Advertisement

Clays and Clay Minerals

, Volume 66, Issue 3, pp 261–273 | Cite as

Effects of Fe and V States on the Fenton Catalytic Activity of Natural Rutile

  • Yanzhang Li
  • Zemin Luo
  • Yan LiEmail author
  • Feifei Liu
  • Anhuai Lu
  • Jing Wu
  • Shan Qin
  • Changqiu Wang
Article

Abstract

As a common mineral phase on Earth and Martian regolith, natural rutile was reported as a potential candidate for use as a Fenton catalyst in this study. The influences of Fe and V in various chemical states on the generation of reactive oxygen species (ROSs) and the catalytic activity of rutile were examined. A series of rutile samples with various surface and bulk states of Fe and V were obtained initially by hydrogen annealing of natural rutile at ~773–1173 K. X-ray diffraction, electron paramagnetic resonance spectra, and X-ray photoelectron spectroscopy demonstrated that the atomic fractions of Fe(III) and V(V) decreased sharply with increasing temperature, along with the accumulation of surface Fe(II) and bulk V(III). All as-prepared materials showed enhanced Fenton degradation efficiency on methylene blue (MB) compared with P25-TiO2, and the treated samples exhibited up to 3.5-fold improvement in efficiency at pH 3 compared to the untreated sample. The improved efficiency was attributed mainly to Fenton catalysis involving Fe(II) and V(III). The dissolved Fe2+ played a crucial role in the homogeneous Fenton reaction, while the bound V(III) favored adsorption primarily and may have facilitated heterogeneous Fenton reaction and the regeneration of Fe2+. The pH regulated the reaction mechanism among homogeneous (pH = 3) and heterogeneous (pH = 3.7) Fenton catalysis and physical adsorption (pH = 5, 6). The aim of the present study was to improve the understanding of the potential role of natural rutile with advanced oxidation functions in Earth systems and even on Mars, which also provide an inspiration for screening natural rutile and any other similar, Earth-abundant, low-cost minerals for environmental application.

