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Title: A Generalizable Multigram Synthesis and Mechanistic Investigation of YMnO 3 Nanoplates

Abstract

We present that the reproducible gram-scale synthesis of crystalline nanoscale multiferroics is critical for the development of the next generation of commercially relevant electronic devices. Of the subset of multiferroic materials, yttrium manganese oxide (YMnO 3) is highly attractive, because of its large magneto-electric coupling constants and the recent observation of giant polarization under pressure in these types of rare earth manganites. Utilizing a unique synthetic methodology that combines metal–oleate thermal degradation with the use of a molten salt protocol, we were able to reproducibly generate monodisperse distributions of morphologically distinctive yttrium manganese oxides. Specifically, using a molten NaCl flux, we were able to synthesize phase-pure, single-crystalline hexagonal YMnO 3 nanoplates, measuring 441 ± 241 nm in diameter and 46 ± 6 nm in height. Moreover, these nanoplates gave rise to multiferroic behavior, which was confirmed by the observation of a ferroelectric phase from a combination of high-resolution TEM (HRTEM) and selected-area electron diffraction (SAED) analysis. Magnetic measurements are consistent with the onset of a spin glass state below 5 K. To highlight the generalizability of the synthetic method we have developed herein, as a demonstration of principle, we have also successfully used the same protocol to produce nanocubes ofmore » lanthanum aluminum oxide (LaAlO 3).« less

Authors:
 [1];  [1];  [2];  [3];  [4];  [5];  [1];  [6];  [1];  [6];  [4];  [5];  [7]; ORCiD logo [8]
  1. State University of New York at Stony Brook, Stony Brook, NY (United States). Department of Chemistry
  2. US Nano, LLC, Sarasota, FL (United States)
  3. Farmingdale State College, Farmingdale, NY (United States). Department of Physics
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Division
  5. Texas A & M Univ., College Station, TX (United States). Department of Physics and Astronomy
  6. Manhattan College, Riverdale, NY (United States). Department of Chemistry
  7. Farmingdale State College, Farmingdale, NY (United States). Department of Physics ; State University of New York at Stony Brook, Stony Brook, NY (United States). Department of Physics and Astronomy
  8. State University of New York at Stony Brook, Stony Brook, NY (United States). Department of Chemistry ; Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Division
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1357306
Alternate Identifier(s):
OSTI ID: 1376090
Report Number(s):
BNL-113859-2017-JA
Journal ID: ISSN 0888-5885; R&D Project: PM037; MA015MACA; KC0201030; KC0201010
Grant/Contract Number:
SC0012704; SC-00112704
Resource Type:
Journal Article: Published Article
Journal Name:
Industrial and Engineering Chemistry Research
Additional Journal Information:
Journal Volume: 56; Journal Issue: 19; Journal ID: ISSN 0888-5885
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

McBean, Coray L., Lewis, Crystal S., Tiano, Amanda L., Simonson, Jack W., Han, Myung-Geun, Gannon, William J., Yue, Shiyu, Patete, Jonathan M., Corrao, Adam A., Santulli, Alexander C., Wu, Lijun, Aronson, Meigan C., Zhu, Yimei, and Wong, Stanislaus S. A Generalizable Multigram Synthesis and Mechanistic Investigation of YMnO3 Nanoplates. United States: N. p., 2017. Web. doi:10.1021/acs.iecr.7b00113.
McBean, Coray L., Lewis, Crystal S., Tiano, Amanda L., Simonson, Jack W., Han, Myung-Geun, Gannon, William J., Yue, Shiyu, Patete, Jonathan M., Corrao, Adam A., Santulli, Alexander C., Wu, Lijun, Aronson, Meigan C., Zhu, Yimei, & Wong, Stanislaus S. A Generalizable Multigram Synthesis and Mechanistic Investigation of YMnO3 Nanoplates. United States. doi:10.1021/acs.iecr.7b00113.
McBean, Coray L., Lewis, Crystal S., Tiano, Amanda L., Simonson, Jack W., Han, Myung-Geun, Gannon, William J., Yue, Shiyu, Patete, Jonathan M., Corrao, Adam A., Santulli, Alexander C., Wu, Lijun, Aronson, Meigan C., Zhu, Yimei, and Wong, Stanislaus S. Fri . "A Generalizable Multigram Synthesis and Mechanistic Investigation of YMnO3 Nanoplates". United States. doi:10.1021/acs.iecr.7b00113.
@article{osti_1357306,
title = {A Generalizable Multigram Synthesis and Mechanistic Investigation of YMnO3 Nanoplates},
author = {McBean, Coray L. and Lewis, Crystal S. and Tiano, Amanda L. and Simonson, Jack W. and Han, Myung-Geun and Gannon, William J. and Yue, Shiyu and Patete, Jonathan M. and Corrao, Adam A. and Santulli, Alexander C. and Wu, Lijun and Aronson, Meigan C. and Zhu, Yimei and Wong, Stanislaus S.},
abstractNote = {We present that the reproducible gram-scale synthesis of crystalline nanoscale multiferroics is critical for the development of the next generation of commercially relevant electronic devices. Of the subset of multiferroic materials, yttrium manganese oxide (YMnO3) is highly attractive, because of its large magneto-electric coupling constants and the recent observation of giant polarization under pressure in these types of rare earth manganites. Utilizing a unique synthetic methodology that combines metal–oleate thermal degradation with the use of a molten salt protocol, we were able to reproducibly generate monodisperse distributions of morphologically distinctive yttrium manganese oxides. Specifically, using a molten NaCl flux, we were able to synthesize phase-pure, single-crystalline hexagonal YMnO3 nanoplates, measuring 441 ± 241 nm in diameter and 46 ± 6 nm in height. Moreover, these nanoplates gave rise to multiferroic behavior, which was confirmed by the observation of a ferroelectric phase from a combination of high-resolution TEM (HRTEM) and selected-area electron diffraction (SAED) analysis. Magnetic measurements are consistent with the onset of a spin glass state below 5 K. To highlight the generalizability of the synthetic method we have developed herein, as a demonstration of principle, we have also successfully used the same protocol to produce nanocubes of lanthanum aluminum oxide (LaAlO3).},
doi = {10.1021/acs.iecr.7b00113},
journal = {Industrial and Engineering Chemistry Research},
number = 19,
volume = 56,
place = {United States},
year = {Fri May 05 00:00:00 EDT 2017},
month = {Fri May 05 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.iecr.7b00113

