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Title: Evolution in the structure of akaganeite and hematite during hydrothermal growth: an in situ synchrotron X-ray diffraction analysis

Abstract

Synchrotron X-ray diffraction was used to monitor the hydrothermal precipitation of akaganeite ( β-FeOOH) and its transformation to hematite (Fe 2O 3) in situ. Akaganeite was the first phase to form and hematite was the final phase in our experiments with temperatures between 150 and 200 °C. Akaganeite was the only phase that formed at 100 °C. Rietveld analyses revealed that the akaganeite unit-cell volume contracted until the onset of dissolution, and subsequently expanded. This reversal at the onset of dissolution was associated with a substantial and rapid increase in occupancy of the Cl site, perhaps by OH -or Fe 3+. Rietveld analyses supported the incipient formation of an OH-rich, Fe-deficient hematite phase in experiments between 150 and 200 °C. The inferred H concentrations of the first crystals were consistent with “hydrohematite.” With continued crystal growth, the Fe occupancies increased. Contraction in both a- and c-axes signaled the loss of hydroxyl groups and formation of a nearly stoichiometric hematite.

Authors:
; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - OTHERNSF
OSTI Identifier:
1483872
Resource Type:
Journal Article
Journal Name:
Powder Diffraction
Additional Journal Information:
Journal Volume: 33; Journal Issue: 4; Journal ID: ISSN 0885-7156
Publisher:
Cambridge University Press
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Peterson, Kristina M., Heaney, Peter J., and Post, Jeffrey E. Evolution in the structure of akaganeite and hematite during hydrothermal growth: an in situ synchrotron X-ray diffraction analysis. United States: N. p., 2018. Web. doi:10.1017/S0885715618000623.
Peterson, Kristina M., Heaney, Peter J., & Post, Jeffrey E. Evolution in the structure of akaganeite and hematite during hydrothermal growth: an in situ synchrotron X-ray diffraction analysis. United States. doi:10.1017/S0885715618000623.
Peterson, Kristina M., Heaney, Peter J., and Post, Jeffrey E. Mon . "Evolution in the structure of akaganeite and hematite during hydrothermal growth: an in situ synchrotron X-ray diffraction analysis". United States. doi:10.1017/S0885715618000623.
@article{osti_1483872,
title = {Evolution in the structure of akaganeite and hematite during hydrothermal growth: an in situ synchrotron X-ray diffraction analysis},
author = {Peterson, Kristina M. and Heaney, Peter J. and Post, Jeffrey E.},
abstractNote = {Synchrotron X-ray diffraction was used to monitor the hydrothermal precipitation of akaganeite (β-FeOOH) and its transformation to hematite (Fe2O3)in situ. Akaganeite was the first phase to form and hematite was the final phase in our experiments with temperatures between 150 and 200 °C. Akaganeite was the only phase that formed at 100 °C. Rietveld analyses revealed that the akaganeite unit-cell volume contracted until the onset of dissolution, and subsequently expanded. This reversal at the onset of dissolution was associated with a substantial and rapid increase in occupancy of the Cl site, perhaps by OH-or Fe3+. Rietveld analyses supported the incipient formation of an OH-rich, Fe-deficient hematite phase in experiments between 150 and 200 °C. The inferred H concentrations of the first crystals were consistent with “hydrohematite.” With continued crystal growth, the Fe occupancies increased. Contraction in both a- and c-axes signaled the loss of hydroxyl groups and formation of a nearly stoichiometric hematite.},
doi = {10.1017/S0885715618000623},
journal = {Powder Diffraction},
issn = {0885-7156},
number = 4,
volume = 33,
place = {United States},
year = {2018},
month = {9}
}

Works referenced in this record:

Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries
journal, March 2013

  • Reddy, M. V.; Subba Rao, G. V.; Chowdari, B. V. R.
  • Chemical Reviews, Vol. 113, Issue 7
  • DOI: 10.1021/cr3001884

Inner structure and properties of diamond-shaped and spherical ?-Fe2O3 particles
journal, July 1994

