Cs-exchange in birnessite: Reaction mechanisms inferred from time-resolved x-ray diffraction and transmission electron microscopy

Christina L. Lopano, Peter J. Heaney, Jeffrey E. Post

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

We have explored the exchange of Cs for interlayer Na in birnessite using several techniques, including transmission electron microscopy (TEM) and time-resolved synchrotron X-ray diffraction (XRD). Our goal was to test which of two possible exchange mechanisms is operative during the reaction: (1) diffusion of cations in and out of the interlay er or (2) dissolution of Na-birnessite and reprecipitation of Cs-bimessite. The appearance of distinct XRD peaks for Na- and Cs-rich phases in partially exchanged samples offered support for a simple diffusion model, but it was inconsistent with the compositional and crystallographic homogeneity of (Na, Cs)-bimessite platelets from core to rim as ascertained by TEM. Time-resolved XRD revealed systematic changes in the structure of the emergent Cs-rich birnessite phase during exchange, in conflict with a dissolution and reprecipitation model. Instead, we propose that exchange occurred by sequential delamination of Mn oxide octahedral sheets. Exfoliation of a given interlayer region allowed for wholesale replacement of Na by Cs and was rapidly followed by reassembly. This model accounts for the rapidity of metal exchange in birnessite, the co-existence of distinct Na- and Cs-bimessite phases during the process of exchange, and the uniformly mixed Na- and Cs-compositions ascertained from point analyses by selected area electron diffraction and energy dispersive spectroscopy of partially exchanged grains.

Original languageEnglish (US)
Pages (from-to)816-826
Number of pages11
JournalAmerican Mineralogist
Volume94
Issue number5-6
DOIs
StatePublished - May 1 2009

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birnessite
diffraction
transmission electron microscopy
x ray diffraction
Diffraction
Transmission electron microscopy
X rays
interlayers
X-ray diffraction
dissolving
X ray diffraction
Dissolution
x rays
dissolution
platelets
rims
homogeneity
delamination
synchrotrons
electron diffraction

All Science Journal Classification (ASJC) codes

  • Geophysics
  • Geochemistry and Petrology

Cite this

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title = "Cs-exchange in birnessite: Reaction mechanisms inferred from time-resolved x-ray diffraction and transmission electron microscopy",
abstract = "We have explored the exchange of Cs for interlayer Na in birnessite using several techniques, including transmission electron microscopy (TEM) and time-resolved synchrotron X-ray diffraction (XRD). Our goal was to test which of two possible exchange mechanisms is operative during the reaction: (1) diffusion of cations in and out of the interlay er or (2) dissolution of Na-birnessite and reprecipitation of Cs-bimessite. The appearance of distinct XRD peaks for Na- and Cs-rich phases in partially exchanged samples offered support for a simple diffusion model, but it was inconsistent with the compositional and crystallographic homogeneity of (Na, Cs)-bimessite platelets from core to rim as ascertained by TEM. Time-resolved XRD revealed systematic changes in the structure of the emergent Cs-rich birnessite phase during exchange, in conflict with a dissolution and reprecipitation model. Instead, we propose that exchange occurred by sequential delamination of Mn oxide octahedral sheets. Exfoliation of a given interlayer region allowed for wholesale replacement of Na by Cs and was rapidly followed by reassembly. This model accounts for the rapidity of metal exchange in birnessite, the co-existence of distinct Na- and Cs-bimessite phases during the process of exchange, and the uniformly mixed Na- and Cs-compositions ascertained from point analyses by selected area electron diffraction and energy dispersive spectroscopy of partially exchanged grains.",
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Cs-exchange in birnessite : Reaction mechanisms inferred from time-resolved x-ray diffraction and transmission electron microscopy. / Lopano, Christina L.; Heaney, Peter J.; Post, Jeffrey E.

In: American Mineralogist, Vol. 94, No. 5-6, 01.05.2009, p. 816-826.

Research output: Contribution to journalArticle

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AB - We have explored the exchange of Cs for interlayer Na in birnessite using several techniques, including transmission electron microscopy (TEM) and time-resolved synchrotron X-ray diffraction (XRD). Our goal was to test which of two possible exchange mechanisms is operative during the reaction: (1) diffusion of cations in and out of the interlay er or (2) dissolution of Na-birnessite and reprecipitation of Cs-bimessite. The appearance of distinct XRD peaks for Na- and Cs-rich phases in partially exchanged samples offered support for a simple diffusion model, but it was inconsistent with the compositional and crystallographic homogeneity of (Na, Cs)-bimessite platelets from core to rim as ascertained by TEM. Time-resolved XRD revealed systematic changes in the structure of the emergent Cs-rich birnessite phase during exchange, in conflict with a dissolution and reprecipitation model. Instead, we propose that exchange occurred by sequential delamination of Mn oxide octahedral sheets. Exfoliation of a given interlayer region allowed for wholesale replacement of Na by Cs and was rapidly followed by reassembly. This model accounts for the rapidity of metal exchange in birnessite, the co-existence of distinct Na- and Cs-bimessite phases during the process of exchange, and the uniformly mixed Na- and Cs-compositions ascertained from point analyses by selected area electron diffraction and energy dispersive spectroscopy of partially exchanged grains.

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