Skip to main content
SpringerLink
Log in

Mechanistic study on boron adsorption and isotopic separation with magnetic magnetite nanoparticles

  • Chemical routes to materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Good boron removal and isotopic separation behavior was observed on magnetic magnetite nanoparticles (MMNs) in a previous study, but the mechanism of boron adsorption and isotopic separation remains unclear. Here, experimental studies accompanied by quantum chemistry calculations were implemented for the first time to reveal the nature of boron adsorption and isotopic separation on MMN. First, the fitted peaks of Fe2p of MMN by X-ray photoelectron spectrometry (XPS) before and after adsorption showed decrease in Fe(II)/Fe(III) ratio, which validated the formation of Fe–O–B interaction. Fe–O–B bond was also observed through fitted peaks of O1s and dihydroxy complexation where MMNs prefer to adsorb [B(OH)4]−(H3BO3) at pH <  = pHzpc (pH > pHzpc) identified by the ratio of integrated peaks. ATR-FTIR revealed the hydroxyl moiety as the main adsorptive group. The selectivity of MMN toward [B(OH)4]− at pH <  = pHzpc and toward H3BO3 at pH > pHzpc was figured out by calculating the ratio between the integrated areas of B–O bands at different pH values. As a result, the trend of adsorption capacity as well as the isotopic separation factor with pH was well illustrated. The concluded adsorption mechanism from the experiment was further verified with the simulated adsorption energies (ΔE) and isotopic separation factors (S) calculated by DFT quantum simulation.

Graphical abstract

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

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11

Similar content being viewed by others

References

  1. Nasef M, Nallappan M, Ujang Z (2014) Polymer-based chelating adsorbents for the selective removal of boron from water and wastewater: a review. React Funct Polym 85:54–68

    CAS  Google Scholar 

  2. Geffen N, Semiat R, Eisen MS, Balazs Y (2006) Boron removal from water by complexation to polyol compounds. J Membr Sci 286:45–51

    CAS  Google Scholar 

  3. Öztürk N, Kavak D, Köse TE (2008) Boron removal from aqueous solution by reverse osmosis. Desalination 223:1–9

    Google Scholar 

  4. Scott VE (1940) Effects of boron deficiency and excess on plants. Plant Physiol 15:95–107

    Google Scholar 

  5. Hilal N, Kim GJ, Somerfield C (2011) Boron removal from saline water: a comprehensive review. Desalination 273:23–35

    CAS  Google Scholar 

  6. Cengeloglu Y, Tor A, Arslan G, Ersoz M, Gezgin S (2007) Removal of boron from aqueous solution by using neutralized red mud. J Hazard Mater 142:412–417

    CAS  Google Scholar 

  7. Wang L, Qi T, Zhang Y (2006) Novel organic–inorganic hybrid mesoporous materials for boron adsorption. Colloid Surf A 275:73–78

    CAS  Google Scholar 

  8. Guo Q, Zhang Y, Cao Y, Wang Y, Yan W (2013) Boron sorption from aqueous solution by hydrotalcite and its preliminary application in geothermal water deboronation. Environ Sci Pollut Res 20:8210–8219

    CAS  Google Scholar 

  9. Özdemir M, Kıpçak İ (2007) Boron recovery from borax sludge using solid–liquid extraction followed by sorption with a boron selective resin in column. Environ Prog 26:375–383

    Google Scholar 

  10. Yoneda Y, Uchijima T, Makishima S (1959) Separation of boron isotopes by ion exchange. J Phys Chem 63:2057–2058

    CAS  Google Scholar 

  11. Zawisky M, Bastürk M, Derntl R, Dubus F, Lehmann E, Vontobel P (2004) Non-destructive 10B analysis in neutron transmission experiments. Appl Radiat Isot 61:517–523

    CAS  Google Scholar 

  12. Masoudi SF, Rasouli FS, Ghasemi M (2017) BNCT of skin tumors using the high-energy D-T neutrons. Appl Radiot Isot 122:158–163

