Issue

Vol. 10 No. 4 (2018)

Mesoporous SiO2 Nanoparticles: A Unique Platform Enabling Sensitive Detection of Rare Earth Ions with Smartphone Camera

https://doi.org/10.1007/s40820-018-0208-2
Xinyan Dai
Department of Chemistry, Temple University, 1901 North 13th Street, Philadelphia, PA 19122, USA
Kowsalya D. Rasamani
Department of Chemistry, Temple University, 1901 North 13th Street, Philadelphia, PA 19122, USA
Feng Hu
Department of Chemistry, Temple University, 1901 North 13th Street, Philadelphia, PA 19122, USA
Yugang Sun
Department of Chemistry, Temple University, 1901 North 13th Street, Philadelphia, PA 19122, USA

Corresponding Author: Yugang Sun

ygsun@temple.edu

Nano-Micro Letters, Vol. 10 No. 4 (2018), Article Number: 55

Abstract

Fast and sensitive detection of dilute rare earth species still represents a challenge for an on-site survey of new resources and evaluation of the economic value. In this work, a robust and low-cost protocol has been developed to analyze the concentration of rare earth ions using a smartphone camera. The success of this protocol relies on mesoporous silica nanoparticles (MSNs) with large-area negatively charged surfaces, on which the rare earth cations (e.g., Eu3+) are efficiently adsorbed through electrostatic attraction to enable a “concentrating effect”. The initial adsorption rate is as fast as 4025 mg (g min)−1, and the adsorption capacity of Eu3+ ions in the MSNs is as high as 4730 mg g−1 (equivalent to ~ 41.2 M) at 70 °C. The concentrated Eu3+ ions in the MSNs can form a complex with a light sensitizer of 1,10-phenanthroline to significantly enhance the characteristic red emission of Eu3+ ions due to an “antenna effect” that relies on the efficient energy transfer from the light sensitizer to the Eu3+ ions. The positive synergy of “concentrating effect” and “antenna effect” in the MSNs enables the analysis of rare earth ions in a wide dynamic range and with a detection limit down to ~ 80 nM even using a smartphone camera. Our results highlight the promise of the protocol in fieldwork for exploring valuable rare earth resources.


Highlights:


1 A protocol for quantitative measurement of Eu3+ ions is developed using mesoporous silica nanoparticles.
2 A “concentrating effect” of mesoporous silica nanoparticles is responsible for high adsorption capacity (4730 mg g−1) of Eu3+ ions. An “antenna effect” of 1,10-phenanthroline enables enhanced photoemission of adsorbed Eu3+ ions.
3 The detection limit of Eu3+ ions is 80 nM even with smartphone camera.