Key Words

Fe and V co-doping Fenton reaction Heterogeneous catalysis Homogeneous catalysis Hydrogen annealing Natural rutile 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Allen, B.L. and Hajek, B.F. (1989) Mineral occurrence in soil environments. Mammal Review, 28, 1–52.Google Scholar
  2. Amorelli, A., Evans, J.C., Rowlands, C.C., and Egerton, T.A. (1987) An electron spin resonance study of rutile and anatase titanium dioxide polycrystalline powders treated with transition-metal ions. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 83, 3541–3548.Google Scholar
  3. Baird, A.K., Clark, B.C., Jr, R.H., Keil, K., Christian, R.P., and Gooding, J.L. (1976) Mineralogic and petrologic implications of Viking geochemical results from Mars: interim report. Science, 194, 1288–1293.CrossRefGoogle Scholar
  4. Bhattacharyya, K., Varma, S., Tripathi, A.K., Bharadwaj, S.R., and Tyagi, A.K. (2008) Effect of vanadia doping and its oxidation state on the photocatalytic activity of TiO2 for gas-phase oxidation of ethene. The Journal of Physical Chemistry C, 112, 19102–19112.CrossRefGoogle Scholar
  5. Bossmann, S.H., Oliveros, E., Göb, S., Siegwart, S., Dahlen, E.P., Payawan, L., Straub, J.M., Wörner, M., and Braun, A.M. (1998) New evidence against hydroxyl radicals as reactive intermediates in the thermal and photochemically enhanced Fenton reactions. The Journal of Physical Chemistry A, 102, 5542–5550.CrossRefGoogle Scholar
  6. Brückner, A. (2006) Spin-spin exchange in vanadiumcontaining catalysts studied by in situ EPR: a sensitive monitor for disorder-related activity. Topics in Catalysis, 38, 133–139.Google Scholar
  7. Bullock, M.A., Stoker, C.R., Mckay, C.P., and Zent, A.P. (1994) A coupled soil-atmosphere model of H2O2 on Mars. Icarus, 107, 142–154.CrossRefGoogle Scholar
  8. Cavani, F., Centi, G., Foresti, E., and Trifir, F. (1988) Surface structure and reactivity of vanadium oxide supported on titanium dioxide. V2O5/TiO2 (rutile) catalysts prepared by hydrolysis. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 84, 237–254.Google Scholar
  9. Chakradhar, R.P.S., Yasoda, B., Rao, J.L., and Gopal, N.O. (2006) Mixed alkali effect in Li2O-Na2O-B2O3, glasses containing Fe2O3 — an EPR and optical absorption study. Materials Research Bulletin, 41, 1646–1656.CrossRefGoogle Scholar
  10. Chou, S., Huang, C., and Huang, Y.H. (2001) Heterogeneous and homogeneous catalytic oxidation by supported γ-FeOOH in a fluidized-bed reactor: kinetic approach. Environmental Science & Technology, 35, 1247–1251.CrossRefGoogle Scholar
  11. Chuan, X.Y., Lu, A.H., Chen, J., Li, N., and Guo, Y.J. (2008) Microstructure and photocatalytic activity of natural rutile from China for oxidation of methylene blue in water. Mineralogy and Petrology, 93, 143–152.CrossRefGoogle Scholar
  12. Clancy, R.T., Sandor, B.J., and Moriarty-Schieven, G.H. (2004) A measurement of the 362 GHz absorption line of Mars atmospheric H2O2. Icarus, 168, 116–121.CrossRefGoogle Scholar
  13. Dolcater, D.L., Syers, J.K., and Jackson, M.L. (1970) Titanium as free oxide and substituted forms in kaolinites and other soil minerals. Clays and Clay Minerals, 18, 71–79.CrossRefGoogle Scholar
  14. Dong, Y., Chen, S., Zhang, X., Yang, J., Liu, X., and Meng, G. (2006) Fabrication and characterization of low cost tubular mineral-based ceramic membranes for micro-filtration from natural zeolite. Journal of Membrane Science, 281, 592–599.CrossRefGoogle Scholar
  15. Egerton, T.A., Harris, E., John Lawson, E., Mile, B., and Rowlands, C.C. (2001) An EPR study of diffusion of iron into rutile. Physical Chemistry Chemical Physics, 3, 497–504.CrossRefGoogle Scholar