    CAS  Google Scholar 

  13. Wu X, Bai P, Guo X, He N (2014) 2,4-Difluoro anisole: a promising complexing agent for boron isotopes separation by chemical exchange reaction and distillation. J Radioanal Nucl Ch 300:897–902

    CAS  Google Scholar 

  14. Nagasawa H, Iizuka A, Yamasaki A, Yanagisawa Y (2011) Utilization of bipolar membrane electrodialysis for the removal of boron from aqueous solution. Ind Eng Chem Res. 50:6325–6330

    CAS  Google Scholar 

  15. Jjiang YX (2008) Technologies for boron removal. Ind Eng Chem Res 47:16–24

    Google Scholar 

  16. Guan Z, Lv J, Bai P, Guo X (2016) Boron removal from aqueous solutions by adsorption—a review. Desalination 383:29–37

    CAS  Google Scholar 

  17. Zhang N, Lyu J, Bai P, Guo X (2018) Boron isotopic separation with pyrocatechol-modified resin by chromatography technology: experiment and numerical simulation. J Ind Eng Chem 57:244–253

    CAS  Google Scholar 

  18. Lyu J, Zeng Z, Zhang N, Liu H, Bai P, Guo X (2017) Pyrocatechol-modified resins for boron recovery from water: synthesis, adsorption, and isotopic separation studies. React Funct Polym 112:1–8

    CAS  Google Scholar 

  19. Lyu J, Liu H, Zhang J, Zeng Z, Peng B, Guo X (2017) Metal–organic frameworks (MOFs) as highly efficient agents for boron removal and boron isotope separation. Rsc Adv 7:16022–16026

    CAS  Google Scholar 

  20. Chen T, Wang Q, Lyu J, Bai P, Guo X (2020) Boron removal and reclamation by magnetic magnetite (Fe3O4) nanoparticle: An adsorption and isotopic separation study. Sep Purif Technol 231:115930

  21. Peak D, Luther GW, Sparks DL (2003) ATR-FTIR spectroscopic studies of boric acid adsorption on hydrous ferric oxide. Geochim Cosmochim Acta 67:2551–2560

    CAS  Google Scholar 

  22. Rajput S, Pittman CU Jr, Mohan D (2016) Magnetic magnetite (Fe3O4) nanoparticle synthesis and applications for lead (Pb2+) and chromium (Cr6+) removal from water. J Colloid Interface Sci 468:334–346

    CAS  Google Scholar 

  23. Su C, Suarez D (1995) Coordination of adsorbed boron: a FTIR spectroscopic study. Environ Sci Technol 29:302–311

    CAS  Google Scholar 

  24. Ji H, Du P, Zhao D, et al. (2020) 2D/1D graphitic carbon nitride/titanate nanotubes heterostructure for efficient photocatalysis of sulfamethazine under solar light: catalytic “hot spots” at the rutile–anatase–titanate interfaces. Appl Catal B-Environ 263:118357

  25. Ma M, Chen L, Zhao J, Liu W, Ji H (2019) Efficient activation of peroxymonosulfate by hollow cobalt hydroxide for degradation of ibuprofen and theoretical study. Chin Chem Lett 30:2191–3195

    CAS  Google Scholar 

  26. Zhou F, Zhang J, Bai P (2018) Theoretical study on complexes and reactions of boron isotopic exchange separation with fluorinated anisoles as novel donors. J Radioanal Nucl Chem 316:587–594

    CAS  Google Scholar 

  27. Rath S, Sinha N, Sahoo H, Das B, Mishra BK (2014) Molecular modeling studies of oleate adsorption on iron oxides. Appl Surf Sci 295:115–122

    CAS  Google Scholar 

  28. Zhou F, Zhang J, Bai P, Guo X (2016) Theoretical calculation of boron isotopic separation factors in ion-exchange chromatography. J Chem Eng Data 62:525–531