Keywords

Mesoporous silica nanoparticles Rare earth ions Quantitative detection Antenna effect
Dai, Xinyan, Kowsalya D. Rasamani, Feng Hu, and Yugang Sun. 2018. “Mesoporous SiO2 Nanoparticles: A Unique Platform Enabling Sensitive Detection of Rare Earth Ions With Smartphone Camera”. Nano-Micro Letters 10 (4):55. https://doi.org/10.1007/s40820-018-0208-2.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. S. Gai, C. Li, P. Yang, J. Lin, Recent progress in rare earth micro/nanocrystals: soft chemical synthesis, luminescent properties, and biomedical applications. Chem. Rev. 114(4), 2343–2389 (2013). https://doi.org/10.1021/cr4001594
  2. K.M. Goodenough, F. Wall, D. Merriman, The rare earth elements: demand, global resources, and challenges for resourcing future generations. Nat. Resour. Res. 27(2), 201–216 (2017). https://doi.org/10.1007/s11053-017-9336-5
  3. R. Boonsin, G. Chadeyron, J.P. Roblin, D. Boyer, R. Mahiou, Development of rare-earth-free phosphors for eco-energy lighting based LEDs. J. Mater. Chem. C 3(37), 9580–9587 (2015). https://doi.org/10.1039/C5TC01516B
  4. D. Haranath, S. Mishra, A.G. Joshi, S. Sahai, V. Shanker, Effective doping of rare-earth ions in silica gel: a novel approach to design active electronic devices. Nano-Micro Lett. 3(3), 141–145 (2011). https://doi.org/10.1007/bf03353664
  5. R. John, R. Rajakumari, Synthesis and characterization of rare earth ion doped nano ZnO. Nano-Micro Lett. 4(2), 65–72 (2012). https://doi.org/10.1007/bf03353694
  6. Y. Pu, K. Tang, D.C. Zhu, T. Han, C. Zhao, L.L. Peng, Synthesis and luminescence properties of (Y, Gd) (P, V)O4:Eu3+, Bi3+ red nano-phosphors with enhanced photoluminescence by Bi3+, Gd3+ doping. Nano-Micro Lett. 5(2), 117–123 (2013). https://doi.org/10.1007/bf03353738
  7. S. Massari, M. Ruberti, Rare earth elements as critical raw materials: focus on international markets and future strategies. Resour. Policy 38(1), 36–43 (2013). https://doi.org/10.1016/j.resourpol.2012.07.001
  8. R. Lin, B.H. Howard, E.A. Roth, T.L. Bank, E.J. Granite, Y. Soong, Enrichment of rare earth elements from coal and coal by-products by physical separations. Fuel 200, 506–520 (2017). https://doi.org/10.1016/j.fuel.2017.03.096
  9. E. Roth, T. Bank, B. Howard, E. Granite, Rare earth elements in Alberta oil sand process streams. Energy Fuels 31(5), 4714–4720 (2017). https://doi.org/10.1021/acs.energyfuels.6b03184
  10. W.C. Wilfong, B.W. Kail, T.L. Bank, B.H. Howard, M.L. Gray, Recovering rare earth elements from aqueous solution with porous amine–epoxy networks. ACS Appl. Mater. Interfaces 9(21), 18283–18294 (2017). https://doi.org/10.1021/acsami.7b03859
  11. T. Dutta, K.H. Kim, M. Uchimiya, E.E. Kwon, B.H. Jeon, A. Deep, S.T. Yun, Global demand for rare earth resources and strategies for green mining. Environ. Res. 150, 182–190 (2016). https://doi.org/10.1016/j.envres.2016.05.052
  12. S. Maes, W.Q. Zhuang, K. Rabaey, L. Alvarez-Cohen, T. Hennebel, Concomitant leaching and electrochemical extraction of rare earth elements from Monazite. Environ. Sci. Technol. 51(3), 1654–1661 (2017). https://doi.org/10.1021/acs.est.6b03675
  13. C.W. Noack, D.A. Dzombak, A.K. Karamalidis, Determination of rare earth elements in hypersaline solutions using low-volume, liquid–liquid extraction. Environ. Sci. Technol. 49(16), 9423–9430 (2015). https://doi.org/10.1021/acs.est.5b00151
  14. J. Roosen, S. Van Roosendael, C.R. Borra, T. Van Gerven, S. Mullens, K. Binnemans, Recovery of scandium from leachates of Greek bauxite residue by adsorption on functionalized chitosan–silica hybrid materials. Green Chem. 18(7), 2005–2013 (2016). https://doi.org/10.1039/C5GC02225H
  15. D. Kim, L.E. Powell, L.H. Delmau, E.S. Peterson, J. Herchenroeder, R.R. Bhave, Selective extraction of rare earth elements from permanent magnet scraps with membrane solvent extraction. Environ. Sci. Technol. 49(16), 9452–9459 (2015). https://doi.org/10.1021/acs.est.5b01306
  16. V. Funari, S.N.H. Bokhari, L. Vigliotti, T. Meisel, R. Braga, The rare earth elements in municipal solid waste incinerators ash and promising tools for their prospecting. J. Hazard. Mater. 301, 471–479 (2016). https://doi.org/10.1016/j.jhazmat.2015.09.015
  17. D. Golightly, F.O. Simon, Methods for sampling and inorganic analysis of coal (US Government Printing Office, 1989), pp. 35–57
