Journal of Materials Science

, Volume 53, Issue 14, pp 10095–10110 | Cite as

On the investigation of acid and surfactant modification of natural clay for photocatalytic water remediation

  • Vineet Kumar Soni
  • Toran Roy
  • Suman Dhara
  • Ganpat Choudhary
  • Pragati R. Sharma
  • Rakesh K. Sharma


In this study, a series of mineral and organic acids are introduced to natural clay modification. Several analytical techniques are employed to identify the physical and chemical changes in clay. The effect of surfactants on these properties is also investigated. The samples are prepared using simple acid treatment without filtration. The alteration in surface morphology is proportional to the acid strength as evident from SEM and XRD analyses. Therefore, the treatment with mineral acid and organic acid/HNO3 results in the formation of new layers by surface modification as depicted in SEM images, and a higher degree of suppression in characteristic XRD reflections of clay is noticed. However, the treatment with organic acids modifies the existing interlayer spacing of clay, and therefore, the XRD characteristic reflections of clay are less affected. These observations are also supported by FT-IR analysis. The surface area of modified clay is dependent on the acid strength, composition and size of counter-anion of acid. An increase in surface area and porosity is noticed after surfactant modification of HNO3-treated clay, where the change is more prominent at the concentration higher than their respective critical micelle concentration. Thermal stability is dependent on the chemical composition and surface area of clay materials. A relatively higher absorbance is observed for modified clay materials compared with untreated clay during DRS analysis. The catalytic efficiency of modified clay materials in Eriochrome Black T degradation has been demonstrated.



The authors acknowledge the DBT-PAN IIT center for bioenergy (BT/EB/PANIIT/2012) for financial assistance.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2018_2308_MOESM1_ESM.docx (14.5 mb)
Supplementary material 1 (DOCX 14895 kb)


  1. 1.
    Bergaya F, Theng BKG, Lagaly G (eds) (2013) Developments in clay science, handbook of clay science. Elsevier, AmsterdamGoogle Scholar
  2. 2.
    Yuan P, Thill A, Bergaya F (eds) (2016) Developments in clay science, nanosized tubular clay minerals. Elsevier, AmsterdamGoogle Scholar
  3. 3.
    Harvey CC, Murray HH (1997) Industrial clays in the 21st century: a perspective of exploration, technology and utilization. Appl Clay Sci 11:285–310CrossRefGoogle Scholar
  4. 4.
    Vaccari A (1999) Clays and catalysis: a promising future. Appl Clay Sci 14:161–198CrossRefGoogle Scholar
  5. 5.
    Murray HH (2000) Traditional and new applications for kaolin, smectite, and palygorskite: a general overview. Appl Clay Sci 17:207–221CrossRefGoogle Scholar
  6. 6.
    Verma RS (2002) Clay and clay-supported reagents in organic synthesis. Tetrahedron 58:1235–1255CrossRefGoogle Scholar
  7. 7.
    Wallis PJ, Gates WP, Patti AF, Scott JL, Teoh E (2007) Assessing and improving the catalytic activity of K-10 montmorillonite. Green Chem 9:980–986CrossRefGoogle Scholar
  8. 8.
    Dasgupta S, Torok B (2008) Application of clay catalysts in organic synthesis. A review. Org Prep Proced Int 4:01–65CrossRefGoogle Scholar
  9. 9.
    Nagendrappa G (2011) Organic synthesis using clay and clay-supported catalysts. Appl Clay Sci 53:106–138CrossRefGoogle Scholar
  10. 10.
    Zhou CH (2011) An overview on strategies towards clay-based designer catalysts for green and sustainable catalysis. Appl Clay Sci 53:87–96CrossRefGoogle Scholar
  11. 11.
    Kumar BS, Dhakshinamoorthy A, Pitchumani K (2014) K10 montmorillonite clays as environmentally benign catalysts for organic reactions. Catal Sci Technol 4:2378–2396CrossRefGoogle Scholar
  12. 12.
