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

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Abstract

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.

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References

  1. Bergaya F, Theng BKG, Lagaly G (eds) (2013) Developments in clay science, handbook of clay science. Elsevier, Amsterdam

    Google Scholar 

  2. Yuan P, Thill A, Bergaya F (eds) (2016) Developments in clay science, nanosized tubular clay minerals. Elsevier, Amsterdam

    Google Scholar 

  3. Harvey CC, Murray HH (1997) Industrial clays in the 21st century: a perspective of exploration, technology and utilization. Appl Clay Sci 11:285–310

    Article  Google Scholar 

  4. Vaccari A (1999) Clays and catalysis: a promising future. Appl Clay Sci 14:161–198

    Article  Google Scholar 

  5. Murray HH (2000) Traditional and new applications for kaolin, smectite, and palygorskite: a general overview. Appl Clay Sci 17:207–221

    Article  Google Scholar 

  6. Verma RS (2002) Clay and clay-supported reagents in organic synthesis. Tetrahedron 58:1235–1255

    Article  Google Scholar 

  7. Wallis PJ, Gates WP, Patti AF, Scott JL, Teoh E (2007) Assessing and improving the catalytic activity of K-10 montmorillonite. Green Chem 9:980–986

    Article  Google Scholar 

  8. Dasgupta S, Torok B (2008) Application of clay catalysts in organic synthesis. A review. Org Prep Proced Int 4:01–65

    Article  Google Scholar 

  9. Nagendrappa G (2011) Organic synthesis using clay and clay-supported catalysts. Appl Clay Sci 53:106–138

    Article  Google Scholar 

  10. Zhou CH (2011) An overview on strategies towards clay-based designer catalysts for green and sustainable catalysis. Appl Clay Sci 53:87–96

    Article  Google Scholar 

  11. Kumar BS, Dhakshinamoorthy A, Pitchumani K (2014) K10 montmorillonite clays as environmentally benign catalysts for organic reactions. Catal Sci Technol 4:2378–2396

    Article  Google Scholar 

  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 53:10095–10098

    Article  Google Scholar 

  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 118:8787–8796

    Article  Google Scholar 

  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 49:7784–7792

    Article  Google Scholar 

  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 119:161–169

    Article  Google Scholar 

  16. Siddiqui MHK (1968) Bleaching earths. Pergamon Press, London

    Google Scholar 

  17. Hussin F, Aroua MK, Daud WMAW (2011) Textural characteristics, surface chemistry and activation of bleaching earth: a review. Chem Eng J 170:90–106

    Article  Google Scholar 

  18. Falaras P, Lezou F, Seiragakis G, Petrakis D (2000) Bleaching properties of alumina-pillared acid-activated montmorillonite. Clay Clay Miner 48:549–556

    Article  Google Scholar 

  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 36:37–50

    Article  Google Scholar 

  20. Wu Q, Li Z, Hong H, Jiang WT (2013) Desorption of ciprofloxacin from clay mineral surfaces. Water Res 47:259–268

    Article  Google Scholar 

  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 90:18–26

    Article  Google Scholar 

  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 46:73–80

    Article  Google Scholar 

  23. Carretero MI, Pozo M (2010) Clay and non-clay minerals in the pharmaceutical and cosmetic industries Part II, active ingredients. Appl Clay Sci 47:171–181

    Article  Google Scholar 

  24. White JL, Hem SL (1983) Pharmaceutical aspects of clay-organic interactions. Ind Eng Chem Prod Res Dev 22:665–671

    Article  Google Scholar 

  25. Slamova R, Trckova M, Vondruskova H, Zraly Z, Pavlik I (2011) Clay minerals in animal nutrition. Appl Clay Sci 51:395–398

    Article  Google Scholar 

  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 115:174–178

    Article  Google Scholar 

  27. Pinnavaia TJ, Beall GW (2001) Polymer-clay nanocomposites. Wiley, Berlin

    Google Scholar 

  28. Theng BKG (2012) Developments in clay science, formation and properties of clay-polymer complexes. Elsevier, Amsterdam

    Google Scholar 

  29. Salam H, Dong Y, Davies IJ (2015) Fillers and reinforcements for advanced nanocomposites. Woodhead Publishing, UK, pp 101–132

    Book  Google Scholar 

  30. Kiliaris P, Papaspyrides CD (2010) Polymer/layered silicate (clay) nanocomposites: an overview of flame retardancy. Prog Polymer Sci 35:902–958

    Article  Google Scholar 

  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 51:438–444

    Article  Google Scholar 

  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 6:914–921

    Article  Google Scholar 

  33. Adeyemo AA, Adeoye IO, Bello OS (2017) Adsorption of dyes using different types of clay: a review. Appl Water Sci 7:543–568

    Article  Google Scholar 

  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 209:172–184

    Article  Google Scholar 

  35. Gil A, Assis FCC, Albeniz S, Korili SA (2011) Removal of dyes from wastewaters by adsorption on pillared clays. Chem Eng J 168:1032–1040

