Micro- and Nano-Hollow Spheres in Heavy Metal Removals from Water

  • Jayeeta ChattopadhyayEmail author
Part of the Nanotechnology in the Life Sciences book series (NALIS)


Metal micro-/nano-hollow spheres have enormously been applied in numerous fields during last decade. This review will only focus on the synthetic strategies to synthesize hollow spherical structures in the enhancement of their absorption activity, especially the metal and carbon hollow spherical materials. We present comprehensive overview of synthetic strategies for hollow spherical structures which have been approached specifically in absorptivity quality towards heavy metals and arsenic. These synthetic methods are mainly categorized as hard templates, soft templates, sacrificial templates, and without templates. The review further includes application approaches towards heavy metal removals from ground water.


Metal hollow sphere Carbon sphere Heavy metals Arsenic Ground water 


  1. Appelo T (ed) (2006) Arsenic in groundwater—a world problem. Netherlands National Committee of the IAH, Deltares, UtrechtGoogle Scholar
  2. Arnold LL, Eldan M, Nyska A, van Gemert M, Cohen SM (2006) Dimethylarsinic acid: results of chronic toxicity/oncogenicity studies in F344 rats and in B6C3F1 mice. Toxicology 223:82–100CrossRefGoogle Scholar
  3. Balaji T, Matsunaga H (2003) Adsorption characteristics of As(III) and As(V) with titanium dioxide loaded Amberlite XAD-7 resin. Anal Sci 18:1345–1349CrossRefGoogle Scholar
  4. Bednar AJ, Garbarino JR, Ranville JF, Wildeman TR (2002) Preserving the distribution of inorganic arsenic species in groundwater and acid mine drainage samples. J Agric Food Chem 50:7340–7344CrossRefGoogle Scholar
  5. Bissen M, Frimmel FH (2003) Arsenic—a review. Part II: oxidation of arsenic and its removal in water treatment. Acta Hydrochim Hydrobiol 31:97–107CrossRefGoogle Scholar
  6. Brinkel J, Khan MH, Kraemer A (2009) A systematic review of arsenic exposure and its social and mental health effects with special reference to Bangladesh. Int J Environ Res Public Health 6:1609–1619CrossRefGoogle Scholar
  7. Cao CY, Cui ZM, Chen CQ, Song WG, Cai W (2010) Ceria hollow nanospheres produced by a template-free microwave-assisted hydrothermal method for heavy metal ion removal and catalysis. J Phys Chem C 114:9865–9870CrossRefGoogle Scholar
  8. Cao CY, Qu J, Wei F, Liu H, Song WG (2012a) Superb adsorption capacity and mechanism of flowerlike magnesium oxide nanostructures for lead and cadmium ions. ACS Appl Mater Interfaces 4:4283–4287CrossRefGoogle Scholar
  9. Cao CY, Qu J, Yan WS, Zhu YJ, Wu ZY, Song WG (2012b) Low-cost synthesis of flowerlike α-Fe2O3 nanostructures for heavy metal ion removal: adsorption property and mechanism. Langmuir 28:4573–4579CrossRefGoogle Scholar
  10. Chen YH, Li FA (2010) Kinetic study on removal of copper (II) using goethite and hematite nano-photocatalysts. J Colloid Interface Sci 347:277–281CrossRefGoogle Scholar
  11. Cheng YJ, Zhi LJ, Steffen W, Gutmann JS (2008) Surface-supported, highly ordered macroporous crystalline TiO2 thin films robust up to 1000 °C. Chem Mater 20:6580–6582CrossRefGoogle Scholar
  12. Choong TSY, Chuah TG, Robiah Y, Koay FLG, Azni I (2007) Arsenic toxicity, health hazards and removal techniques from water: an overview. Desalination 217:139–166CrossRefGoogle Scholar
