Skip to main content
SpringerLink
Log in

EXAFS and DFT studies of microscopic structure with different density upon Zn(II) adsorption on anatase TiO2

  • Published:
Adsorption Aims and scope Submit manuscript

Abstract

Microscopic structures of Zn(II) adsorbed on anatase TiO2 surface with different densities were studied using extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) calculation. Quantitative analysis of the EXAFS spectra showed that microscopic structures of Zn(II) were fourfold coordinated complexes, and different microscopic structures were present of the solid surface. Three modes of corner–corner/sharing-corner/sharing-edge adsorptions on anatase (101) face cluster were calculated by the DFT method. The results from DFT method were consistent with the EXAFS fittings. The optimized Zn–O average distance of the Zn–O tetrahedron was determined as about 2.00 Å. The Zn–Ti distance was 3.69 Å for the corner–corner adsorption, 3.35 Å for the sharing-corner adsorption, and 3.02 Å for the sharing-edge adsorption. According to the adsorption energies calculated by the DFT method, the microscopic structure of corner–corner adsorption was less stable than those of the other adsorption modes. With the increasing adsorption density, the corner–corner adsorption mode would be enhanced more intensively than the other adsorption modes.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Ankudinov, A.L., Ravel, B., Rehr, J.J., Conradson, S.D.: Real-space multiple scattering calculation of XANES. Phys. Rev. B 58, 7565–7576 (1998)

    Article  CAS  Google Scholar 

  • Barakat, M.A.: Adsorption behavior of copper and cyanide ions at TiO2–solution interface. J. Colloid Interface Sci. 291, 345–352 (2005)

    Article  CAS  Google Scholar 

  • Bochatay, L., Persson, P.: Metal ion coordination at the water–manganite (γ-MnOOH) interface: II. an EXAFS study of Zn(II). J. Colloid Interface Sci. 229, 593–599 (2000)

    Article  CAS  Google Scholar 

  • Brown Jr, G.E., Parks, G.A., O’Day, P.A.: In: Pattrick, R.A.D., Vaughan, D.J. (eds.) Mineral Surfaces, pp. 129–183. Chapman and Hall, London (1995)

    Google Scholar 

  • Brummer, G., Tiller, K.G., Herms, U., Clayton, P.M.: Adsorption–desorption and/or precipitation–dissolution processes of Zn in soils. Geoderma 31, 337–354 (1983)

    Article  Google Scholar 

  • Charlet, L., Manceau, A.: Environmental analytical and physical chemistry series. In: Buffle, J., van Leeuwen, H.P. (eds.) Environmental Particles, vol. 2, pp. 117–164. Lewis Publishers, Boca Raton (1993)

    Google Scholar 

  • Combes, J.M., Manceau, A., Calas, G., Bottero, J.Y.: Formation of ferric oxides from aqueous solutions: a polyhedral approach by X-ray absorption spectroscdpy: I. hydrolysis and formation of ferric gels. Geochim. Cosmochim. Acta 53, 583–594 (1989)

    Article  CAS  Google Scholar 

  • Coston, J.A., Fuller, C.C., Davis, J.A.: Pb2 + and Zn2 + adsorption by a natural Aluminum- and Iron-bearing surface coating on an aquifer sand. Geochim. Cosmochim. Acta 59, 3535–3547 (1995)

    Article  CAS  Google Scholar 

  • Frich, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery Jr, J.A., Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M., Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E., Hratchian, H.P., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador, P., Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S., Daniels, A.D., Strain, M.C., Farkas, O., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Ortiz, J.V., Cm, Q., Baboul, A.G., Clifford, S., Cioslowski, J., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challa-combe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Gonzalez, C., Pople, J.A.: Gaussian 03, Revision C.02. Gaussian, Wallingford (2004)

    Google Scholar 

  • Kiekens, L.: In: Alloway, B.J. (ed.) Heavy Metals in Soils, p. 284. Blackie, London (1990)

    Google Scholar 

  • Kim, M.S., Chung, J.G.: A study on the adsorption characteristics of orthophosphates on rutile-type titanium dioxide in aqueous solutions. J. Colloid Interface Sci. 233, 31–37 (2001)