    Article  Google Scholar 

  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 581:392–397

    Article  Google Scholar 

  37. Ejhieh AZ, Khorsandi M (2010) Photodecolorization of Eriochrome Black T using NiS–P zeolite as a heterogeneous catalyst. J Haz Mat 176:629–637

    Article  Google Scholar 

  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 42:320–326

    Article  Google Scholar 

  39. Hsueh CC, Chen BY (2007) Comparative study on reaction selectivity of azo dye decolorization by Pseudomonas luteola. J Haz Mater 141:842–849

    Article  Google Scholar 

  40. Komadel P (2016) Acid activated clays: materials in continuous demand. Appl Clay Sci 131:84–99

    Article  Google Scholar 

  41. Chitnis SR, Sharma MM (1997) Industrial applications of acid-treated clays as catalysts. React Funct Polym 32:93–115

    Article  Google Scholar 

  42. Murray HH (2007) Applied clay mineralogy. Occurrences, processing and application of kaolins, bentonites, palygorskite-sepiolite, and common clays. Elsevier, Amsterdam

    Google Scholar 

  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 55:100–107

    Article  Google Scholar 

  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 191:25–31

    Article  Google Scholar 

  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 126:98–106

    Article  Google Scholar 

  46. Bharadwaj SK, Boruah PK, Gogoi PK (2014) Phosphoric acid modified montmorillonite clay: a new heterogeneous catalyst for nitration of arenes. Catal Commun 57:124–128

    Article  Google Scholar 

  47. Belver C, Munoz MAB, Vicente M (2002) Chemical activation of a kaolinite under acid and alkaline conditions. Chem Mater 14:2033–2043

    Article  Google Scholar 

  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 101:237–245

    Article  Google Scholar 

  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 311:537–543

    Article  Google Scholar 

  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 104:286–294

    Article  Google Scholar 

  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 414:160–166

    Article  Google Scholar 

  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 49:156–162

    Article  Google Scholar 

  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 49:541–549

    Article  Google Scholar 

  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 153:115–129

    Article  Google Scholar 

  55. Connolly GC (1943) Catalyst. US Patent 2330685

  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 99:207–214

    Article  Google Scholar 

  57. Siddiqui MKH (1968) Bleaching earths, 1st edn. Pergamon Press, London

    Google Scholar 

  58. Kumar S, Panda AK, Singh RK (2013) Preparation and characterization of acids and alkali treated Kaolin Clay. Bull Chem React Eng Catal 8:61–69

    Article  Google Scholar 

  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 42:435–488

    Article  Google Scholar 

  60. Nafees M, Waseem A (2014) Organoclays as sorbent material for phenolic compounds: a review. Clean Soil Air Water 42:1500–1508

    Article  Google Scholar 

  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 354:292–305

    Article  Google Scholar 

  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 406:196–208

    Article  Google Scholar 

  63. Liu P (2007) Polymer modified clay minerals: a review. Appl Clay Sci 38:64–76

    Article  Google Scholar 

  64. Dutta A, Singh N (2015) Surfactant-modified bentonite clays: preparation, characterization, and atrazine removal. Environ Sci Pollut Res 22:3876–3885

    Article  Google Scholar 

  65. Soni VK, Sharma RK (2016) Pd nanoparticles intercalated montmorillonite clay: a green catalyst for solvent free chemoselective hydrogenation of squalene. ChemCatChem 8:1763–1768

    Article  Google Scholar 

  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 5:5351–5359

    Article  Google Scholar 

  67. Garg N, Skibsted J (2014) Thermal activation of a pure montmorillonite clay and its reactivity in cementitious systems. J Phys Chem C 118:11464–11477

    Article  Google Scholar 

  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 38:289–299

    Article  Google Scholar 

  69. Senthilkumar L, Ghanty TK, Ghosh SK, Kolandaivel P (2006) Hydrogen bonding in substituted formic acid dimers. J Phys Chem A 110:12623–12628

    Article  Google Scholar 

  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 3:676–681

    Article  Google Scholar 

  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 64:273–278

    Article  Google Scholar 

  72. Korichi S, Elias A, Mefti A (2009) Characterization of smectite after acid activation with microwave irradiation. Appl Clay Sci 42:432–438

    Article  Google Scholar 

  73. Suquet H (1989) Effects of dry grinding and leaching on the crystal structure of chrysotile. Clays Clay Miner 37:439–445

    Article  Google Scholar 

  74. Truex TJ, Hammerle RH, Armstrong RA (1977) The thermal decomposition of aluminium sulphate. Thermochim Acta 19:301–304

    Article  Google Scholar 

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Acknowledgements

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

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Correspondence to Rakesh K. Sharma.

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Soni, V.K., Roy, T., Dhara, S. et al. On the investigation of acid and surfactant modification of natural clay for photocatalytic water remediation. J Mater Sci 53, 10095–10110 (2018). https://doi.org/10.1007/s10853-018-2308-2

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