  • Kandori, K.; Tamura, S.; Ishikawa, T.
  • Colloid & Polymer Science, Vol. 272, Issue 7
  • DOI: 10.1007/BF00652422

A study of the non-stoichiometrical halogen and water content of β-FeOOH
journal, May 1984


Buried iron archaeological artefacts: Corrosion mechanisms related to the presence of Cl-containing phases
journal, June 2007


Interaction of inorganic anions with iron-mineral adsorbents in aqueous media — A review
journal, January 2014

  • Kumar, Eva; Bhatnagar, Amit; Hogland, William
  • Advances in Colloid and Interface Science, Vol. 203
  • DOI: 10.1016/j.cis.2013.10.026

CO 2 Sequestration through Mineral Carbonation of Iron Oxyhydroxides
journal, December 2011

  • Lammers, Kristin; Murphy, Riley; Riendeau, Amber
  • Environmental Science & Technology, Vol. 45, Issue 24
  • DOI: 10.1021/es202571k

Rational screening low-cost counter electrodes for dye-sensitized solar cells
journal, March 2013

  • Hou, Yu; Wang, Dong; Yang, Xiao Hua
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2547

Nanostructured hematite: synthesis, characterization, charge carrier dynamics, and photoelectrochemical properties
journal, January 2012

  • Wheeler, Damon A.; Wang, Gongming; Ling, Yichuan
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee00001f

Formation of monodispersed colloidal cubic haematite particles in ethanol + water solutions
journal, January 1982

  • Hamada, Shuichi; Matijević, Egon
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 78, Issue 7
  • DOI: 10.1039/f19827802147

Mineralogy of a Mudstone at Yellowknife Bay, Gale Crater, Mars
journal, December 2013


A Habitable Fluvio-Lacustrine Environment at Yellowknife Bay, Gale Crater, Mars
journal, December 2013


Neutron and temperature-resolved synchrotron X-ray powder diffraction study of akaganéite
journal, May 2003

  • Post, Jeffrey E.; Heaney, Peter J.; Von Dreele, Robert B.
  • American Mineralogist, Vol. 88, Issue 5-6
  • DOI: 10.2138/am-2003-5-607

Volatile and Organic Compositions of Sedimentary Rocks in Yellowknife Bay, Gale Crater, Mars
journal, December 2013


Investigation of the structure of protohematite — metastable phase of ferrum (III) oxide
journal, September 2000

  • Burgina, E. B.; Kustova, G. N.; Isupova, L. A.
  • Journal of Molecular Catalysis A: Chemical, Vol. 158, Issue 1
  • DOI: 10.1016/S1381-1169(00)00086-8

Elemental Geochemistry of Sedimentary Rocks at Yellowknife Bay, Gale Crater, Mars
journal, December 2013


A kinetic analysis of the transformation from akaganeite to hematite: An in situ time-resolved X-ray diffraction study
journal, December 2016


In situ study of the goethite-hematite phase transformation by real time synchrotron powder diffraction
journal, June 1999

  • Gualtieri, Alessandro F.; Venturelli, Paolo
  • American Mineralogist, Vol. 84, Issue 5-6
  • DOI: 10.2138/am-1999-5-624

Rietveld refinement of Debye–Scherrer synchrotron X-ray data from Al 2 O 3
journal, April 1987

  • Thompson, P.; Cox, D. E.; Hastings, J. B.
  • Journal of Applied Crystallography, Vol. 20, Issue 2
  • DOI: 10.1107/S0021889887087090

Artificial weathering of the ordinary chondrite Allegan; implications for the presence of Cl (super -) as a structural component in akaganeite
journal, December 1997

  • Bland, P. A.; Kelley, S. P.; Berry, F. J.
  • American Mineralogist, Vol. 82, Issue 11-12
  • DOI: 10.2138/am-1997-11-1215

Saltonseaite, K3NaMn2+Cl6, the Mn analogue of rinneite from the Salton Sea, California
journal, December 2012