    Carniato F, Bisio C, Psaro R, Marchese L, Guidotti M (2014) Niobium(V) saponite clay for the catalytic oxidative abatement of chemical warfare agents. Angew Chem Int Ed 53:10095–10098CrossRefGoogle Scholar
  13. 13.
    Sihvonen SK, Schill GP, Lyktey NA, Veghte DP, Tolbert MA, Freedman MA (2014) Chemical and physical transformations of aluminosilicate clay minerals due to acid treatment and consequences for heterogeneous ice nucleation. J Phys Chem A 118:8787–8796CrossRefGoogle Scholar
  14. 14.
    Tian H, Guo Y, Pan B, Gu C, Li H, Boyd SA (2015) Enhanced photoreduction of nitro-aromatic compounds by hydrated electrons derived from indole on natural montmorillonite. Environ Sci Technol 49:7784–7792CrossRefGoogle Scholar
  15. 15.
    Wu H, Xie H, He G, Guan Y, Zhang Y (2016) Effects of the pH and anions on the adsorption of tetracycline on iron-montmorillonite. Appl Clay Sci 119:161–169CrossRefGoogle Scholar
  16. 16.
    Siddiqui MHK (1968) Bleaching earths. Pergamon Press, LondonGoogle Scholar
  17. 17.
    Hussin F, Aroua MK, Daud WMAW (2011) Textural characteristics, surface chemistry and activation of bleaching earth: a review. Chem Eng J 170:90–106CrossRefGoogle Scholar
  18. 18.
    Falaras P, Lezou F, Seiragakis G, Petrakis D (2000) Bleaching properties of alumina-pillared acid-activated montmorillonite. Clay Clay Miner 48:549–556CrossRefGoogle Scholar
  19. 19.
    Viseras C, Aguzzi C, Cerezo P, Lopez-Galindo A (2007) Uses of clay minerals in semisolid health care and therapeutic products. Appl Clay Sci 36:37–50CrossRefGoogle Scholar
  20. 20.
    Wu Q, Li Z, Hong H, Jiang WT (2013) Desorption of ciprofloxacin from clay mineral surfaces. Water Res 47:259–268CrossRefGoogle Scholar
  21. 21.
    Das G, Kalita RD, Gogoi P, Buragohain AK, Karak N (2014) Antibacterial activities of copper nanoparticle-decorated organically modified montmorillonite/epoxy nanocomposites. Appl Clay Sci 90:18–26CrossRefGoogle Scholar
  22. 22.
    Carretero MI MI, Pozo M (2009) Clay and non-clay minerals in the pharmaceutical industry Part I. Excipients and medical applications. Appl Clay Sci 46:73–80CrossRefGoogle Scholar
  23. 23.
    Carretero MI, Pozo M (2010) Clay and non-clay minerals in the pharmaceutical and cosmetic industries Part II, active ingredients. Appl Clay Sci 47:171–181CrossRefGoogle Scholar
  24. 24.
    White JL, Hem SL (1983) Pharmaceutical aspects of clay-organic interactions. Ind Eng Chem Prod Res Dev 22:665–671CrossRefGoogle Scholar
  25. 25.
    Slamova R, Trckova M, Vondruskova H, Zraly Z, Pavlik I (2011) Clay minerals in animal nutrition. Appl Clay Sci 51:395–398CrossRefGoogle Scholar
  26. 26.
    Petra L, Billik P, Komadel P (2015) Preparation and characterization of hybrid materials consisting of high-energy ground montmorillonite and α-amino acids. Appl Clay Sci 115:174–178CrossRefGoogle Scholar
  27. 27.
    Pinnavaia TJ, Beall GW (2001) Polymer-clay nanocomposites. Wiley, BerlinGoogle Scholar
  28. 28.
    Theng BKG (2012) Developments in clay science, formation and properties of clay-polymer complexes. Elsevier, AmsterdamGoogle Scholar
  29. 29.