  16. Encrenaz, T., Bezard, B., Greathouse, T.K., Richter, M.J., Lacy, J.H., Atreya, S.K., Wong, A.S., Lebonnois, S., Lefevre, F., and Forget, F. (2004) Hydrogen peroxide on Mars: evidence for spatial and seasonal variations. Icarus, 170, 424–429.CrossRefGoogle Scholar
  17. Fiedor, J.N., Bostick, W.D., Jarabek, R.J., and Farrell, J. (1998) Understanding the mechanism of uranium removal from groundwater by zero-valent iron using X-ray photoelectron spectroscopy. Environmental Science & Technology, 32, 1466–1473.CrossRefGoogle Scholar
  18. Fujii, T., De Groot, F.M.F., Sawatzky, G.A., Voogt, F.C., Hibma, T., and Okada, K. (1999) In situ XPS analysis of various iron oxide films grown by NO2-assisted molecularbeam epitaxy. Physical Review B, 59, 3195–3202.CrossRefGoogle Scholar
  19. Gallay, R., Van der Klink, J.J., and Moser, J. (1986) EPR study of vanadium (4+) in the anatase and rutile phases of TiO2. Physical Review B, 34, 3060–3068.CrossRefGoogle Scholar
  20. Geng, B., Jin, Z., Li, T., and Qi, X. (2009) Preparation of chitosan-stabilized Fe(0) nanoparticles for removal of hexavalent chromium in water. Science of the Total Environment, 407, 4994–5000.CrossRefGoogle Scholar
  21. Gómez-Hortigüela, L., Pinar, A.B., Pérez-Pariente, J., Sani, T., Chebude, Y., and Díaz, I. (2014) Ion-exchange in natural zeolite stilbite and significance in defluoridation ability. Microporous and Mesoporous Materials, 193, 93–102.CrossRefGoogle Scholar
  22. Gopal, N.O., Narasimhulu, K.V., and Rao, J.L. (2004) EPR, optical, infrared and Raman spectral studies of actinolite mineral. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 60, 2441–2448.CrossRefGoogle Scholar
  23. Griffin, R.A., Au, A., and Frost, R.R. (1977) Effect of pH on adsorption of chromium from landfill leachate by clay minerals. Journal of Environmental Science & Health Part A - Environmental Science & Engineering, 12, 431–449.CrossRefGoogle Scholar
  24. Gülay, A., Tatari, K., Musovic, S., Mateiu, R.V., Albrechtsen, H.J., and Smets, B.F. (2014) Internal porosity of mineral coating supports microbial activity in rapid sand filters for groundwater treatment. Applied and Environmental Microbiology, 80, 7010–7020.CrossRefGoogle Scholar
  25. Hazen, R.M., Papineau, D., Leeker, W.B., Downs, R.T., Ferry, J.M., McCoy, T.J., Sverjensky, D.A., and Yang, H.X. (2008) Mineral evolution. American Mineralogist, 93, 1693–1720.CrossRefGoogle Scholar
  26. Jackson, M.L., Tyler, S.A., Willis, A.L., Bourbeau, G.A., and Pennington, R.P. (1948) Weathering sequence of clay-size minerals in soils and sediments. I. Fundamental generalizations. The Journal of Physical Chemistry, 52, 1237–1260.Google Scholar
  27. Karner, J.M., Sutton, S.R., Papike, J.J., Shearer, C.K., Jones, J.H., and Newville, M. (2006) Application of a new vanadium valence oxybarometer to basaltic glasses from the Earth, Moon, and Mars. American Mineralogist, 91, 270–277.CrossRefGoogle Scholar
  28. Kera, Y. and Matsukaze, Y. (1986) Dynamical change in the crystal field around the V (IV) ion on titanium dioxide (rutile) surface accompanied by the interaction with adsorbed oxygen molecules. The Journal of Physical Chemistry, 90, 5752–5755.CrossRefGoogle Scholar
  29. Klosek, S. and Raftery, D. (2001) Visible light driven V-doped TiO2 photocatalyst and its photooxidation of ethanol. The Journal of Physical Chemistry B, 105, 2815–2819.CrossRefGoogle Scholar
  30. Knapp, M.J., Krzystek, J., Brunel, L.C., and Hendrickson, D.N. (2000) High-frequency EPR study of the ferrous ion in the reduced rubredoxin model [Fe(SPh)4]2. Inorganic Chemistry, 39, 281–288.CrossRefGoogle Scholar
