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Title: The Role of Bi 3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid

Abstract

Abstract Metal oxo clusters and metal oxides assemble and precipitate from water in processes that depend on pH, temperature, and concentration. Other parameters that influence the structure, composition, and nuclearity of “molecular” and bulk metal oxides are poorly understood, and have thus not been exploited. Herein, we show that Bi 3+ drives the formation of aqueous Fe 3+ clusters, usurping the role of pH. We isolated and structurally characterized a Bi/Fe cluster, Fe 3 BiO 2 (CCl 3 COO) 8 (THF)(H 2 O) 2 , and demonstrated its conversion into an iron Keggin ion capped by six Bi 3+ irons ( Bi 6 Fe 13 ). The reaction pathway was documented by X‐ray scattering and mass spectrometry. Opposing the expected trend, increased cluster nuclearity required a pH decrease instead of a pH increase. We attribute this anomalous behavior of Bi/Fe(aq) solutions to Bi 3+ , which drives hydrolysis and condensation. Likewise, Bi 3+ stabilizes metal oxo clusters and metal oxides in strongly acidic conditions, which is important in applications such as water oxidation for energy storage.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [1]
  1. Department of Chemistry Oregon State University Corvallis OR 97331 USA
  2. Rigaku Oxford Diffraction 9009 New Trails Drive the Woodlands TX 77381 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1434542
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Name: Angewandte Chemie Journal Volume: 130 Journal Issue: 21; Journal ID: ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Sadeghi, Omid, Amiri, Mehran, Reinheimer, Eric W., and Nyman, May. The Role of Bi 3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid. Germany: N. p., 2018. Web. doi:10.1002/ange.201802915.
Sadeghi, Omid, Amiri, Mehran, Reinheimer, Eric W., & Nyman, May. The Role of Bi 3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid. Germany. https://doi.org/10.1002/ange.201802915
Sadeghi, Omid, Amiri, Mehran, Reinheimer, Eric W., and Nyman, May. Wed . "The Role of Bi 3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid". Germany. https://doi.org/10.1002/ange.201802915.
@article{osti_1434542,
title = {The Role of Bi 3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid},
author = {Sadeghi, Omid and Amiri, Mehran and Reinheimer, Eric W. and Nyman, May},
abstractNote = {Abstract Metal oxo clusters and metal oxides assemble and precipitate from water in processes that depend on pH, temperature, and concentration. Other parameters that influence the structure, composition, and nuclearity of “molecular” and bulk metal oxides are poorly understood, and have thus not been exploited. Herein, we show that Bi 3+ drives the formation of aqueous Fe 3+ clusters, usurping the role of pH. We isolated and structurally characterized a Bi/Fe cluster, Fe 3 BiO 2 (CCl 3 COO) 8 (THF)(H 2 O) 2 , and demonstrated its conversion into an iron Keggin ion capped by six Bi 3+ irons ( Bi 6 Fe 13 ). The reaction pathway was documented by X‐ray scattering and mass spectrometry. Opposing the expected trend, increased cluster nuclearity required a pH decrease instead of a pH increase. We attribute this anomalous behavior of Bi/Fe(aq) solutions to Bi 3+ , which drives hydrolysis and condensation. Likewise, Bi 3+ stabilizes metal oxo clusters and metal oxides in strongly acidic conditions, which is important in applications such as water oxidation for energy storage.},
doi = {10.1002/ange.201802915},
journal = {Angewandte Chemie},
number = 21,
volume = 130,
place = {Germany},
year = {2018},
month = {4}
}

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