    Salam H, Dong Y, Davies IJ (2015) Fillers and reinforcements for advanced nanocomposites. Woodhead Publishing, UK, pp 101–132CrossRefGoogle Scholar
  30. 30.
    Kiliaris P, Papaspyrides CD (2010) Polymer/layered silicate (clay) nanocomposites: an overview of flame retardancy. Prog Polymer Sci 35:902–958CrossRefGoogle Scholar
  31. 31.
    Jankovič L, Madejová J, Komadel P, Jochec-Mošková D, Chodák I (2011) Characterization of systematically selected organo-montmorillonites for polymer nanocomposites. Appl Clay Sci 51:438–444CrossRefGoogle Scholar
  32. 32.
    Carniato F, Bisio C, Gatti G, Guidotti M, Sordelli L, Marchese L (2011) Organic-inorganic hybrid saponites obtained by intercalation of titano-silsesquioxane. Chem Asian J 6:914–921CrossRefGoogle Scholar
  33. 33.
    Adeyemo AA, Adeoye IO, Bello OS (2017) Adsorption of dyes using different types of clay: a review. Appl Water Sci 7:543–568CrossRefGoogle Scholar
  34. 34.
    Yagub MT, Sen TK, Afroze S, Ang HM (2014) Dye and its removal from aqueous solution by adsorption: a review. Adv Colloid Interface Sci 209:172–184CrossRefGoogle Scholar
  35. 35.
    Gil A, Assis FCC, Albeniz S, Korili SA (2011) Removal of dyes from wastewaters by adsorption on pillared clays. Chem Eng J 168:1032–1040CrossRefGoogle Scholar
  36. 36.
    Kansal SK, Sood S, Umar A, Mehta SK (2013) Photocatalytic degradation of Eriochrome Black T dye using well-crystalline anatase TiO2 nanoparticles. J Alloy Compd 581:392–397CrossRefGoogle Scholar
  37. 37.
    Ejhieh AZ, Khorsandi M (2010) Photodecolorization of Eriochrome Black T using NiS–P zeolite as a heterogeneous catalyst. J Haz Mat 176:629–637CrossRefGoogle Scholar
  38. 38.
    Barka N, Abdennouri M, Makhfouk MEL (2011) Removal of Methylene Blue and Eriochrome Black T from aqueous solutions by biosorption on Scolymus hispanicus L.: kinetics, equilibrium and thermodynamics. J Taiwan Inst Chem Eng 42:320–326CrossRefGoogle Scholar
  39. 39.
    Hsueh CC, Chen BY (2007) Comparative study on reaction selectivity of azo dye decolorization by Pseudomonas luteola. J Haz Mater 141:842–849CrossRefGoogle Scholar
  40. 40.
    Komadel P (2016) Acid activated clays: materials in continuous demand. Appl Clay Sci 131:84–99CrossRefGoogle Scholar
  41. 41.
    Chitnis SR, Sharma MM (1997) Industrial applications of acid-treated clays as catalysts. React Funct Polym 32:93–115CrossRefGoogle Scholar
  42. 42.
    Murray HH (2007) Applied clay mineralogy. Occurrences, processing and application of kaolins, bentonites, palygorskite-sepiolite, and common clays. Elsevier, AmsterdamGoogle Scholar
  43. 43.
    Pentrák M, Czímerová A, Madejová J, Komadel P (2012) Changes in layer charge of clay minerals upon acid treatment as obtained from their interactions with methylene blue. Appl Clay Sci 55:100–107CrossRefGoogle Scholar
  44. 44.
    Chmielarz L, Wojciechowska M, Rutkowska M, Adamski A, Węgrzyn A, Kowalczyk A, Dudek B, Boroń P, Michalik M, Matusiewicz A (2012) Acid-activated vermiculites as catalysts of the DeNOx process. Catal Today 191:25–31CrossRefGoogle Scholar
  45. 45.