  31. Kremer, M.L. (2008) Kinetics of aerobic and anaerobic oxidations of ethanol by Fenton’s reagent. International Journal of Chemical Kinetics, 40, 541–553.CrossRefGoogle Scholar
  32. Laiju, A.R., Sivasankar, T., and Nidheesh, P.V. (2014) Ironloaded mangosteen as a heterogeneous Fenton catalyst for the treatment of landfill leachate. Environmental Science and Pollution Research, 21, 10900–10907.CrossRefGoogle Scholar
  33. Lasne, J., Noblet, A., Szopa, C., Navarro-González, R., Cabane, M., Poch, O., Stalport, F., François, P., Atreya, S.K., and Coll, P. (2016) Oxidants at the surface of Mars: a review in light of recent exploration results. Astrobiology, 16, 977.CrossRefGoogle Scholar
  34. Li, Y., Li, Y., Yin, Y., Xia, D., Ding, H., Ding, C., Wu, J., Yan, Y., Liu, Y., Chen, N., Wong, P.K., and Lu, A. (2018) Facile synthesis of highly efficient ZnO/ZnFe2O4 photocatalyst using earth-abundant sphalerite and its visible light photocatalytic activity. Applied Catalysis B: Environmental, 226, 324–336.CrossRefGoogle Scholar
  35. Liang, X., Zhu, S., Zhong, Y., Zhu, J., Yuan, P., He, H., and Zhang, J. (2010a) The remarkable effect of vanadium doping on the adsorption and catalytic activity of magnetite in the decolorization of methylene blue. Applied Catalysis B Environmental, 97, 151–159.CrossRefGoogle Scholar
  36. Liang, X., Zhong, Y., Zhu, S., Zhu, J., Yuan, P., He, H., and Zhang, J. (2010b) The decolorization of Acid Orange II in non-homogeneous Fenton reaction catalyzed by natural vanadium-titanium magnetite. Journal of Hazardous Materials, 181, 112–120.CrossRefGoogle Scholar
  37. Liang, X., He, Z., Zhong, Y., Tan, W., He, H., Yuan, P., Zhu, J., and Zhang, J. (2013) The effect of transition metal substitution on the catalytic activity of magnetite in heterogeneous Fenton reaction: in interfacial view. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 435, 28–35.CrossRefGoogle Scholar
  38. Lu, A., Liu, J., Zhao, D., Guo, Y., Li, Q., and Li, N. (2004) Photocatalysis of V-bearing rutile on degradation of halohydrocarbons. Catalysis Today, 90, 337–342.Google Scholar
  39. Lu, A., Li, Y., Lv, M., Wang, C., Yang, L., Liu, J., Wang Y., Wong, K.H., and Wong, P.K. (2007) Photocatalytic oxidation of methyl orange by natural V-bearing rutile under visible light. Solar Energy Materials & Solar Cells, 91, 1849–1855.CrossRefGoogle Scholar
  40. Lu, A., Li, Y., Jin, S., Wang, X., Wu, X.L., Zeng, C., Li, Y, Ding, H., Hao, R., Lv, M., Wang, C., Tang, Y., and Dong, H. (2012) Growth of non-phototrophic microorganisms using solar energy through mineral photocatalysis. Nature Communications, 3, 768.CrossRefGoogle Scholar
  41. Luo, Z., Lu, A., Li, Y., Zhuang, W., Wu, J., Qin, S., and Wang, C. (2012) Enhanced visible-light response of natural Vbearing rutile by annealing under argon. European Journal of Mineralogy, 24, 551–557.CrossRefGoogle Scholar
  42. Matta, R., Hanna, K., Kone, T., and Chiron, S. (2008) Oxidation of 2,4,6-trinitrotoluene in the presence of different iron-bearing minerals at neutral pH. Chemical Engineering Journal, 144, 453–458.CrossRefGoogle Scholar
  43. Mehmood, A., Akhtar, M.S., Deng, Y., Dixon, J.B., Imran, M., and Rukh, S. (2015) Iron oxide minerals in soils derived from different parent materials. International Journal of Plant and Soil Science, 5, 110–116.CrossRefGoogle Scholar