  • Kampf, A. R.; Mills, S. J.; Nestola, F.
  • American Mineralogist, Vol. 98, Issue 1
  • DOI: 10.2138/am.2013.4214

Ferric hydrous oxide sols
journal, March 1978


“In rust we trust”. Hematite – the prospective inorganic backbone for artificial photosynthesis
journal, January 2013

  • Bora, Debajeet K.; Braun, Artur; Constable, Edwin C.
  • Energy Environ. Sci., Vol. 6, Issue 2
  • DOI: 10.1039/C2EE23668K

The Iron Oxides Strike Back: From Biomedical Applications to Energy Storage Devices and Photoelectrochemical Water Splitting
journal, July 2011

  • Tartaj, Pedro; Morales, Maria P.; Gonzalez-Carreño, Teresita
  • Advanced Materials, Vol. 23, Issue 44
  • DOI: 10.1002/adma.201101368

Global Iron Connections Between Desert Dust, Ocean Biogeochemistry, and Climate
journal, April 2005


Role of Chlorine in β-FeOOH on Its Thermal Change and Reactivity to Sulfur Dioxide
journal, May 1975

  • Ishikawa, Tatsuo; Inouye, Katsuya
  • Bulletin of the Chemical Society of Japan, Vol. 48, Issue 5
  • DOI: 10.1246/bcsj.48.1580

x-Ray Studies on the Hydrous Oxides. V. Beta Ferric Oxide Monohydrate
journal, February 1935

  • Weiser, Harry B.; Milligan, W. O.
  • Journal of the American Chemical Society, Vol. 57, Issue 2
  • DOI: 10.1021/ja01305a003

Hydrothermal Treatment of a Hematite Film Leads to Highly Oriented Faceted Nanostructures with Enhanced Photocurrents
journal, April 2011

  • Bora, Debajeet K.; Braun, Artur; Erni, Rolf
  • Chemistry of Materials, Vol. 23, Issue 8
  • DOI: 10.1021/cm102826n

β-FeOOH · Cln (akaganéite) and Fe1-xO (wüstite) in hot brine from the Atlantis II Deep (Red Sea) and the uptake of amino acids by synthetic β-FeOOH · Cln
journal, August 1983


Characterization of oxides of stainless steel UNS S30400 formed in offshore environment
journal, February 2012


Growth Mechanisms of Iron Oxide Particles of Differing Morphologies from the Forced Hydrolysis of Ferric Chloride Solutions
journal, April 1993

  • Bailey, Joseph K.; Brinker, C. Jeffrey; Mecartney, Martha L.
  • Journal of Colloid and Interface Science, Vol. 157, Issue 1
  • DOI: 10.1006/jcis.1993.1150

Akaganéite (β-FeOOH) precipitation in inland acid sulfate soils of south-western New South Wales (NSW), Australia
journal, November 2011

  • Bibi, Irshad; Singh, Balwant; Silvester, Ewen
  • Geochimica et Cosmochimica Acta, Vol. 75, Issue 21
  • DOI: 10.1016/j.gca.2011.08.019

In situ growth of β-FeOOH nanorods on graphene oxide with ultra-high relaxivity for in vivo magnetic resonance imaging and cancer therapy
journal, January 2013

  • Chen, Mei-Ling; Shen, Li-Ming; Chen, Shuai
  • Journal of Materials Chemistry B, Vol. 1, Issue 20
  • DOI: 10.1039/c3tb20234h

Use of Nanoporous FeOOH as a Catalytic Support for NaHCO 3 Decomposition Aimed at Reduction of Energy Requirement of Na 2 CO 3 /NaHCO 3 Based CO 2 Separation Technology
journal, July 2011

  • Dutcher, Bryce; Fan, Maohong; Leonard, Brian
  • The Journal of Physical Chemistry C, Vol. 115, Issue 31
  • DOI: 10.1021/jp204899r

The comparative lithium storage properties of urchin-like hematite spheres: hollow vs. solid
journal, January 2012