    Gao W, Zhao S, Wu H, Deligeer W, Asuha S (2016) Direct acid activation of kaolinite and its effects on the adsorption of methylene blue. Appl Clay Sci 126:98–106CrossRefGoogle Scholar
  46. 46.
    Bharadwaj SK, Boruah PK, Gogoi PK (2014) Phosphoric acid modified montmorillonite clay: a new heterogeneous catalyst for nitration of arenes. Catal Commun 57:124–128CrossRefGoogle Scholar
  47. 47.
    Belver C, Munoz MAB, Vicente M (2002) Chemical activation of a kaolinite under acid and alkaline conditions. Chem Mater 14:2033–2043CrossRefGoogle Scholar
  48. 48.
    Chmielarz L, Rutkowska M, Jablonska M, Wegrzyn A, Kowalczyk A, Boron P, Piwowarska Z, Matusiewicz A (2014) Acid-treated vermiculites as effective catalysts of high-temperature N2O decomposition. Appl Clay Sci 101:237–245CrossRefGoogle Scholar
  49. 49.
    Lenarda M, Storaro L, Talona A, Moretti E, Riello P (2007) Solid acid catalysts from clays: Preparation of mesoporous catalysts by chemical activation of metakaolin under acid conditions. J Colloid Interface Sci 311:537–543CrossRefGoogle Scholar
  50. 50.
    Santos SSG, Silva HRM, de Souza AG, Alves APM, da Silva Filho EC, Fonseca MG (2015) Acid-leached mixed vermiculites obtained by treatment with nitric acid. Appl Clay Sci 104:286–294CrossRefGoogle Scholar
  51. 51.
    Timofeevaa MN, Panchenkoa VN, Volcho KP, Zakusine SV, Krupskaya VV, Gil A, Mikhalchenko OS, Vicente MA (2016) Effect of acid modification of kaolin and metakaolin on Brønsted acidity and catalytic properties in the synthesis of octahydro-2H-chromen-4-ol from vanillin and isopulegol. J Mol Catal A: Chem 414:160–166CrossRefGoogle Scholar
  52. 52.
    Chmielarz L, Kowalczyk A, Michalik M, Dudek B, Piwowarska Z, Matusiewicz A (2010) Acid-activated vermiculites and phlogophites as catalysts for the DeNOx process. Appl Clay Sci 49:156–162CrossRefGoogle Scholar
  53. 53.
    Taxiarchou M, Douni I (2014) The effect of oxalic acid activation on the bleaching properties of a bentonite from Milos Island, Greece. Clay Miner 49:541–549CrossRefGoogle Scholar
  54. 54.
    Stawinski W, Freitas O, Chmielarz L, Wegrzyn A, Komedera K, Błachowski A, Figueiredo S (2016) The influence of acid treatments over vermiculite based material as adsorbent for cationic textile dyestuffs. Chemosphere 153:115–129CrossRefGoogle Scholar
  55. 55.
    Connolly GC (1943) Catalyst. US Patent 2330685Google Scholar
  56. 56.
    Kong M, Huang L, Lia L, Zhang Z, Zheng S, Wang MK (2014) Effects of oxalic and citric acids on three clay minerals after incubation. Appl Clay Sci 99:207–214CrossRefGoogle Scholar
  57. 57.
    Siddiqui MKH (1968) Bleaching earths, 1st edn. Pergamon Press, LondonGoogle Scholar
  58. 58.
    Kumar S, Panda AK, Singh RK (2013) Preparation and characterization of acids and alkali treated Kaolin Clay. Bull Chem React Eng Catal 8:61–69CrossRefGoogle Scholar
  59. 59.
    Sarkar B, Xi Y, Megharaj M, Krishnamurti GSR, Bowman M, Rose H, Naidu R (2012) Bioreactive organoclay: a new technology for environmental remediation. Crit Rev Env Sci Technol 42:435–488CrossRefGoogle Scholar
  60. 60.