  18. F.G. Pinto, R.E. Junior, T.D. Saint’Pierre, Sample preparation for determination of rare earth elements in geological samples by ICP-MS: a critical review. Anal. Lett. 45(12), 1537–1556 (2012). https://doi.org/10.1080/00032719.2012.677778
  19. T.L. Bank, E.A. Roth, P. Tinker, E. Granite, Analysis of rare earth elements in geologic samples using inductively coupled plasma mass spectrometry, US DOE Topical Report-DOE/NETL-2016/1794 (No. NETL-PUB-20441). National Energy Technology Lab (NETL), Pittsburgh, PA, 2016. https://doi.org/10.2172/1415779
  20. L.A. Rocha, J. Freiria, J.M. Caiut, S.J.L. Ribeiro, Y. Messaddeq, M. Verelst, J. Dexpert-Ghys, Luminescence properties of Eu-complex formations into ordered mesoporous silica particles obtained by the spray pyrolysis process. Nanotechnology 26(33), 335604 (2015). https://doi.org/10.1088/0957-4484/26/33/335604
  21. A. Ishii, M. Hasegawa, An interfacial europium complex on SiO2 nanoparticles: reduction-induced blue emission system. Sci. Rep. 5, 11714 (2015). https://doi.org/10.1038/srep11714
  22. I.V. Taydakov, A.A. Akkuzina, R.I. Avetisov, A.V. Khomyakov, R.R. Saifutyarov, I.C. Avetissov, Effective electroluminescent materials for OLED applications based on lanthanide 1.3-diketonates bearing pyrazole moiety. J. Lumin. 177, 31–39 (2016). https://doi.org/10.1016/j.jlumin.2016.04.017
  23. A. Ishii, M. Hasegawa, The ethanol-induced interfacial reduction of a europium complex on SiO2 nanoparticles. Chem. Lett. 45(11), 1265–1267 (2016). https://doi.org/10.1246/cl.160698
  24. L. Jiang, J.W. Zheng, W.C. Chen, J.J. Ye, L.E. Mo et al., Tuning coordination environment: better photophysical performance of europium (iii) complex. J. Phys. Chem. C 121(11), 5925–5930 (2017). https://doi.org/10.1021/acs.jpcc.6b12756
  25. Y. Wan, S.H. Yu, Polyelectrolyte controlled large-scale synthesis of hollow silica spheres with tunable sizes and wall thicknesses. J. Phys. Chem. C 112(10), 3641–3647 (2008). https://doi.org/10.1021/jp710990b
  26. Y. Liu, C.Y. Song, X.S. Luo, J. Lu, X.W. Ni, Fluorescence spectrum characteristic of ethanol–water excimer and mechanism of resonance energy transfer. Chin. Phys. 16(5), 1300 (2007). https://doi.org/10.1088/1009-1963/16/5/023
  27. Y. Wan, D.Y. Zhao, On the controllable soft-templating approach to mesoporous silicates. Chem. Rev. 107(7), 2821–2860 (2007). https://doi.org/10.1021/cr068020s
  28. S. Tosonian, C.J. Ruiz, A. Rios, E. Frias, J.F. Eichler, Synthesis, characterization, and stability of iron (III) complex ions possessing phenanthroline-based ligands. Open J. Inorg. Chem. 3(1), 7–13 (2013). https://doi.org/10.4236/ojic.2013.31002
  29. M.J. Lochhead, P.R. Wamsley, K.L. Bray, Luminescence spectroscopy of europium(III) nitrate, chloride, and perchlorate in mixed ethanol–water solutions. Inorg. Chem. 33(9), 2000–2003 (1994). https://doi.org/10.1021/ic00087a041
  30. J.C. Bünzli, C. Piguet, Taking advantage of luminescent lanthanide ions. Chem. Soc. Rev. 34, 1048–1077 (2005). https://doi.org/10.1039/B406082M
  31. A.M. Nonat, A.J. Harte, K. Senechal-David, J.P. Leonard, T. Gunnlaugsson, Luminescent sensing and formation of mixed f–d metal ion complexes between a Eu(III)-cyclen-phen conjugate and Cu(II), Fe(II), and Co(II) in buffered aqueous solution. Dalton Trans. 24, 4703–4711 (2009). https://doi.org/10.1039/B901567A
  32. F.H. Spedding, J.E. Powell, E.J. Wheelwright, The separation of adjacent rare earths with ethylenediamine-tetraacetic acid by elution from an ion-exchange resin. J. Am. Chem. Soc. 76(2), 612–613 (1994). https://doi.org/10.1021/ja01631a091
  33. F. Xie, T.A. Zhang, D. Dreisinger, F. Doyle, A critical review on solvent extraction of rare earths from aqueous solutions. Miner. Eng. 56, 10–28 (2014). https://doi.org/10.1016/j.mineng.2013.10.021
  34. G.A. Martoyan, G.G. Karamyan, G.A. Vardan, New technology of extracting the amount of rare earth metals from the red mud. IOP Conf. Ser.: Mater. Sci. Eng. 112, 012033 (2016). https://doi.org/10.1088/1757-899X/112/1/012033
  35. T.V. Hoogerstraete, S. Wellens, K. Verachtert, K. Binnemans, Removal of transition metals from rare earths by solvent extraction with an undiluted phosphonium ionic liquid: separations relevant to rare-earth magnet recycling. Green Chem. 15, 919–927 (2013). https://doi.org/10.1039/C3GC40198G
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY MATERIAL
Statistic
Read Counter : 3892 Download : 2947

Most read articles by the same author(s)