    Google Scholar 

  29. Zuo J, Spence JC, Petuskey W (1990) Charge ordering in magnetite at low temperatures. Phys Rev B Condens Matter 42:8451–8464

    CAS  Google Scholar 

  30. Parr R, Gadre S (1979) Local density functional theory of atoms and molecules. P Natl Acad Sci USA 76:2522–2526

    CAS  Google Scholar 

  31. Segall M, Lindan D (2002) First-principles simulation: ideas, illustrations and the CASTEP code. J Phys Condens Matter 14:2717–2744

    CAS  Google Scholar 

  32. Perdew J, Burke K, Wang M (1996) Generalized gradient approximation for the exchange-correlation hole of a many-electron system. Phys Rev B Condens Matter 54:16533–16539

    CAS  Google Scholar 

  33. Ernzerhof M, Scuseria G (1999) Assessment of the Perdew-Burke-Ernzerhof exchange-correlation functional. J Chem Phys 110:5029–5030

    CAS  Google Scholar 

  34. Kovács SÁ, Lo CS (2010) Electronic structure and charge ordering in magnetite: implications for the Fe3O4 (001)–water interface. Mol Simulat 36:1289–1296

    Google Scholar 

  35. Oi T, Yanase S (2001) Calculations of reduced partition function ratios of hydrated monoborate anion by the ab initio moleculaSr orbital theory. J Nucl Sci Technol 38:429–432

    CAS  Google Scholar 

  36. Vanderbilt D (1985) Optimally smooth norm-conserving pseudopotentials. Phys Rev B Condens Matter 32:8412–8415

    CAS  Google Scholar 

  37. Edzwald JK, Haarhoff J (2011) Seawater pretreatment for reverse osmosis: chemistry, contaminants, and coagulation. Water Res 45:5428–5440

    CAS  Google Scholar 

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

    Google Scholar 

  39. Afkhami A, Moosavi R (2010) Adsorptive removal of Congo red, a carcinogenic textile dye, from aqueous solutions by maghemite nanoparticles. J Hazard Mater 174:398–403

    CAS  Google Scholar 

  40. Wu Y, Chen R, Liu H, Wei Y, Wu D (2013) Feasibility and mechanism of p -nitrophenol decomposition in aqueous dispersions of ferrihydrite and H2O2 under irradiation. React Kinet Mech Cat 110:87–99

    CAS  Google Scholar 

  41. Honma T, Sato R, Benino Y, Komatsu T (2000) Electronic polarizability, optical basicity and XPS spectra of Sb2O3–B2O3 glasses. J Non-Cryst Solids 272:1–13

    CAS  Google Scholar 

  42. Fujii T, Groot F, Sawatzky GA (1999) In situ XPS analysis of various iron oxide films grown by NO2—assisted molecular-beam epitaxy. Phys Rev B 4:3195–3202

    Google Scholar 

  43. Gebhardt J, Koch RJ, Zhao W, Höfert O, Gotterbarm K (2013) Growth and electronic structure of boron-doped graphene. Phys Rev B 87:1–9

    Google Scholar 

  44. Lakshminarayana G, Baki SO, Lira A et al (2017) X-ray photoelectron spectroscopy (XPS) and radiation shielding parameters investigations for zinc molybdenum borotellurite glasses containing different network modifiers. J Mater Sci 52:7394–7414. https://doi.org/10.1007/s10853-017-0974-0

    Article  CAS  Google Scholar 

  45. Hu Q, Liu Y, Gu X, Zhao Y (2017) Adsorption behavior and mechanism of different arsenic species on mesoporous MnFe2O4 magnetic nanoparticles. Chemosphere 181:328–336

    CAS  Google Scholar 

  46. Li X, Liu R, Wu S, Liu J, Cai S, Chen D (2011) Efficient removal of boron acid by N-methyl-D-glucamine functionalized silica-polyallylamine composites and its adsorption mechanism. J Colloid Interface Sci 361:232–237

