Skip to main content
SpringerLink
Log in

Synthesis of magnetic hollow carbon nanospheres with superior microporosity for efficient adsorption of hexavalent chromium ions

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Microporous hollow carbon nanospheres were prepared through the polymerization of 2,4-dihydroxybenzoic acid and formaldehyde in the presence of ammonia and tactfully using chelating zinc species as dynamic porogens during the carbonization step to create extra micropores. The Cr(VI) maximum adsorption capacity of microporous hollow carbon spheres consequently increase from 139.8 mg g−1 of pristine hollow carbon spheres to 199.2 mg g−1. Owing to the presence of the carboxyl groups in the polymer matrix, Zn2+ ions can be easily introduced into the hollow polymer spheres through complexation process. During carbonization, high temperature treatment results in the reduction of Zn2+ to metallic Zn and subsequent evaporation of Zn, consequently forming nanospaces and nanopaths in the carbon shell. As little as 8.6 wt.% Zn2+ in the polymer matrix can increase the micropore volume by 133% and the specific surface area by 86%. The microporous hollow carbon spheres can be made magnetic by anchoring them to 14.0 wt.% γ-Fe2O3 nanoparticles, thus producing a highly efficient Cr(VI) adsorbent. The maximum adsorption capacity measured was 233.1 mg g−1, which is significantly higher than other reported carbon- based adsorbents. After adsorption, the magnetic microporous hollow carbon spheres can be flexibly separated using an external magnet.

中文摘要

本文采用螯合的锌物种作为制孔剂, 运用原位刻蚀的方法, 制备了具有丰富微孔的空心纳米炭球. 通过一步真空浸渍Fe(NO3)3, 得到磁性纳米空心炭球 (γ-Fe2O3含量为14 wt.%), 其Cr(VI)吸附量可达233.1 mg g−1, 高于其它文献报道值. 结果表明: 聚合物母体中仅 负载8.6 wt.%的Zn2+能使炭球的微孔孔容积增加133%, 比表面积增加86%, 这是由于高温炭化过程中锌组分的挥发在炭壁上形成的微孔孔道所致. 由于微孔的强吸附势和高的比面积, 磁性炭球在作为Cr(VI)吸附剂时, 表现出吸附速率快和吸附量高的优异性能. 吸附完成 后, 吸附剂可通过外加磁场回收.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Ali I. New generation adsorbents for water treatment. Chem Rev, 2012; 112: 5073–5091

    Article  Google Scholar 

  2. Miretzky P, Cirelli AF. Cr(VI) and Cr(III) removal from aqueous solution by raw and modified lignocellulosic materials. J Hazard Mater, 2010; 180: 1–19

    Article  Google Scholar 

  3. Sun X, Yang L, Li Q, et al. Amino-functionalized magnetic cellulose nanocomposite as adsorbent for removal of Cr(VI): synthesis and adsorption studies. Chem Eng J, 2014; 241: 175–183

    Article  Google Scholar 

  4. Qiu B, Guo J, Zhang X, et al. Polyethylenimine facilitated ethyl cellulose for hexavalent chromium removal with a wide pH range. ACS Appl Mater Interfaces, 2014, 6: 19816–19824

    Article  Google Scholar 

  5. Yang Y, Wang G, Deng Q, Ng DHL, Zhao H. Microwave-assisted fabrication of nanoparticulate TiO2 microspheres for synergistic photocatalytic removal of Cr(VI) and methyl orange. ACS Appl Mater Interfaces, 2014; 6: 3008–3015

    Article  Google Scholar 

  6. Zhong LS, Hu JS, Liang HP, et al. Self-assembled 3D flowerlike iron oxide nanostructures and their application in water treatment. Adv Mater, 2006, 18: 2426–2431

    Article  Google Scholar 

  7. Liu Z, Chen L, Zhang L, et al. Ultrafast Cr(VI) removal from polluted water by microwave synthesized iron oxide submicron wires. Chem Commun, 2014; 50: 8036–8039

    Article  Google Scholar 

  8. Wei Z, Xing R, Zhang X, et al. Facile template-free fabrication of hollow nestlike a-Fe2O3 nanostructures for water treatment. ACS Appl Mater Interfaces, 2013; 5: 598–604

    Article  Google Scholar 

  9. Mu Y, Ai ZH, Zhang LZ, Song FH. Insight into core-shell dependent an oxic Cr(VI) removal with Fe@Fe2O3 nanowires: indispensable role of surface bound Fe(II). ACS Appl Mater Interfaces, 2015; 7: 1997–2005

    Article  Google Scholar 

  10. Hu J, Chen G, Lo IM. Removal and recovery of Cr(VI) from wastewater by maghemite nanoparticles. Water Res, 2005; 39: 4528–4536

