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

Sadeghi, Omid; Amiri, Mehran; Reinheimer, Eric W.; Nyman, May

doi:10.1002/ange.201802915

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

Journal Article · 25 April 2018 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201802915 · OSTI ID:1434542

^[1]; Amiri, Mehran ^[1]; Reinheimer, Eric W. ^[2];

^[1]

Department of Chemistry Oregon State University Corvallis OR 97331 USA
Rigaku Oxford Diffraction 9009 New Trails Drive the Woodlands TX 77381 USA

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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0010802

OSTI ID:: 1434542

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 21 Vol. 130; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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