    CAS  Google Scholar 

  47. Pistorius T (1959) Potential function of boric acid. J Chem Phys 31:1454–1457

    CAS  Google Scholar 

  48. Karahan S, Yurdakoc M, Seki Y, Yurdakoc K (2006) Removal of boron from aqueous solution by clays and modified clays. J Colloid Interface Sci 293:36–42

    CAS  Google Scholar 

  49. Fei P, Liao L, Cheng B, Song J (2017) Quantitative analysis of cellulose acetate with a high degree of substitution by FTIR and its application. Anal Methods 9:6194–6201

    CAS  Google Scholar 

  50. Rafiee M, Nematollahi D (2008) Electrochemical study of catechol–boric acid complexes. Electrochim Acta 53:2751–2756

    CAS  Google Scholar 

  51. Meng MX, Korfiatis GP, Jing C (2006) Adsorption mechanism of arsenicon nanocrystalline titanium dioxide. Environ Sci Technol 40:1257–1262

    Google Scholar 

  52. Oi T, Shimazaki H, Ishii R, Hosoe M (1997) Boron isotope fractionation in liquid chromatography with boron-specific Resins as column packing material. Sep Sci 32:1821–1834

    CAS  Google Scholar 

  53. Tao Y, Wen X, Ren J, Yong-Wang L, Wang J, Huo C (2010) Surface structures of Fe3O4 (111), (110), and (001)—a density functional theory study. Chem Tech Fuels Oil 38:121–128

    Google Scholar 

  54. Wang H, Sun X, Han E (2018) The Interactions between high temperature water and Fe3O4 (111) by first-principles molecular dynamics simulation. Int J Electrochem Sci 13:2430–2440

    CAS  Google Scholar 

  55. Mulakaluri N, Pentcheva R, Wieland M, Moritz W, Scheffler M (2009) Partial dissociation of water on Fe3O4 (001): adsorbate induced charge and orbital order. Phys Rev Lett 103:1–4

    Google Scholar 

  56. Roldan A, de Leeuw NH (2017) A kinetic model of water adsorption, clustering and dissociation on the Fe3S4 {001} surface. Phys Chem Chem Phys 19:12045–12055

    CAS  Google Scholar 

Download references

Acknowledgements

This project was supported by National Natural Science Foundation of China (No. 22078235, No. 22008176) and China Postdoctoral Science Foundation (2019M661022).

Author information

Author notes

  1. Tao Chen and Jiafei Lyu have contributed equally to this work.

Authors and Affiliations

  1. Department of Pharmaceutical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, China

    Tao Chen, Jiafei Lyu, Qingfeng Wang, Peng Bai & Xianghai Guo

  2. Key Laboratory of Systems Bioengineering (Ministry of Education), Tianjin University, Tianjin, 300072, China

    Tao Chen, Jiafei Lyu, Qingfeng Wang, Peng Bai & Xianghai Guo

  3. The School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510641, Guangdong, China

    Ying Wu

  4. School of Marine Science and Technology, Tianjin University, Tianjin, 300072, China

    Xianghai Guo

Authors
  1. Tao Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jiafei Lyu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qingfeng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Peng Bai
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ying Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Xianghai Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

The manuscript was written through the contribution of all authors. All authors have given approval to the final version of the manuscript.

Corresponding author

Correspondence to Xianghai Guo.

Ethics declarations

Conflict of interest

The authors declare no competing financial interest.

Additional information

Handling Editor: Dale Huber

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

10853_2020_5546_MOESM1_ESM.docx

Supplementary file1. Details of prepared MMN, adsorption schematic diagram,characterization results, model diagram of density function theory (DFT) calculationswere described as Fig. S1–S16, Table S1–S7. (DOC 1026 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, T., Lyu, J., Wang, Q. et al. Mechanistic study on boron adsorption and isotopic separation with magnetic magnetite nanoparticles. J Mater Sci 56, 4624–4640 (2021). https://doi.org/10.1007/s10853-020-05546-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-020-05546-x

Search

Navigation