    Article  CAS  Google Scholar 

  • Ladeira, A.C.Q., Ciminell, V.S.T., Duarte, H.A., Alves, M.C.M., Ramos, A.Y.: Mechanism of anion retention from EXAFS and density functional calculations: arsenic (V) adsorbed on gibbsite. Geochim. Cosmochim. Acta 65, 1211–1217 (2001)

    Article  CAS  Google Scholar 

  • Lee, S., Anderson, P.R., Bunker, G.B., Karanfil, C.: EXAFS study of Zn sorption mechanisms on montmorillonite. Environ. Sci. Technol. 385, 426–5432 (2004)

    Google Scholar 

  • Li, X., Pan, G., Qin, Y., Hu, T., Xie, Y., Chen, H.: EXAFS studies on adsorption microscopic structures of Zn at manganite-water interface. J. High Energy Phys. Nucl. Phys. 27, 23–27 (2003). Chinese edition

    Google Scholar 

  • Li, X., Pan, G., Qin, Y., Hu, T., Wu, Z., Xie, Y.: EXAFS studies on adsorption–desorption reversibility at manganese oxide–water interfaces: II. reversible adsorption of Zn on δ-MnO2. J. Colloid Interface Sci. 271, 35–40 (2004)

    Article  CAS  Google Scholar 

  • Li, W., Pan, G., Zhang, M.Y., Zhao, D.Y., Yang, Y.H., Chen, H., He, G.Z.: EXAFS studies on adsorption irreversibility of Zn(II) on TiO2: temperature dependence. J. Colloid Interface Sci. 319, 385–391 (2008)

    Article  CAS  Google Scholar 

  • Muller, B., Sigg, L.: Interaction of trace metals with natural particle surfaces: comparison between adsorption experiments and field measurements. Aquat. Sci. 52, 75–92 (1990)

    Article  Google Scholar 

  • Nachtegaal, M., Sparks, D.L.: Effect of iron oxide coatings on zinc sorption mechanisms at the clay-mineral/water interface. J. Colloid Interface Sci. 276, 13–23 (2004)

    Article  CAS  Google Scholar 

  • Pan, G., Qin, Y., Li, X., Hu, T., Wu, Z., Xie, Y.: EXAFS studies on adsorption–desorption reversibility at manganese oxides–water interfaces: I. irreversible adsorption of Zn onto manganite (γ-MnOOH). J. Colloid Interface Sci. 271, 28–34 (2004)

    Article  CAS  Google Scholar 

  • Papelis, C., Brown Jr, G.E., Parks, G.A., Leckie, J.O.: X-ray absorption spectroscopic studies of cadmium and selenite adsorption on aluminum oxides. Langmuir 11, 2041–2048 (1995)

    Article  CAS  Google Scholar 

  • Ragnarsdottir, K.V., Collins, C.R.: The mechanism of cadmium surface complexation on iron oxyhydroxide minerals. Geochim. Cosmochim. Acta 63, 2971–2987 (1999)

    Article  Google Scholar 

  • Ravel, B.: ATOMS, crystallography for the X-ray absorption spectroscopist. J. Synchroton Radiat. 8, 314–316 (2001)

    Article  CAS  Google Scholar 

  • Ressler, T.: WinXAS, a program for X-ray absorption spectroscopy data analysis under MS-windows. J. Synchrotron Radiat. 5, 118–122 (1998)

    Article  CAS  Google Scholar 

  • Roe, A.L., Hayes, K.F., Chisholm-Brause, C.J., Brown Jr, G.E., Parks, G.A., Hodgson, K.O., Leckie, J.O.: In-situ X-ray absorption study of lead ion surface complexes at the goethite-water interface. Langmuir 7, 367–373 (1991)

    Article  CAS  Google Scholar 

  • Scheidigger, A.M., Lamble, G.M., Sparks, D.L.: Spectroscopic evidence for the formation of mixed-cation hydroxide phases upon metal sorption on clays and Aluminum Oxides. J. Colloid Interface Sci. 186, 118–128 (1997)

    Article  Google Scholar 

  • Shock, E.L., Koretsky, C.M.: Etal-organic complexes in geochemical processes: calculation of standard partial molal thermodynamic properties of aqueous acetate complexes at high pressures and temperatures. Geochim. Cosmochim. Acta 57, 4899–4922 (1993)

