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Title: Simple synthetic route to manganese-containing nanowires with the spinel crystal structure

Abstract

This report describes a new route to synthesize single-crystalline manganese-containing spinel nanowires (NWs) by a two-step hydrothermal and solid-state synthesis. Interestingly, a nanowire or nanorod morphology is maintained during conversion from MnO{sub 2}/MnOOH to CuMn{sub 2}O{sub 4}/Mg{sub 2}MnO{sub 4}, despite the massive structural rearrangement this must involve. Linear sweep voltammetry (LSV) curves of the products give preliminary demonstration that CuMn{sub 2}O{sub 4} NWs are catalytically active towards the oxygen evolution reaction (OER) in alkaline solution, exhibiting five times the magnitude of current density found with pure carbon black. - Highlights: • Synthesis of single-crystalline manganese-containing spinel nanowires. • Binary oxide nanowire converted to ternary oxide wire through solid state reaction. • Approach to structure conversion with shape retention could be generally applicable. • Copper and Manganese display multiple oxidation states with potential for catalysis. • CuMn{sub 2}O{sub 4} nanowires show promise as catalysts for the oxygen evolution reaction.

Authors:
; ; ; ; ;
Publication Date:
OSTI Identifier:
22584174
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 240; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; CARBON BLACK; CATALYSTS; CRYSTAL STRUCTURE; CURRENT DENSITY; MANGANESE; MANGANESE OXIDES; MONOCRYSTALS; NANOWIRES; OXIDATION; OXYGEN; OXYGEN ENHANCEMENT RATIO; SOLIDS; SPINELS; SYNTHESIS; VOLTAMETRY