  13. Dada AO, Olalekan AP, Olatunya AM, Dada O (2012) Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms studies of equilibrium sorption of Zn2+ unto phosphoric acid modified rice husk. IOSR J Appl Chem 3:38–45CrossRefGoogle Scholar
  14. Dhar RK, Biswas BK, Samanta G, Mandal BK, Chakraborti D, Roy S, Jafar A (1997) Groundwater arsenic calamity in Bangladesh. Curr Sci 73:48–59Google Scholar
  15. Dujardin E, Mann S (2002) Bio-inspired materials chemistry, bio-inspired materials chemistry. Adv Mater 14:775–788CrossRefGoogle Scholar
  16. Feng XJ, Shankar K, Varghese OK, Paulose M, Latempa TJ, Grimes CA (2008) Vertically aligned single crystal TiO2 nanowire arrays grown directly on transparent conducting oxide coated glass: synthesis details and applications. Nano Lett 8:3781–3786CrossRefGoogle Scholar
  17. Fu F, Wang Q (2011) Removal of heavy metal ions from wastewaters: a review. Environ Manag 92:407–418Google Scholar
  18. Giles CH, MacEwan TH, Nakhwa SN, Smith D (1960) Studies in adsorption. Part XI.* A system of classification of solution adsorption isotherms, and its use in diagnosis of adsorption mechanisms and in measurement of specific surface areas of solids. J Chem Soc 111:3973–3993CrossRefGoogle Scholar
  19. Guan XH, Ma J, Dong HR, Jiang L (2009) Removal of arsenic from water: effect of calcium ions on As(III) removal in the KMnO4–Fe(II) process. Water Res 43:5119–5128CrossRefGoogle Scholar
  20. Guan X, Du J, Meng X, Sun Y, Sun B, Hu Q (2012) Application of titanium dioxide in arsenic removal from water: a review. J Hazard Mater 215–216:1–16CrossRefGoogle Scholar
  21. Guo J, Cai X, Li Y, Zhai R, Zhou S, Na P (2013) The preparation and characterization of a three-dimensional titanium dioxide nanostructure with high surface hydroxyl group density and high performance in water treatment. Chem Eng J 221:342–352CrossRefGoogle Scholar
  22. Hao QY, Liu SA, Yin XM, Du ZF, Zhang M, Li LM, Wang YG, Wang TH, Li QH (2011) Flexible morphology-controlled synthesis of mesoporous hierarchical α-Fe2O3 architectures and their gas-sensing properties. CrystEngComm 13:806–812CrossRefGoogle Scholar
  23. Heikens A, Panaullah GM, Meharg AA (2007) Arsenic behaviour from water and soil to crops: impacts on agriculture and food safety. Rev Environ Contam Toxicol 189:43–87PubMedGoogle Scholar
  24. Hu JS, Zhong LS, Song WG, Wan LJ (2008) Synthesis of hierarchically structured metal oxides and their application in heavy metal ion removal. Adv Mater 20:2977–2982CrossRefGoogle Scholar
  25. Jamil M, Zia MS, Qasim M (2010) Contamination of agro-ecosystem and human health hazards from wastewater used for irrigation. J Chem Soc Pak 32:370–378Google Scholar
  26. Kasuga T, Hiramatsu M, Hoson A, Sekino T, Niihara K (1999) Titania nanotubes prepared by chemical processing. Langmuir 14:3160–3163CrossRefGoogle Scholar
  27. Kenyon EM, Hughes MF (2001) A concise review of the toxicity and carcinogenicity of dimethylarsinic acid. Toxicology 160:227–236CrossRefGoogle Scholar
  28. Khan S, Cao Q, Zheng YM, Huang YZ, Zhu YG (2008) Health risks of heavy metals in contaminated soils and food crops irrigated with wastewater in Beijing, China. Environ Pollut 152:686–692CrossRefGoogle Scholar
  29. Kurniawan TA, Chan GYS, Lo WH, Babel S (2006) Physico-chemical treatment techniques for wastewater laden with heavy metals. Chem Eng J 118:83–98CrossRefGoogle Scholar
  30. Levan MD, Vermeulen T (1981) Binary Langmuir and Freundlich isotherms for ideal adsorbed solutions. J Phys Chem 85:3247–3250CrossRefGoogle Scholar