    Article  Google Scholar 

  11. Wang P, Lo IM. Synthesis of mesoporous magnetic γ-Fe2O3 and its application to Cr(VI) removal from contaminated water. Water Res, 2009; 43: 3727–3734

    Article  Google Scholar 

  12. Baikousi M, Bourlinos AB, Douvalis A, et al. Synthesis and characterization of γ-Fe2O3/carbon hybrids and their application in removal of hexavalent chromium ions from aqueous solutions. Langmuir, 2012; 28: 3918–3930

    Article  Google Scholar 

  13. Liu Y, Wang Y, Zhou S, et al. Synthesis of high saturation magnetization superparamagnetic Fe3O4 hollow microspheres for swift chromium removal. ACS Appl Mater Interfaces, 2012; 4: 4913–4920

    Article  Google Scholar 

  14. Liu G, Deng Q, Wang H, et al. Synthesis and characterization of nanostructured Fe3O4 micron-spheres and their application in removing toxic Cr ions from polluted water. Chemistry, 2012, 18: 13418–13426

    Article  Google Scholar 

  15. Zhang WB, Deng M, Sun CX, Wang SB. Ultrasound-enhanced adsorption of chromium(VI) on Fe3O4 magnetic particles. Ind Eng Chem Res, 2014; 53: 333–339

    Article  Google Scholar 

  16. Parsons JG, Hernandez J, Gonzalez CM, Gardea-Torresdey JL. Sorption of Cr(III) and Cr(VI) to high and low pressure synthetic nano-magnetite (Fe3O4) particles. Chem Eng J, 2014; 254: 171–180

    Article  Google Scholar 

  17. Dui J, Zhu G, Zhou S. Facile and economical synthesis of large hollow ferrites and their applications in adsorption for As(V) and Cr(VI). ACS Appl Mater Interfaces, 2013, 5: 10081–10089

    Article  Google Scholar 

  18. Chowdhury SR, Yanful EK, Pratt AR. Chemical states in XPS and raman analysis during removal of Cr(VI) from contaminated water by mixed maghemite-magnetite nanoparticles. J Hazard Mater, 2012, 235–236: 246–256

    Article  Google Scholar 

  19. Zhang XQ, Guo Y, Li WC. Efficient removal of rexavalent chromium by high surface area Al2O3 rods. RSC Adv, 2015, 5: 25896–25903

    Article  Google Scholar 

  20. Neghlani PK, Rafizadeh M, Taromi FA. Preparation of aminated- polyacrylonitrile nanofiber membranes for the adsorption of metal ions: comparison with microfibers. J Hazard Mater, 2011; 186: 182–189

    Article  Google Scholar 

  21. Wang Y, Zou B, Gao T, et al. Synthesis of orange-like Fe3O4/PPy composite microspheres and their excellent Cr(VI) ion removal properties. J Mater Chem, 2012; 22: 9034–9040

    Article  Google Scholar 

  22. Bhaumik M, Maity A, Srinivasu VV, Onyango MS. Enhanced removal of Cr(VI) from aqueous solution using polypyrrole/Fe3O4 magnetic nanocomposite. J Hazard Mater, 2011; 190: 381–390

    Article  Google Scholar 

  23. Avila M, Burks T, Akhtar F, et al. Surface functionalized nanofibers for the removal of chromium(VI) from aqueous solutions. Chem Eng J, 2014; 245: 201–209

    Article  Google Scholar 

  24. Chen JH, Xing HT, Guo HX, et al. Investigation on the adsorption properties of Cr(VI) ions on a novel graphene oxide (GO) based composite adsorbent. J Mater Chem A, 2014, 2: 12561–12570

    Article  Google Scholar 

  25. Arulkumar M, Thirumalai K, Sathishkumar P, Palvannan T. Rapid removal of chromium from aqueous solution using novel prawn shell activated carbon. Chem Eng J, 2012, 185-186: 178–186

    Article  Google Scholar 

  26. Chen S, Yue Q, Gao B, Li Q, Xu X. Removal of Cr(VI) from aqueous solution using modified corn stalks: characteristic equilibrium kinetic and thermodynamic study. Chem Eng J, 2011; 168: 909–917

    Article  Google Scholar 

  27. Yin C, Aroua M, Daud W. Review of modifications of activated carbon for enhancing contaminant uptakes from aqueous solutions. Sep Purif Technol, 2007; 52: 403–415

    Article  Google Scholar 

  28. Liu H, Liang S, Gao J, et al. Enhancement of Cr(VI) removal by modifying activated carbon developed from zizania caduciflora with tartaric acid during phosphoric acid activation. Chem Eng J, 2014; 246: 168–174

