014.01.001
Nguyen VH, Shim JJ (2015) Green synthesis and characterization of carbon nanotubes/polyaniline nanocomposites. J Spectrosc. https://doi.org/10.1155/2015/297804
Leon-Almazan CMD, Estrada-Moreno IA, Páramo-García U, Rivera-Armenta JL (2018) Polyaniline/clay nanocomposites. A comparative approach on the doping acid and the clay spacing technique. Synth Met 236:61–67
Yamabe K, Goto H (2018) Synthesis and surface observation of montmorillonite/polyaniline composites. J Compos Sci 2:15. https://doi.org/10.3390/jcs2010015
Hattab Y, Benharrats N (2019) Electrical and thermal properties of PANI–Mmt nanocomposites in strongly acidic aqueous media. SN Appl Sci 1:750. https://doi.org/10.1007/s42452-019-0703-1
Nigam V, Lal G (2008) Review on recent trends in polymer layered clay nanocomposites. Proc Indian Natn Sci Acad 74(2):87–96
Benhebal H, Chaib M, Leonard AL, Crine M, Lambert SD (2014) Preparation of polyaniline-modified local clay and study of its sorption capacity. J Nanost Chem 4:98
Qureshi UA, Gubbuk IH, Ersoz M, Solangi AR, Taqvi SIH, Memon SQ (2016) Preparation of polyaniline montmorillonite clay composites for the removal of diethyl hexyl phthalate from aqueous solutions. Sep Sci Technol 51(2):214–228
Ramedani A, Yazdanpanah A, Abrishamkar A, Nasrollahi M, Milan PB, Moghadam ZS, Chauhan NPS, Sefat F, Mozafari M (2019) Advanced characterization tools for PANI and PANI-clay nanocomposites. Fundam Emerg Appl Polyaniline. https://doi.org/10.1016/B978-0-12-817915-4.00012-9
Buruga K, Song H, Shang J, Bolan N, Kalathi JT, Kim K-H (2019) A review on functional polymer-clay based nanocomposite membranes for treatment of water. J Hazard Mater 379:120584. https://doi.org/10.1016/j.jhazmat.2019.04.067
Zeggai FZ, Belbachir M, Hachemao A (2017) In-situ preparation of conducting polymers/copper (II)-maghnite clay nanocomposites. Mat Sci Res India 14(2):204–211
Banimahd Keivani M, Zare K, Aghaie H, Ansari R (2009) Removal of methylene blue dye by application of polyaniline nano composite from aqueous solutions. J Phys Theor Chem 6(1):50–56
Rahimi R, Kerdari H, Rabbania M (2014) Adsorptive removal of crystal violet (CV), a carcinogenic textile dye, from aqueous. In: 14th International electronic conference on synthetic organic chemistry ECSOC-14
Ansari R, Mosayebzadeh Z (2011) Application of polyaniline as an efficient and novel adsorbent for azo dyes removal from textile wastewaters. Chem Pap 65(1):1–8
Janaki V, Vijayaraghavan K, Oh BT, Lee KJ, Muthuchelian K, Ramasamy AK, Kannan SK (2012) Starch/polyaniline nanocomposite for enhanced removal of reactive dyes from synthetic effluent. Carbohydr Polym 90:1437–1444
Baseri JR, Palanisamy PN, Sivakumar P (2012) Application of polyaniline nano composite for the adsorption of acid dye from aqueous solutions. J Chem 9(3):1266–1275
Ansari R, Dezhampanah H (2013) Application of polyaniline /sawdust composite for removal of acid green 25 from aqueous solutions: kinetics and thermodynamic studies. Eur Chem Bull 2(4):220–225. https://doi.org/10.17628/ecb.2013.2.220-225
Karthikaikumar S, Karthikeyan M, Satheesh Kumar KK (2014) Removal of congo red dye from aqueous solution by polyaniline- montmorillonite composite. Chem Sci Rev Lett 2(8):606–614
Olad A, Azhar FF (2014) Eco-friendly biopolymer/clay/conducting polymer nanocomposite: characterization and its application in reactive dye removal. Fiber Polym 15:1321–1329
Shahabuddin S, Sarih NM, Kamboh MA, Nodeh HR, Mohamad S (2016) Synthesis of polyaniline-coated graphene Oxide@SrTiO3 nanocube nanocomposites for enhanced removal of carcinogenic dyes from aqueous solution. Polymers 8(9):305
Khairy M, Kamal R, Amin NH, Mousa MA (2016) Kinetics and isotherm studies of Remazol Red adsorption onto polyaniline/ cerium oxide nanocomposites. J Bas Environ Sci 3:123–132
Gemeay AH, Elsharkawy RB, Aboelfetoh EF (2018) Graphene oxide/polyaniline/manganese oxide ternary nanocomposites, facile synthesis, characterization, and application for indigo carmine removal. J Polym Environ 26:655–669
Soltani H, Belmokhtar A, Zeggal FZ, Benyoucef A, Bousalem S, Bachari K (2019) Copper(II) removal from aqueous solutions by PANI-clay hybrid material: fabrication, characterization, adsorption and kinetics study. J Inorg Organomet Polym Mater 29:841–850