  44. Ming, D.W., Gellert, R., Morris, R.V., Arvidson, R.E., Brückner, J., Clark, B.C., Cohen, B.A., d’Uston, C., Economou, T., Fleischer, I., Klingelhöfer, G., McCoy, T.J., Mittlefehldt, D.W., Schmidt, M.E., Schröder, C., Squyres, S.W., Tréguier, E., Yen, A.S., and Zipfel, J. (2008) Geochemical properties of rocks and soils in Gusev Crater, Mars: results of the Alpha Particle X-ray spectrometer from Cumberland Ridge to Home Plate. Journal of Geophysical Research, 113, E12S39.Google Scholar
  45. Occhiuzzi, M., Cordischi, D., and Dragone, R. (2003) Manganese ions in the monoclinic, tetragonal and cubic phases of zirconia: an XRD and EPR study. Physical Chemistry Chemical Physics, 5, 4938–4945.CrossRefGoogle Scholar
  46. Papike, J.J., Karner, J.M., and Shearer, C.K. (2005) Comparative planetary mineralogy: Valence state partitioning of Cr, Fe, Ti, and V among crystallographic sites in olivine, pyroxene, and spinel from planetary basalts. 36th Annual Lunar and Planetary Science Conference (Vol. 36). 36th Annual Lunar and Planetary Science Conference.Google Scholar
  47. Pecchi, G., Reyes, P., Lopez, T., Gomez, R., Moreno, A., Fierro, J.L.G., and Martínez-Arias, A. (2003) Catalytic combustion of methane on Fe-TiO2 catalysts prepared by sol-gel method. Journal of Sol-Gel Science and Technology, 27, 205–214.CrossRefGoogle Scholar
  48. Pereira, M.C., Oliveira, L.C.A., and Murad, E. (2012) Iron oxide catalysts: Fenton and Fenton-like reactions — a review. Clay Minerals, 47, 285–302.CrossRefGoogle Scholar
  49. Pignatello, J.J., Oliveros, E., and MacKay, A. (2006) Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry. Critical Reviews in Environmental Science and Technology, 36, 1–84.CrossRefGoogle Scholar
  50. Rieder, R., Economou, T., Wanke, H., Turkevich, A., Crisp, J., Bruckner, J., Dreibus, G., and McSween, H.Y. (1997) The chemical composition of Martian soil and rocks returned by the mobile alpha proton X-ray spectrometer: preliminary results from the X-ray mode. Science, 278, 1771–1774.CrossRefGoogle Scholar
  51. Rodella, C.B., Franco, R.W., Magon, C.J., Donoso, J.P., Nunes, L.A., Saeki, M.J., Aegerter, M.A., Sargentelli, A., and Florentino, A.O. (2002) V2O5/TiO2 catalytic xerogels Raman and EPR studies. Journal of Sol-Gel Science and Technology, 25, 83–88.CrossRefGoogle Scholar
  52. Sawatzky, G.A. and Post, D. (1979) X-ray photoelectron and Auger spectroscopy study of some vanadium oxides. Physical Review B, 20, 1546.CrossRefGoogle Scholar
  53. Sayin, M. (1975) Anatase and rutile determination in kaolinite deposits. Clays and Clay Minerals, 23, 437–443.CrossRefGoogle Scholar
  54. Seki, M., Akther Hossain, A.K.M., Kawai, T., and Tabata, H. (2005) High-temperature cluster glass state and photomagnetism in Zn- and Ti-substituted NiFe2O4 films. Journal of Applied Physics, 97, 516.CrossRefGoogle Scholar
  55. Shi, L., Dong, H., Reguera, G., Beyenal, H., Lu, A., Liu, J., Yu, H.Q., and Fredrickson, J.K. (2016) Extracellular electron transfer mechanisms between microorganisms and minerals. Nature Reviews Microbiology, 14, 651–662.CrossRefGoogle Scholar
  56. Shimizu, A., Tokumura, M., Nakajima, K., and Kawase, Y. (2012) Phenol removal using zero-valent iron powder in the presence of dissolved oxygen: roles of decomposition by the Fenton reaction and adsorption/precipitation. Journal of Hazardous Materials, 201, 60–67.CrossRefGoogle Scholar
  57. Soria, J., Conesa, J.C., Augugliaro, V., Palmisano, L., Schiavello, M., and Sclafani, A. (1991) Dinitrogen photoreduction to ammonia over titanium dioxide powders doped with ferric ions. Cheminform, 22, 274–282.Google Scholar
  58. Suzuki, Y. and Pavasupree, S. (2005) Natural rutile-derived titanate nanofibers prepared by direct hydrothermal processing. Journal of Materials Research, 20, 1063–1070.CrossRefGoogle Scholar