    Article  Google Scholar 

  29. Stein A, Wang Z, Fierke MA. Functionalization of porous carbon materials with designed pore architecture. Adv Mater, 2009; 21: 265–293

    Article  Google Scholar 

  30. Xu GR, Wang JN, Li CJ. Preparation of hierarchically nanofibrous membrane and its high adaptability in hexavalent chromium removal from water. Chem Eng J, 2012, 198-199: 310–317

    Article  Google Scholar 

  31. Liu DH, Guo Y, Zhang LH, et al. Switchable transport strategy to deposit active Fe/Fe3C cores into hollow microporous carbons for efficient chromium removal. Small, 2013; 9: 3852–3857

    Article  Google Scholar 

  32. Zhang LH, Sun Q, Liu DH, Lu AH. Magnetic hollow carbon nanospheres for removal of chromium ions. J Mater Chem A, 2013; 1: 9477–9483

    Article  Google Scholar 

  33. Zhu J, Wei S, Gu H, et al. One-pot synthesis of magnetic graphene nanocomposites decorated with core@double-shell nanoparticles for fast chromium removal. Environ Sci Technol, 2012; 46: 977–985

    Article  Google Scholar 

  34. Gupta VK, Agarwal S, Saleh TA. Chromium removal by combining the magnetic properties of iron oxide with adsorption properties of carbon nanotubes. Water Res, 2011; 45: 2207–2212

    Article  Google Scholar 

  35. Zhang D, Wei S, Kaila C, et al. Carbon-stabilized iron nanoparticles for environmental remediation. Nanoscale, 2010; 2: 917–919

    Article  Google Scholar 

  36. Zhu J, Gu H, Guo J, et al. Mesoporous magnetic carbon nanocomposite fabrics for highly efficient Cr(VI) removal. J Mater Chem A, 2014; 2: 2256–2265

    Article  Google Scholar 

  37. Cui HJ, Cai JK, Zhao H, et al. One step solvothermal synthesis of functional hybrid γ-Fe2O3/carbon hollow spheres with superior capacities for heavy metal removal. J Colloid Interface Sci, 2014; 425: 131–135

    Article  Google Scholar 

  38. Wang GH, Sun Q, Zhang R, et al. Weak acid-base interaction induced assembly for the synthesis of diverse hollow nanospheres. Chem Mater, 2011; 23: 4537–4542

    Article  Google Scholar 

  39. Lu AH, Li WC, Salabas EL, Spliethoff B, Schüth F. Low temperature catalytic pyrolysis for the synthesis of high surface area nanostructured graphitic carbon. Chem Mater, 2006; 18: 2086–2094

    Article  Google Scholar 

  40. Lu AH, Li WC, Hao GP, et al. Easy synthesis of hollow polymer, carbon, and graphitized microspheres. Angew Chem Int Ed, 2010; 49: 1615–1618

    Article  Google Scholar 

  41. Qian D, Lei C, Wang EM, Li WC, Lu AH. A method for creating microporous carbon materials with excellent CO2 adsorption capacity and selectivity. Chem Sus Chem, 2014; 7: 291–298

    Article  Google Scholar 

  42. Sun Q, Guo CZ, Wang GH, et al. Fabrication of magnetic yolkshell nanocatalysts with spatially resolved functionalities and high activity for nitrobenzene hydrogenation. Chem Eur J, 2013; 19: 6217–6220

    Article  Google Scholar 

  43. Wang H, Yuan X, Wu Y, et al. Adsorption characteristics and behaviors of graphene oxide for Zn(II) removal from aqueous solution. Appl Surf Sci, 2013; 279: 432–440

    Article  Google Scholar 

  44. Simon-Kutscher J, Gericke A, Hühnerfuss H. Effect of bivalent Ba, Cu, Ni, and Zn cations on the structure of octadecanoic acid monolayers at the air-water interface as determined by external infrared reflection-absorption spectroscopy. Langmuir, 1996; 12: 1027–1034

    Article  Google Scholar 

  45. Cesano F, Scarano D, Bertarione S, et al. Synthesis of ZnO-carbon composites and imprinted carbon by the pyrolysis of ZnCl2-catalyzed furfuryl alcohol polymers. J Photochem Photobiol A, 2008; 196: 143–153

    Article  Google Scholar 

  46. Zhang L, Hu YH. A systematic investigation of decomposition of nano Zn4O(C8H4O4)3 metal-organic framework. J Phys Chem C, 2010; 114: 2566–2572

    Article  Google Scholar 

  47. Jiang HL, Liu B, Lan YQ, et al. From metal-organic framework to nanoporous carbon: toward a very high surface area and hydrogen uptake. J Am Chem Soc, 2011, 133: 11854–11857

    Article  Google Scholar 

  48. Zhang H, Yan Y, Yang L. Preparation of activated carbon from sawdust by zinc chloride activation. Adsorption, 2010; 16: 161–166