Zehhaf A, Morallon E, Benyoucef A (2013) Polyaniline/montmorillonite nanocomposites obtained by in situ intercalation and oxidative polymerization in cationic modified-clay (sodium, copper and iron). J Inorg Organomet Polym Mater 23:1485–1491
HambateGomdje V, Rahman AN, Wahabou A, BenoitLoura, Chtaini A (2017) Synthesis of organoclay and its applications in electrochemical detection of paracetamol. Der Chem Sin 8(1):206–217
Tyagi B, Chudasama CD, Jasra RV (2006) Determination of structural modification in acid activated montmorillonite clay by FT-IR spectroscopy. Spectrochim Acta A 64:273–278
Gomes EC, Oliveira MAS (2012) Chemical polymerization of aniline in hydrochloric acid (HCl) and formic acid (HCOOH) media. Differences between the two synthesized polyanilines. Am J Polym Sci 2:5–13
Cole KC (2008) Use of infrared spectroscopy to characterize clay intercalation and exfoliation in polymer nanocomposites. Macromolecules 41:834–843
Qiu M, Zhang Y, Wen B (2018) Facile synthesis of polyaniline nanostructures with effective electromagnetic interference shielding performance. J Mater Sci-Mater El 29:10437–10444
Nadaf LI, Venkatesh KS (2015) Polyaniline-copper oxide nano-composites: Synthesis and characterization. Mat Sci Res India 12(2):108–111. https://doi.org/10.13005/msri/120204
Sui X, Chu Y, Xing S, Liu C (2004) Synthesis of PANI/AgCl, PANI/BaSO4 and PANI/TiO2 nanocomposites in CTAB/hexanol/water reverse micelle. Mater Lett 58:1255–1259
Vivekanandan J, Ponnusamy V, Mahudeswaran A, Vijayanand PS (2011) Synthesis, characterization and conductivity study of polyaniline prepared by chemical oxidative and electrochemical methods. Arch Appl Sci Res 3(6):147–153
Jayasudha S, Priya L, Vasudevan KT (2014) Preparation and characterization of Polyaniline/Ag nanocomposites. Int J Chem Tech Res 6(3):1821–1823
Yoshimoto S, Ohashi F, Kameyama T (2005) Characterization and thermal degradation studies on polyaniline-intercalated montmorillonite nanocomposites prepared by a solvent-free mechanochemical route. J Polym Sci B 43:2705–2714
Sun F, Pan Y, Wang J, Wang Z, Hu C, Dong Q (2009) Synthesis of conducting polyaniline-montmorillonite nanocomposites via inverse emulsion polymerization in supercritical carbon dioxide. Polym Compos 31:163. https://doi.org/10.1002/pc.20783
Salem MA, Elsharkawy RG, Hablas MF (2016) Adsorption of brilliant green dye by polyaniline/silver nanocomposite: kinetic, equilibrium, and thermodynamic studies. Eur Polym J 75:577–590. https://doi.org/10.1016/j.eurpolymj.2015.12.027
Sobhanardakani S, Zandipak R (2015) Removal of anionic dyes (Direct Blue 106 and Acid Green 25) from aqueous solutions using oxidized multi-walled carbon nanotubes. Iran J Health Sci 3(3):48–57
Inthapanya X, Wu S, Han Z, Zeng G, Wu M, Yang C (2019) Adsorptive removal of anionic dye using calcined oyster shells: isotherms, kinetics, and thermodynamics. Environ Sci Pollut Res 6:5944–5954
Youssef AM, Ahmed AI, El-Bana UA (2012) Adsorption of cationic dye (MB) and anionic dye (AG 25) by physically and chemically activated carbons developed from rice husk. Carbon Lett 13(2):61–72
Parimalam R, Raj V, Sivakumar P (2012) Removal of acid green 25 from aqueous solution by adsorption. E-J Chem 9:1683–1698
Salahuddin NA, Ayad MM, Essa ME (2015) Modified chitosan for efficient dye adsorption in low acid media. J Mater Chem 5(3):54–63. https://doi.org/10.5923/j.ijmc.20150503.02
Acknowledgements
We would like to acknowledge the financial support from UGC (Rajiv Gandhi National Fellowship). We are also thankful to Prof S. N. Upadhyay, Emeritus Professor, Department of Chemical Engineering and Technology, IIT (BHU), for his valuable support.
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Kalotra, S., Mehta, R. Synthesis of polyaniline/clay nanocomposites by in situ polymerization and its application for the removal of Acid Green 25 dye from wastewater. Polym. Bull. 78, 2439–2463 (2021). https://doi.org/10.1007/s00289-020-03222-3
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DOI: https://doi.org/10.1007/s00289-020-03222-3