  31. Li J, Zeng HC (2007) Hollowing Sn-doped TiO2 nanospheres via Ostwald ripening. J Am Chem Soc 129:15839–15847CrossRefGoogle Scholar
  32. Li H, Li W, Zhang YJ, Wang TS, Wang B, Xu W, Jiang L, Song WG, Shu CY, Wang CR (2011) Chrysanthemum-like α-FeOOH microspheres produced by a simple green method and their outstanding ability in heavy metal ion removal. J Mater Chem 21:7878–7881CrossRefGoogle Scholar
  33. Lian JB, Duan XC, Ma JM, Peng P, Kim TI, Zheng WJ (2009) Hematite (α-Fe2O3) with various morphologies: ionic liquid-assisted synthesis, formation mechanism, and properties. ACS Nano 3:3749–3761CrossRefGoogle Scholar
  34. Ma XF, Wang YQ, Gao MJ, Xu HZ, Li GA (2010) A novel strategy to prepare ZnO/PbS heterostructured functional nanocomposite utilizing the surface adsorption property of ZnO nanosheets. Catal Today 158:459–463CrossRefGoogle Scholar
  35. Mazeina L, Alexandra N (2007) Enthalpy of water adsorption and surface enthalpy of goethite (α-FeOOH) and hematite (α-Fe2O3). Chem Mater 19:825–833CrossRefGoogle Scholar
  36. Ming H, Ma Z, Huang H, Lian SY, Li HT, He XD, Yu H, Pan KM, Liu Y, Kang ZH (2011) Nanoporous TiO2 spheres with narrow pore size distribution and improved visible light photocatalytic abilities. Chem Commun 47:8025–8027CrossRefGoogle Scholar
  37. Mishra SP, Singh VK, Tiwari D (1996) Efficient removal of mercury from aqueous solutions by hydrous zirconium oxide. Appl Radiat Isot 47:15–21CrossRefGoogle Scholar
  38. Murray MP, Sharmin R (2015) Groundwater arsenic and education attainment in Bangladesh. J Health Popul Nutr 33:20–30CrossRefGoogle Scholar
  39. Nabi D, Aslam I, Qazi IA (2009) Evaluation of the adsorption potential of titanium dioxide nanoparticles for arsenic removal. J Environ Sci China 21:402–408CrossRefGoogle Scholar
  40. Nagajyoti PC, Lee KD, Sreekanth TVM (2010) Heavy metals, occurrence and toxicity for plants: a review. Environ Chem Lett 8:199–216CrossRefGoogle Scholar
  41. Naser HA (2013) Assessment and management of heavy metal pollution in the marine environment of the Arabian Gulf: a review. Mar Pollut Bull 72:6–13CrossRefGoogle Scholar
  42. O’Connell DW, Birkinshaw C, O’Dwyer TF (2008) Heavy metal adsorbents prepared from the modification of cellulose: a review. Bioresour Technol 99:6709–6724CrossRefGoogle Scholar
  43. Pan BJ, Pan BC, Zhang WM, Lv L, Zhang QX, Zheng SR (2009) Development of polymeric and polymer-based hybrid adsorbents for pollutants removal from waters. Chem Eng J 151:19–29CrossRefGoogle Scholar
  44. Park SD, Cho YH, Kim WW, Kim SJ (1999) Understanding of homogeneous spontaneous precipitation for monodispersed TiO2 ultrafine powders with rutile phase around room temperature. J Solid State Chem 146:230–238CrossRefGoogle Scholar
  45. Pena ME, Korfiatis GP, Patel M, Lippincott L, Meng XG (2005) Adsorption of As(V) and As(III) by nanocrystalline titanium dioxide. Water Res 39:2327–2337CrossRefGoogle Scholar
  46. Rostamiana R, Najafic M, Rafati AA (2011) Synthesis and characterization of thiol-functionalized silica nano hollow sphere as a novel adsorbent for removal of poisonous heavy metal ions from water: kinetics, isotherms and error analysis. Chem Eng J 171:1004–1011CrossRefGoogle Scholar
  47. Serna-Guerrero R, Belmabkhout Y, Sayari A (2010) Modeling CO2 adsorption on amine-functionalized mesoporous silica: 1. A semi-empirical equilibrium model. Chem Eng J 161:173–181CrossRefGoogle Scholar
  48. Sharma VK, Sohn M (2009) Aquatic arsenic: toxicity, speciation, transformations, and remediation. Environ Int 35:743–759CrossRefGoogle Scholar