    Article  Google Scholar 

  49. Qian Q, Machida M, Tatsumoto H. Preparation of activated carbons from cattle-manure compost by zinc chloride activation. Bioresour Technol, 2007; 98: 353–360

    Article  Google Scholar 

  50. Khalili NR, Campbell M, Sandi G, Golas J. Production of microand mesoporous activated carbon from paper mill sludge. Carbon, 2000; 38: 1905–1915

    Article  Google Scholar 

  51. Caturla F, Molina-Sabio M, Rodríguez-Reinoso F. Preparation of activated carbon by chemical activation with ZnCl2. Carbon, 1991; 29: 999–1007

    Article  Google Scholar 

  52. Kim J, Kim HS, Lee N, et al. Multifunctional uniform nanoparticles composed of a magnetite nanocrystal core and a mesoporous silica shell for magnetic resonance and fluorescence imaging and for drug delivery. Angew Chem Int Ed, 2008; 47: 8438–8441

    Article  Google Scholar 

  53. Lu AH, Nitz JJ, Comotti M, et al. Spatially and size selective synthesis of Fe-based nanoparticles on ordered mesoporous supports as highly active and stable catalysts for ammonia decomposition. J Am Chem Soc, 2010, 132: 14152–14162

    Article  Google Scholar 

  54. Wu ZX, Li W, Webley PA, Zhao DY. General and controllable synthesis of novel mesoporous magnetic iron oxide@carbon encapsulates for efficient arsenic removal. Adv Mater, 2012; 24: 485–491

    Article  Google Scholar 

  55. Liu W, Zhang J, Zhang C, Ren L. Preparation and evaluation of activated carbon-based iron-containing adsorbents for enhanced Cr(VI) removal: mechanism study. Chem Eng J, 2012, 189–190: 295–302

    Article  Google Scholar 

  56. Ho YS, McKay G. Pseudo-second order model for sorption processes. Process Biochem, 1999; 34: 451–465

    Article  Google Scholar 

  57. Li R, Liu L, Yang F. A study on the reduction behaviors of Cr(VI) on Fe3O4/PANI. Procedia Environ Sci, 2013; 18: 522–527

    Article  Google Scholar 

  58. Babu BV, Gupta S. Adsorption of Cr(VI) using activated neem leaves: kinetic studies. Adsorption, 2007; 14: 85–92

    Article  Google Scholar 

  59. Fan L, Luo C, Sun M, Qiu H. Synthesis of graphene oxide decorated with magnetic cyclodextrin for fast chromium removal. J Mater Chem, 2012, 22: 24577–24583

    Article  Google Scholar 

  60. Babel S, Kurniawan TA. Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial activated carbon modified with oxidizing agents and/or chitosan. Chemosphere, 2004; 54: 951–967

    Article  Google Scholar 

  61. Aggarwal D, Goyal M, Bansal RC. Adsorption of chromium by activated carbon from aqueous solution. Carbon, 1999; 37: 1989–1997

    Article  Google Scholar 

  62. Deng S, Bai R. Removal of trivalent and hexavalent chromium with aminated polyacrylonitrile fibers: performance and mechanisms. Water Res, 2004; 38: 2423–2431

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, China

    Lu-Hua Zhang, Qiang Sun, Chao Yang & An-Hui Lu

Authors
  1. Lu-Hua Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Qiang Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Chao Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. An-Hui Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to An-Hui Lu.

Additional information

Lu-Hua Zhang was born in 1990. She received her BSs degree from Qingdao University of Science & Technology, Qingdao, China, in 2011. Then she joined Dalian University of Technology and conducted research under the supervision of Prof. An-Hui Lu. Her research interests include the controllable synthesis, surface modification and functionalization of magnetic carbon nanospheres.

An-Hui Lu was born in 1972. He is currently a professor at the State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, since 2008. He received his PhD degree from the Institute of Coal Chemistry, Chinese Academy of Sciences in 2001. After postdoctoral work (as a Max Planck research fellow and Alexander von Humboldt fellow) in the group of Prof. F. Schüth at Max-Planck-Institutfür Kohlenforschung, he was promoted to group leader in 2005. His research interests include designed synthesis of porous carbon-based solids, nanostructured energy-related materials, multifunctional magnetic nanomaterials, and their applications in heterogeneous catalysis, adsorption, energy storage, and conversion.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, LH., Sun, Q., Yang, C. et al. Synthesis of magnetic hollow carbon nanospheres with superior microporosity for efficient adsorption of hexavalent chromium ions. Sci. China Mater. 58, 611–620 (2015). https://doi.org/10.1007/s40843-015-0076-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-015-0076-8

Keywords

Search

Navigation