Citation Metrics:
Cited by: 2works
Citation information provided by
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  • We present that the reproducible gram-scale synthesis of crystalline nanoscale multiferroics is critical for the development of the next generation of commercially relevant electronic devices. Of the subset of multiferroic materials, yttrium manganese oxide (YMnO 3) is highly attractive, because of its large magneto-electric coupling constants and the recent observation of giant polarization under pressure in these types of rare earth manganites. Utilizing a unique synthetic methodology that combines metal–oleate thermal degradation with the use of a molten salt protocol, we were able to reproducibly generate monodisperse distributions of morphologically distinctive yttrium manganese oxides. Specifically, using a molten NaCl flux,more » we were able to synthesize phase-pure, single-crystalline hexagonal YMnO 3 nanoplates, measuring 441 ± 241 nm in diameter and 46 ± 6 nm in height. Moreover, these nanoplates gave rise to multiferroic behavior, which was confirmed by the observation of a ferroelectric phase from a combination of high-resolution TEM (HRTEM) and selected-area electron diffraction (SAED) analysis. Magnetic measurements are consistent with the onset of a spin glass state below 5 K. To highlight the generalizability of the synthetic method we have developed herein, as a demonstration of principle, we have also successfully used the same protocol to produce nanocubes of lanthanum aluminum oxide (LaAlO 3).« less
  • We present that the oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating “high aspect ratio” LaNiO 3 and LaMnO 3more » nanostructures. As the main focus of our demonstration of principle, we prepared as-synthesized LaNiO 3 rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. In addition, we observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO 3 rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO 2.« less
    Cited by 1
  • Graphical abstract: Thermodynamically stable α-MoO{sub 3} nanoplates and nanorods were synthesized using organic structure controlling agents and demonstrated sun light enhanced photocatalytic degradation of methylene blue (MB) and rhodamine blue (Rh-B) dyes in aqueous solution. - Highlights: • α-MoO{sub 3} hexagonal nanoplates using organic structure controlling agents. • Tunable optical band gap of MoO{sub 3}. • Demonstrated strong sun light mediated enhanced photodegradation of methylene blue and rhodamine blue. • Photodegradation did not use any other external oxidizing agents. - Abstract: Thermodynamically stable α-MoO{sub 3} nanoplates were synthesized using organic aliphatic acids as structure controlling agents and investigated photocatalytic degradationmore » of methylene blue (MB) and rhodamine blue (Rh-B) in presence of sun light. Three different organic aliphatic acids, citric acid (CA), tartaric acid (TA) and ethylene diamine tetra-acetic acid (EDTA), were employed to control morphologies. CA and TA predominantly produced extended hexagonal plates where EDTA gave nanorods as well as nanoplates. PXRD studies confirmed the formation of α-MoO{sub 3} nanoparticles. HR-TEM and FE-SEM reveal the formation of plate morphologies with 20–40 nm thickness, 50–100 nm diameter and 600 nm lengths. The different morphologies of α-MoO{sub 3} nanoparticles lead to the tunable optical band gap between 2.80 and 2.98 eV which was obtained from diffused reflectance spectra (DRS). Interestingly, the synthesized α-MoO{sub 3} nanoplates exhibited strong photocatalytic degradation of MB and Rh-B up to 99% in presence of sun light without using any oxidizing agents.« less
  • We report an experimental study of the domain structure of ferroelectric YMnO{sub 3} and YMn{sub 0.9}Fe{sub 0.1}O{sub 3} using polycrystalline samples prepared by direct hydrothermal crystallisation at 240 °C, well below their structural phase transition temperatures. Powder X-ray diffraction shows the expected P6{sub 3}cm space group for both samples with an increase in a and a small decrease in c with Fe incorporation, consistent with an adjustment of MnO{sub 5} tilting, while XANES spectra at the Mn and Fe K edges show the oxidation state of both metals are maintained at +3 in the doped sample. High resolution TEM shows thatmore » curved stripe, annular and vortex domains can all be observed in the YMnO{sub 3} crystals, proving that the structural phase transition is not the only driving force for the occurrence of the annular and vortex domains. Furthermore, the absence of the annular and vortex domains in YMn{sub 0.9}Fe{sub 0.1}O{sub 3} indicates that the tilting state of MnO{sub 5} bipyramids plays an important role in the domain formation. Atomic resolution STEM images confirm that the ferroelectric domain walls correspond to structural antiphase boundaries similar to the crystals made via high temperature solid-state reactions.« less