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Comparison of isoelectric points of single-crystal and polycrystalline α-Al2O3 and α-Fe2O3 surfaces

  • Yingge Wang , Per Persson , F. Marc Michel and Gorden E. Brown EMAIL logo
Published/Copyright: September 30, 2016
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American Mineralogist
From the journal American Mineralogist Volume 101 Issue 10

Abstract

The surface charging behavior as a function of pH and isoelectric points (IEPs) of single-crystal α-Al2O3 (0001) and (1102) and α-Fe2O3 (0001) was determined by streaming potential measurements using an electrokinetic analyzer. The IEPs of α-Al2O3 (0001) and (11¯02) and α-Fe2O3 (0001) were found to be 4.5, 5.1, and 6.5, respectively. These IEP values for oriented single crystals of α-Al2O3 are in good agreement with literature values, whereas the new IEP value for α-Fe2O3 (0001) is significantly lower than four reported values (IEP = 8–8.5) for single-crystal α-Fe2O3 (0001) (Eggleston and Jordan 1998; Zarzycki et al. 2011; Chatman et al. 2013; Lützenkirchen et al. 2013) and significantly higher than one (IEP = 4) recently measured by Lützenkirchen et al. (2015) on a fresh α-Fe2O3 (0001) surface. Most of the single-crystal IEP values measured recently are lower than IEP values reported for polycrystalline α-Al2O3 and α-Fe2O3, which are generally in the pH range of 8 to 10. Calculations of the IEP values based on estimated Ka values of α-Fe2O3 and α-Al2O3 surfaces in contact with water as a function of defect type and concentration suggest that highly reactive surface defect sites (primarily singly coordinated aquo groups) on the Fe- and Al-oxide powders are possibly a major source of the surface charge differences between polycrystalline samples and their oriented single-crystal counterparts studied here. The results of this study provide a better understanding of the surface charging behavior of Fe and Al-oxides, which is essential for predicting complex processes such as metal-ion sorption occurring at mineral/water interfaces.

Keywords: Isoelectric point (IEP); pH point of zero charge (pHPZC); Fe- and Al-oxides; single crystal; polycrystalline; surface; defects
Present address: Department of Geosciences, Virginia Tech, Blacksburg, Virginia 24061, U.S.A.

Acknowledgments

Financial support for this project was provided by NSF Grant CHE-0431425 (Stanford Environmental Molecular Science Institute) and by the NSF-Center for Environmental Implications for Nanotechnology (based at Duke University) (NSF Cooperative Agreement EF-0830093). One of us (P.P.) acknowledges financial support from the Swedish Research Council, the Wenner-Gren Foundations and the Blaustein Visiting Professorship Fund of the School of Earth, Energy, and Environmental Sciences, Stanford University. We thank Federico Pacheco and Sophie Walewijk for their help with steaming potential measurements. Stefan Sjoberg (Department of Chemistry, Umeâ University, Sweden), Piotr Zarzycki (Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland), and an anonymous referee are also thanked for their helpful comments, which improved the manuscript. Last, G.E.B. thanks his former Stanford colleague George A. Parks for many stimulating discussions about IEP values of metal oxides over the 25 years we overlapped at Stanford University and worked together on many research projects on interface chemistry and geochemistry. This paper is dedicated to the memory of George A. Parks, who passed away on July 15, 2016.

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Received: 2015-8-13
Accepted: 2016-5-23
Published Online: 2016-9-30
Published in Print: 2016-10-1

© 2016 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2016-5531
Keywords for this article
Isoelectric point (IEP); pH point of zero charge (pHPZC); Fe- and Al-oxides; single crystal; polycrystalline; surface; defects

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  14. Error sources in single-clinopyroxene thermobarometry and a mantle geotherm for the Novinka kimberlite, Yakutia
  15. Water in nominally hydrous and anhydrous minerals
  16. Experimental hydration of natural volcanic clinopyroxene phenocrysts under hydrothermal pressures (0.5–3 kbar)
  17. Research Article
  18. Comparison of isoelectric points of single-crystal and polycrystalline α-Al2O3 and α-Fe2O3 surfaces
  19. Research Article
  20. Synthetic olivine capsules for use in experiments
  21. Research Article
  22. Visible and short-wave infrared reflectance spectroscopy of REE phosphate minerals
  23. Research Article
  24. Protolith carbon isotope ratios in cordierite from metamorphic and igneous rocks
  25. Research Article
  26. Empirical electronic polarizabilities of ions for the prediction and interpretation of refractive indices: Oxides and oxysalts
  27. Research Article
  28. A novel protocol for resolving feldspar crystals in synchrotron X-ray microtomographic images of crystallized natural magmas and synthetic analogs
  29. Research Article
  30. Silicic lunar volcanism: Testing the crustal melting model
  31. Research Article
  32. Transition metals in the transition zone: Crystal chemistry of minor element substitution in wadsleyite
  33. Research Article
  34. Experimental evidence of the formation of intermediate phases during transition of kaolinite into metakaolinite
  35. Letter
  36. Further observations related to a possible occurrence of terrestrial ahrensite
  37. Letter
  38. Chemical zoning and lattice distortion in uraninite from Olympic Dam, South Australia
  39. Research Article
  40. New Mineral Names
  41. Book Review
  42. Book review: Layered Intrusions
  43. Book Review
  44. Book Review: Mineral Resources, Economics and the Environment, 2nd edition
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