  49. Shchukin DG, Caruso RA (2004) Template synthesis and photocatalytic properties of porous metal oxide spheres formed by nanoparticle infiltration. Chem Mater 16:2287–2292CrossRefGoogle Scholar
  50. Singh A, Sharma RK, Agrawal M, Marshal FM (2010) Health risk assessment of heavy metals via dietary intake of foodstuffs from the wastewater irrigated site of a dry tropical area of India. Food Chem Toxicol 48:611–619CrossRefGoogle Scholar
  51. Smarsly B, Grosso D, Brezesinski T, Pinna N, Boissière C, Antonietti M, Sanchez C (2004) Highly crystalline cubic mesoporous TiO2 with 10-nm pore diameter made with a new block copolymer template. Chem Mater 16:2948–2952CrossRefGoogle Scholar
  52. Smedley PL, Kinniburgh DG (2002) A review of the source, behaviour and distribution of arsenic in natural waters. Appl Geochem 17:517–568CrossRefGoogle Scholar
  53. Strandwitz NC, Stucky GD (2009) Hollow microporous cerium oxide spheres templated by colloidal silica. Chem Mater 21:4577–4582CrossRefGoogle Scholar
  54. Thirunavukkarasu OS, Viraraghavan T, Subramanian KS, Tanjore S (2002) Organic arsenic removal from drinking water. Urban Water 4:415–421CrossRefGoogle Scholar
  55. Wang J, Lin ZQ (2008) Freestanding TiO2 nanotube arrays with ultrahigh aspect ratio via electrochemical anodization. Chem Mater 20:1257–1261CrossRefGoogle Scholar
  56. Wang YH, Lin SH, Juang RS (2003) Removal of heavy metal ions from aqueous solutions using various low-cost adsorbents. J Hazard Mater 102:291–302CrossRefGoogle Scholar
  57. Wang CSC, Li X, Thornton I (2006) Urban environmental geochemistry of trace metals. Environ Pollut 142:1–16CrossRefGoogle Scholar
  58. Wang J, Zheng S, Liu J, Xu Z (2010) Tannic acid adsorption on amino-functionalized magnetic mesoporous silica. Chem Eng J 165:10–16CrossRefGoogle Scholar
  59. Xu T, Cai Y, O’Shea KE (2007) Adsorption and photocatalyzed oxidation of methylated arsenic species in TiO2 suspensions. Environ Sci Technol 41:5471–5477CrossRefGoogle Scholar
  60. Yanna N, Zhang P, Guo Z, Munroe P, Liu H (2008) Preparation of α-Fe2O3 submicro-flowers by a hydrothermal approach and their electrochemical performance in lithium-ion batteries. Electrochim Acta 53:4213–4218CrossRefGoogle Scholar
  61. Yavuz CT, Mayo JT, Yu WW, Prakash A, Falkner JC, Yean S, Cong LL, Shipley HJ, Kan A, Tomson M, Natelson D, Colvin VL (2006) Low-field magnetic separation of monodisperse Fe3O4 nanocrystals. Science 314:964–967CrossRefGoogle Scholar
  62. Zeng SY, Tang KB, Li TW, Liang ZH, Wang D, Wang YK, Qi YX, Zhou WW (2008) Facile route for the fabrication of porous hematite nanoflowers: its synthesis, growth mechanism, application in the lithium ion battery, and magnetic and photocatalytic properties. J Phys Chem C 112:4836–4843CrossRefGoogle Scholar
  63. Zhao X, Qi L (2012) Rapid microwave-assisted synthesis of hierarchical ZnO hollow spheres and their application in Cr(VI) removal. Nanotechnology 23:235604CrossRefGoogle Scholar
  64. Zhong LS, Hu JS, Liang HP, Cao AM, Song WG, Wan LJ (2006) Self-assembled 3D flowerlike iron oxide nanostructures and their application in water treatment. Adv Mater 18:2426–2431CrossRefGoogle Scholar

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© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Department of ChemistryAmity University JharkhandRanchiIndia

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