    Article  CAS  Google Scholar 

  • Spadini, L., Manceau, A., Schindler, P.W., Charlet, L.: Structure and stability of Cd2+ surface complexes on ferric oxides: 1. Results from EXAFS spectroscopy. J. Colloid Interface Sci. 168, 73–86 (1994)

    Article  CAS  Google Scholar 

  • Tessier, A., Carignan, R., Dubruel, B., Rapin, F.: Partitioning of Zn between the water column and the oxic sediments in lakes. Geochim. Cosmochim. Acta 53, 1511–1522 (1989)

    Article  CAS  Google Scholar 

  • Towle, S.N., Brown, G.E., Parks, G.A.: Sorption of Co(II) on metal oxide surfaces: I. Identification of specific binding sites of Co(II) on (110) and (001) surfaces of TiO2 (rutile) by Grazing-incidence XAFS spectroscopy. J. Colloid Interface Sci. 217, 299–311 (1999)

    Article  CAS  Google Scholar 

  • Trainor, T.P., Brown, G.E., Parks, G.A.: Adsorption and precipitation of aqueous Zn(II) on alumina powders. J. Colloid Interface Sci. 231, 359–372 (2000)

    Article  CAS  Google Scholar 

  • Trivedi, P., Axe, L., Tyson, T.A.: An analysis of Zn sorption to amorphous versus crystalline iron oxides using XAS. J. Colloid Interface Sci. 244, 230–238 (2001)

    Article  CAS  Google Scholar 

  • Ulrike, D.: The surface science of TiO2. Surf. Sci. Rep. 48, 53–229 (2003)

    Article  Google Scholar 

  • Vittadini, A., Selloni, A., Rotzinger, F.P., Gratzel, M.: Structure and energetics of water adsorbed at TiO2 anatase (101) and (001) surfaces. J. Phys. Chem. C 104, 1300–1306 (2000)

    CAS  Google Scholar 

  • Vymazal, J.: Occurrence and chemistry of Zn in freshwaters—its toxicity and bioaccumulation with respect to algae: a review. Part 1: occurrence and chemistry of Zn. Acta Hydrochem. Hydrobiol. 13, 627–654 (1985)

    Article  CAS  Google Scholar 

  • Waychunas, G.A., Rea, B.A., Fuller, C.C., Davis, J.A.: Surface chemistry of ferrihydrite:Part 1.EXAFS study of geometry of coprecipitated and adsorbed arsenate. Geochim. Cosmochim. Acta 57, 2251–2269 (1993)

    Article  CAS  Google Scholar 

  • Waychunas, G.A., Davis, J.A., Fuller, C.C.: Geometry of sorbed arsenate on ferrihydrite and crystalline FeOOH. Geochim. Cosmochim. Acta 59, 3655–3661 (1995)

    Article  CAS  Google Scholar 

  • Zhang, P.C., Brady, P.V., Arthur, S.E., Zhou, W.Q.: Adsorption of barium (II) on montmorillonite: an EXAFS study. Colloids Surf. A 190, 239–249 (2001)

    Article  CAS  Google Scholar 

  • Zhu, M., Pan, G.: Quantum chemical studies of mononuclear zinc species of hydration and hydrolysis. J. Phys. Chem. A 109, 7648–7652 (2005)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors thank the institute of high energy physics Chinese academy of sciences for the EXAFS spectrum unscrambling and soft support, and thank the supercomputing center of Chinese academy of sciences for the DFT soft. This work was financially supported by NNSF of China (Grant No. 21107054).

Author information

Authors and Affiliations

  1. School of Public Health, Nantong University, Nantong, 226019, Jiangsu Province, People’s Republic of China

    Yuhuan Yang & Changqing Ye

  2. State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, People’s Republic of China

    Yuhuan Yang & Hao Chen

Authors
  1. Yuhuan Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hao Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Changqing Ye
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yuhuan Yang.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Yang, Y., Chen, H. & Ye, C. EXAFS and DFT studies of microscopic structure with different density upon Zn(II) adsorption on anatase TiO2 . Adsorption 19, 1019–1025 (2013). https://doi.org/10.1007/s10450-013-9510-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10450-013-9510-y

Keywords

Search

Navigation