Citation Formats

Yu, Lei, Zhang, Yan, Hudak, Bethany M., Wallace, Damon K., Kim, Doo Young, and Guiton, Beth S. Simple synthetic route to manganese-containing nanowires with the spinel crystal structure. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.05.012.
Yu, Lei, Zhang, Yan, Hudak, Bethany M., Wallace, Damon K., Kim, Doo Young, & Guiton, Beth S. Simple synthetic route to manganese-containing nanowires with the spinel crystal structure. United States. doi:10.1016/J.JSSC.2016.05.012.
Yu, Lei, Zhang, Yan, Hudak, Bethany M., Wallace, Damon K., Kim, Doo Young, and Guiton, Beth S. 2016. "Simple synthetic route to manganese-containing nanowires with the spinel crystal structure". United States. doi:10.1016/J.JSSC.2016.05.012.
@article{osti_22584174,
title = {Simple synthetic route to manganese-containing nanowires with the spinel crystal structure},
author = {Yu, Lei and Zhang, Yan and Hudak, Bethany M. and Wallace, Damon K. and Kim, Doo Young and Guiton, Beth S.},
abstractNote = {This report describes a new route to synthesize single-crystalline manganese-containing spinel nanowires (NWs) by a two-step hydrothermal and solid-state synthesis. Interestingly, a nanowire or nanorod morphology is maintained during conversion from MnO{sub 2}/MnOOH to CuMn{sub 2}O{sub 4}/Mg{sub 2}MnO{sub 4}, despite the massive structural rearrangement this must involve. Linear sweep voltammetry (LSV) curves of the products give preliminary demonstration that CuMn{sub 2}O{sub 4} NWs are catalytically active towards the oxygen evolution reaction (OER) in alkaline solution, exhibiting five times the magnitude of current density found with pure carbon black. - Highlights: • Synthesis of single-crystalline manganese-containing spinel nanowires. • Binary oxide nanowire converted to ternary oxide wire through solid state reaction. • Approach to structure conversion with shape retention could be generally applicable. • Copper and Manganese display multiple oxidation states with potential for catalysis. • CuMn{sub 2}O{sub 4} nanowires show promise as catalysts for the oxygen evolution reaction.},
doi = {10.1016/J.JSSC.2016.05.012},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 240,
place = {United States},
year = 2016,
month = 8
}
  • The K-birnessite (K{sub x}MnO{sub 2}.yH{sub 2}O) reduction reaction has been tested in order to obtain manganese spinel nanoparticles. The addition of 0.25 weight percent of hydrazine hydrate, the reducing agent, during 24 hours is efficient to transform the birnessite powder in a hausmanite Mn{sub 3}O{sub 4} powder. Well crystallised square shape nanoparticles are obtained. Different birnessite precursors have been tested and the reaction kinetics is strongly correlated to the crystallinity and granulometry of the precursor. The effects of aging time and hydrazine hydrate amount have been studied. Well crystallised Mn{sub 3}O{sub 4} is obtained in one hour. The presence ofmore » feitknechtite (MnO(OH)) and amorphous nanorods has been detected as an intermediate phase during birnessite conversion into hausmanite. The conversion mechanism is discussed. - Graphical abstract: TEM image showing Mn{sub 3}O{sub 4} particle after treatment of birnessite with an addition of hydrazine during 24 hours.« less
  • Single crystals of mixed valent barium titanium(III/IV) chlorosilicate, Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09}, were grown in a high temperature molten chloride flux involving an in situ reduction step. The fresnoite structure related Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09} crystallizes in the tetragonal space group P4/mbm with lattice parameters of a=8.6717(2) Å, c=18.6492(5) Å. The title compound exhibits a 3D structure consisting of 2D layers of fused Ti{sub 2}O{sub 9} and Si{sub 4}O{sub 12} groups and 2D layers of fused Ti{sub 2}O{sub 9}Cl{sub 2} and Si{sub 2}O{sub 7} groups that are linked via barium atoms. The in situmore » reduction of Ti(IV) to Ti(III) is achieved via the addition of metallic Mg to the flux to function as the reducing agent. The temperature dependence of the magnetic susceptibility shows simple paramagnetism above 100 K. There is a discontinuity in the susceptibility data below 100 K, which might be due to a structural change that takes place resulting in charge ordering. - Graphical abstract: The fresnoite structure related novel reduced barium titanium chlorosilicate, Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09}, were synthesized via flux method. An in situ reduction of Ti(IV) to Ti(III) achieved using Mg metal. The 3D structure consists 2D layers of fused Ti{sub 2}O{sub 9} and Si{sub 4}O{sub 12} and 2D layers of fused Ti{sub 2}O{sub 9}Cl{sub 2} and Si{sub 2}O{sub 7} connected via barium atoms. Compound shows simple paramagnetism above 100 K. - Highlights: • The fresnoite related Ba{sub 3}Ti{sub 2}Si{sub 4}O{sub 14}Cl{sub 0.91}O{sub 0.09} were grown via molten flux method. • The in situ reduction of Ti(IV) to Ti(III) is achieved using metallic Mg. • 2D layers of Ti{sub 2}O{sub 9} and Si{sub 4}O{sub 12} and Ti{sub 2}O{sub 9}Cl{sub 2} and Si{sub 2}O{sub 7} connect via Ba atoms. • The magnetic susceptibility shows simple paramagnetism above 100 K.« less
  • Graphical abstract: This figure shows the specific magnetization curves of the as-prepared MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders obtained from room temperature VSM measurement. These curves are typical for a soft magnetic material and indicate hysteresis ferromagnetism in the field ranges of ±500 Oe, ±1000 Oe, and ±2000 Oe for the CoFe{sub 2}O{sub 4}, MgFe{sub 2}O{sub 4} and MnFe{sub 2}O{sub 4} respectively, whereas the samples of NiFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} show a superparamagnetic behavior. Highlights: ► Nanocrystalline MFe{sub 2}O{sub 4} powders were synthesized by a novel hydrothermal method. ► Metal acetylacetonates andmore » aloe vera plant-extracted solution are used. ► This biosynthetic route is very simple and provides high-yield oxide nanomaterials. ► XRD and TEM results indicate that the prepared samples have only spinel structure. ► The maximum M{sub s} of 68.9 emu/g at 10 kOe were observed for the samples of MnFe{sub 2}O{sub 4}. - Abstract: Nanocrystalline spinel ferrite MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders were synthesized by a novel hydrothermal method using Fe(acac){sub 3}, M(acac){sub 3} (M = Ni, Co, Mn, Mg, Zn) and aloe vera plant extracted solution. The X-ray diffraction and selected-area electron diffraction results indicate that the synthesized nanocrystalline have only spinel structure without the presence of other phase impurities. The crystal structure and morphology of the spinel ferrite powders, as revealed by TEM, show that the NiFe{sub 2}O{sub 4} and CoFe{sub 2}O{sub 4} samples contain nanoparticles, whereas the MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples consist of many nanoplatelets and nanoparticles. Interestingly, the ZnFe{sub 2}O{sub 4} sample contains plate-like structure of networked nanocrystalline particles. Room temperature magnetization results show a ferromagnetic behavior of the CoFe{sub 2}O{sub 4}, MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples, whereas the samples of NiFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} exhibit a superparamagnetic behavior.« less
  • Large-scale CeO{sub 2} nanowires were prepared successfully by an improved sol-gel process within the nanochannels of porous anodic alumina templates. In this process, cerium nitrate and urea were used as precursors, cerium nitrate acted as cerium ions source, and urea offered a basic medium through its hydrolysis. The as-synthesized CeO{sub 2} nanowires can be indexed as a fluorite-structure and the size of nanowires is uniform, with diameters of about 70 nm. The formation mechanism of nanowires is also discussed here. This method is more efficient than a traditional sol-gel template process for small pore diameter templates.
  • Single crystalline copper metagermanate (CuGeO{sub 3}) nanowires with the diameter of 30-300 nm and length of longer than 100 {mu}m have been prepared by a simple hydrothermal deposition route. X-ray diffraction (XRD), selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM) and Raman analyses confirm that the nanowires are orthorhombic single crystals with a main growth direction along <101>. Room temperature photoluminescence (PL) measurement shows a strong blue emission peak at 442 nm with a broad emission band. The blue emission may be ascribed to radiative recombination of oxygen vacancies and oxygen-germanium vacancies. The formation process of CuGeO{sub 3}more » nanowires is also discussed.« less