Mn(II) oxidation catalyzed by nanohematite surfaces and manganite/hausmannite core-shell nanowire formation by self-catalytic reaction

Inoué, Sayako; Yasuhara, Akira; Ai, Haruka; Hochella, Jr., Michael F.; Murayama, Mitsuhiro

doi:10.1016/j.gca.2019.05.011

Mn(II) oxidation catalyzed by nanohematite surfaces and manganite/hausmannite core-shell nanowire formation by self-catalytic reaction

Journal Article · Fri May 24 04:00:00 EDT 2019 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2019.05.011· OSTI ID:1843555

^[1]; Yasuhara, Akira ^[2]; Ai, Haruka ^[2]; Hochella, Jr., Michael F. ^[3]; Murayama, Mitsuhiro ^[4]

Virginia Tech National Center for Earth and Environmental Nanotechnology Infrastructure (NanoEarth), Blacksburg, VA (United States); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Virginia Tech
JEOL Ltd., Tokyo (Japan)
Virginia Tech National Center for Earth and Environmental Nanotechnology Infrastructure (NanoEarth), Blacksburg, VA (United States); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Virginia Tech National Center for Earth and Environmental Nanotechnology Infrastructure (NanoEarth), Blacksburg, VA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

The present study investigated the solid products of heterogeneous catalytic oxidation of aqueous Mn(II) by O₂ in the presence of hematite nanoparticles (NPs) using transmission electron microscopy (TEM), scanning TEM (STEM), and electron energy-loss spectroscopy (EELS). The oxidation experiments were conducted at room temperature (22 ± 2 °C) in solutions containing 10^–3 M Mn(II) at pH 7.5 in the dark. During 48 h of reaction, a single-phase manganite (a Mn oxyhydroxide) nanowire was formed by way of metastable groutite and feitknechtite nanowires, both of which are polymorphs of manganite. Between 48 and 168 h, the manganite further altered to core-shell structured nanowires with hausmannite (a mixed valent Mn oxide) forming a very thin (2 nm) outer-shell on the manganite wire core. The formation of Mn-oxyhydroxide nanowires was catalyzed by the hematite NPs surface through electrochemical pathways. This is described via the electron transfer across a redox couple from adsorbed Mn(II) to another site with adsorbed O₂ via the band structure of the semiconducting hematite. On the other hand, the Ostwald step rule was operative in the sequential crystallization from metastable groutite and feitknechtite to stable manganite, which could have resulted from the differences in the surface free energies, sizes, and morphologies of product polymorphs at the nanoscale. The final product (at least in the time range of our experiments) exhibited manganite/hausmannite core-shell structures. Furthermore, this product is most likely to be formed by the reactions catalyzed by the manganite nanowires themselves. Microscopic investigation of interfacial changes in structure and chemistry at the nanoscale is key, and it can be essential to understand the kinetic and thermodynamic phenomena related to the redox chemistry and phase stability of nanoparticles in complex, heterogeneous systems such as natural environments.

View Accepted Manuscript (DOE)

Research Organization:: Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-06ER15786

OSTI ID:: 1843555

Alternate ID(s):: OSTI ID: 1564433
OSTI ID: 1567184

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 258; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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