    Nafees M, Waseem A (2014) Organoclays as sorbent material for phenolic compounds: a review. Clean Soil Air Water 42:1500–1508CrossRefGoogle Scholar
  61. 61.
    Park Y, Ayoko GA, Frost RL (2011) Application of organoclays for the adsorption of recalcitrant organic molecules from aqueous media. J Colloid Interface Sci 354:292–305CrossRefGoogle Scholar
  62. 62.
    Park Y, Ayoko GA, Kurdi R, Horváth E, Kristóf J, Frost RLJ (2013) Adsorption of phenolic compounds by organoclays: Implications for the removal of organic pollutants from aqueous media. J Colloid Interface Sci 406:196–208CrossRefGoogle Scholar
  63. 63.
    Liu P (2007) Polymer modified clay minerals: a review. Appl Clay Sci 38:64–76CrossRefGoogle Scholar
  64. 64.
    Dutta A, Singh N (2015) Surfactant-modified bentonite clays: preparation, characterization, and atrazine removal. Environ Sci Pollut Res 22:3876–3885CrossRefGoogle Scholar
  65. 65.
    Soni VK, Sharma RK (2016) Pd nanoparticles intercalated montmorillonite clay: a green catalyst for solvent free chemoselective hydrogenation of squalene. ChemCatChem 8:1763–1768CrossRefGoogle Scholar
  66. 66.
    Soni VK, Sharma PR, Choudhary G, Pandey S, Sharma RK (2017) Ni/Co-natural clay as green catalysts for microalgae oil to diesel-grade hydrocarbons conversion. ACS Sustain Chem Eng 5:5351–5359CrossRefGoogle Scholar
  67. 67.
    Garg N, Skibsted J (2014) Thermal activation of a pure montmorillonite clay and its reactivity in cementitious systems. J Phys Chem C 118:11464–11477CrossRefGoogle Scholar
  68. 68.
    Matsuda T, Asanuma M, Kikuchi E (1988) Effect of high-temperature treatment on the activity of montmorillonite pillared by alumina in the conversion of 1,2,4_trimethylbenzene. Appl Catal 38:289–299CrossRefGoogle Scholar
  69. 69.
    Senthilkumar L, Ghanty TK, Ghosh SK, Kolandaivel P (2006) Hydrogen bonding in substituted formic acid dimers. J Phys Chem A 110:12623–12628CrossRefGoogle Scholar
  70. 70.
    Mendioroz S, Pajares J, Benito I, Pesquera C, Gonzalez F, Blanco C (1987) Texture evolution of montmorillonite under progressive acid treatment: change from H3 to H2 type of hysteresis. Langmuir 3:676–681CrossRefGoogle Scholar
  71. 71.
    Tyagi B, Chudasama CD, Jasra RV (2006) Determination of structural modification in acid activated montmorillonite clay by FT-IR spectroscopy. Spectrochim Acta, Part A 64:273–278CrossRefGoogle Scholar
  72. 72.
    Korichi S, Elias A, Mefti A (2009) Characterization of smectite after acid activation with microwave irradiation. Appl Clay Sci 42:432–438CrossRefGoogle Scholar
  73. 73.
    Suquet H (1989) Effects of dry grinding and leaching on the crystal structure of chrysotile. Clays Clay Miner 37:439–445CrossRefGoogle Scholar
  74. 74.
    Truex TJ, Hammerle RH, Armstrong RA (1977) The thermal decomposition of aluminium sulphate. Thermochim Acta 19:301–304CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Vineet Kumar Soni
    • 1
  • Toran Roy
    • 1
  • Suman Dhara
    • 1
  • Ganpat Choudhary
    • 1
  • Pragati R. Sharma
    • 1
  • Rakesh K. Sharma
    • 1
  1. 1.Department of ChemistryIndian Institute of Technology JodhpurKarwad, JodhpurIndia

Personalised recommendations