  • Wang, Bao; Chen, Jun Song; Lou, Xiong Wen (David)
  • Journal of Materials Chemistry, Vol. 22, Issue 19
  • DOI: 10.1039/c2jm31108a

EXPGUI , a graphical user interface for GSAS
journal, April 2001


Synthesis and Characterization of Monodisperse Iron Oxides Microspheres
journal, August 2008

  • Wang, Debao; Song, Caixia; Zhao, Yihong
  • The Journal of Physical Chemistry C, Vol. 112, Issue 33
  • DOI: 10.1021/jp8031644

Mössbauer Characterization of Rust Obtained in an Accelerated Corrosion Test
journal, January 2003


Precipitation and transformation of secondary Fe oxyhydroxides in a Histosol impacted by runoff from a lead smelter
journal, June 2010


Morphology-controlled synthesis of hematite hierarchical structures and their lithium storage performances
journal, January 2013

  • Ma, Ji; Zhang, Xiaodan; Chen, Kezheng
  • Journal of Materials Chemistry A, Vol. 1, Issue 18
  • DOI: 10.1039/c3ta10396j

β-FeOOH thin film as positive electrode for lithium-ion cells
journal, June 2009


A refined monoclinic structure for a variety of "hydrohematite"
journal, February 2015

  • Peterson, K. M.; Heaney, P. J.; Post, J. E.
  • American Mineralogist, Vol. 100, Issue 2-3
  • DOI: 10.2138/am-2015-4807

Surface reaction of β-FeOOH film negative electrode for lithium-ion cells
journal, June 2009


Ni2+/surfactant-assisted route to porous α-Fe2O3 nanoarchitectures
journal, January 2012


Chemically prepared magnetic nanoparticles
journal, June 2004

  • Willard, M. A.; Kurihara, L. K.; Carpenter, E. E.
  • International Materials Reviews, Vol. 49, Issue 3-4
  • DOI: 10.1179/095066004225021882

Synthesis and Anion Exchange of Tunnel Structure Akaganeite
journal, December 2001

  • Cai, Jun; Liu, Jia; Gao, Zi
  • Chemistry of Materials, Vol. 13, Issue 12
  • DOI: 10.1021/cm010310w

Controllable Fabrication, Growth Mechanisms, and Photocatalytic Properties of Hematite Hollow Spindles
journal, January 2009

  • Li, Xun; Yu, Xin; He, Jinghui
  • The Journal of Physical Chemistry C, Vol. 113, Issue 7
  • DOI: 10.1021/jp8079217

The biogeochemical cycle of iron in the ocean
journal, September 2010

  • Boyd, P. W.; Ellwood, M. J.
  • Nature Geoscience, Vol. 3, Issue 10
  • DOI: 10.1038/ngeo964

Naturally occurring iron oxide nanoparticles: morphology, surface chemistry and environmental stability
journal, January 2013

  • Guo, Haibo; Barnard, Amanda S.
  • J. Mater. Chem. A, Vol. 1, Issue 1
  • DOI: 10.1039/C2TA00523A

Synchrotron X-ray diffraction study of the structure and dehydration behavior of todorokite
journal, January 2003

  • Post, Jeffrey E.; Heaney, Peter J.; Hanson, Jonathan
  • American Mineralogist, Vol. 88, Issue 1
  • DOI: 10.2138/am-2003-0117

The role of Cl− ions in the oxidation of iron artifacts from chlorinated archeological environments
journal, April 1992

  • Refait, Ph.; Ouahman, R.; Forrières, C.
  • Hyperfine Interactions, Vol. 70, Issue 1-4
  • DOI: 10.1007/BF02397496

Expeditious organic-free assembly: morphologically controlled synthesis of iron oxides using microwaves
journal, January 2013


New Generation Adsorbents for Water Treatment
journal, June 2012


Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408

Structure of the metastable modification of iron(III) oxide
journal, May 2000

  • Burgina, E. B.; Kustova, G. N.; Tsybulya, S. V.
  • Journal of Structural Chemistry, Vol. 41, Issue 3
  • DOI: 10.1007/BF02741997