  59. Tekbaş, M., Yatmaz, H.C., and Bektaş, N. (2008) Heterogeneous photo-Fenton oxidation of reactive azo dye solutions using iron-exchanged zeolite as a catalyst. Microporous and Mesoporous Materials, 115, 594–602.CrossRefGoogle Scholar
  60. Trifir, F. (1998) The chemistry of oxidation catalysts based on mixed oxides. Catalysis Today, 41, 21–35.CrossRefGoogle Scholar
  61. Thorp, J.S. and Eggleston, H.S. (1985) Rhombic symmetry sites in Fe/TiO2 powders. Journal of Materials Science Letters, 4, 1140–1142.CrossRefGoogle Scholar
  62. Tian, B., Li, C., Gu, F., Jiang, H., Hu, Y., and Zhang, J. (2009) Flame sprayed V-doped TiO2 nanoparticles with enhanced photocatalytic activity under visible light irradiation. Chemical Engineering Journal, 151, 220–227.CrossRefGoogle Scholar
  63. Uddin, M.K. (2017) A review on the adsorption of heavy metals by clay minerals, with special focus on the past decade. Chemical Engineering Journal, 308, 438–462.CrossRefGoogle Scholar
  64. Wagner, C.D. (1979) Handbook of X-ray photoelectron spectroscopy. Perkin-Elmer.Google Scholar
  65. Wagner, C.D. (1983) Sensitivity factors for XPS analysis of surface atoms. Journal of Electron Spectroscopy and Related Phenomena, 32, 99–102.CrossRefGoogle Scholar
  66. Wang, C., Hong, H., Li, Z., Yin, K., Xie, J., Liang, G., Song, B., Song, E., and Zhang, K. (2013) The Eocene-Oligocene climate transition in the Tarim Basin, northwest China: evidence from clay mineralogy. Applied Clay Science, 74, 10–19.CrossRefGoogle Scholar
  67. Wang, S. (2008) A comparative study of Fenton and Fentonlike reaction kinetics in decolourisation of wastewater. Dyes and Pigments, 76, 714–720.CrossRefGoogle Scholar
  68. Xia, D., Ng, T.W., An, T., Li, G., Li, Y., Yip, H.Y., Zhao, J., Lu, A., and Wong, P.K. (2013) A recyclable mineral catalyst for visible-light-driven photocatalytic inactivation of bacteria: natural magnetic sphalerite. Environmental Science & Technology, 47, 11166–11173.CrossRefGoogle Scholar
  69. Xia, D., Yin, R., Sun, J., An, T., Li, G., Wang, W., Zhao, H., and Wong, P.K. (2017) Natural magnetic pyrrhotite as a high-efficient persulfate activator for micropollutants degradation: Radicals identification and toxicity evaluation. Journal of Hazardous Materials, 340, 435–444.CrossRefGoogle Scholar
  70. Yamashita, T. and Hayes, P. (2008) Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Applied Surface Science, 254, 2441–2449.CrossRefGoogle Scholar
  71. Zent, A.P. (1998) On the thickness of the oxidized layer of the Martian regolith. Journal of Geophysical Research Planets, 103, 31491–31498.CrossRefGoogle Scholar
  72. Zent, A.P., Ichimura, A.S., Quinn, R.C., and Harding, H.K. (2008) The formation and stability of the superoxide radical (O2-) on rock-forming minerals: band gaps, hydroxylation state, and implications for mars oxidant chemistry. Journal of Geophysical Research Planets, 113, 102–110.Google Scholar

Copyright information

© Clay Minerals Society 2018

Authors and Affiliations

  • Yanzhang Li
    • 1
  • Zemin Luo
    • 1
    • 2
  • Yan Li
    • 1
    Email author
  • Feifei Liu
    • 1
  • Anhuai Lu
    • 1
  • Jing Wu
    • 1
  • Shan Qin
    • 1
  • Changqiu Wang
    • 1
  1. 1.The Key Laboratory of Orogenic Belts and Crustal Evolution, Beijing Key Laboratory of Mineral Environmental FunctionSchool of Earth and Space Sciences, Peking UniversityBeijingPR China
  2. 2.Center for Innovative Gem Testing Technology, Gemological InstituteChina University of GeosciencesWuhanPR China

Personalised recommendations