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Title: Hydrothermal synthesis and characterization under dynamic conditions of cobalt oxide nanoparticles supported over magnesium oxide nano-plates

Abstract

Here, a nano-catalyst comprised of oxidized Co NPs supported on MgO nano-plates was synthesized via a hydrothermal co-precipitation strategy and calcination in O2 and subsequently in H2 at 250 °C. Spectro-microscopy characterization was performed by scanning transmission electron microscopy, electron energy loss spectroscopy and scanning X-ray transmission microscopy. Surface measurements under H2 and H2 + CO atmospheres were obtained by ambient pressure X-ray photoelectron spectroscopy and in situ X-ray absorption spectroscopy in the 225–480 °C range. These measurements at the atomic and microscopic levels demonstrated that the oxidized Co nanoparticles uniformly decorated the MgO nano-plates. The surfaces are enriched with Co, and with a mixture of Co(OH)2 and CoO under H2 and H2 + CO atmospheres. Under a H2 atmosphere, the outermost surfaces were composed of (lattice) O2-, CO32- and OH-. No inorganic carbonates were observed in the bulk. Chemisorbed CO, likely on the oxidized Co surfaces, was observed at the expense of O2- under 300 mTorr H2 + CO (2:1) at 225 °C. Gas phase CO2 was detected under 32 Torr H2 + CO (2:1) at 225 °C upon prolonged reaction time, and was attributed to a surface chemical reaction between O2- and chemisorbed CO. Furthermore, sp3 like carbonmore » species were detected on the otherwise carbon free surface in H2 + CO, which remained on the surface under the subsequent reaction conditions. The formation of sp3 like hydrocarbons was ascribed to a surface catalytic reaction between the chemisorbed CO and OH- as the apparent hydrogen source.« less

Authors:
 [1];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1464133
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 45; Journal Issue: 24; Related Information: © 2016 The Royal Society of Chemistry.; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Alayoglu, Selim, Rosenberg, Daniel J., and Ahmed, Musahid. Hydrothermal synthesis and characterization under dynamic conditions of cobalt oxide nanoparticles supported over magnesium oxide nano-plates. United States: N. p., 2016. Web. doi:10.1039/c6dt00204h.
Alayoglu, Selim, Rosenberg, Daniel J., & Ahmed, Musahid. Hydrothermal synthesis and characterization under dynamic conditions of cobalt oxide nanoparticles supported over magnesium oxide nano-plates. United States. https://doi.org/10.1039/c6dt00204h
Alayoglu, Selim, Rosenberg, Daniel J., and Ahmed, Musahid. Mon . "Hydrothermal synthesis and characterization under dynamic conditions of cobalt oxide nanoparticles supported over magnesium oxide nano-plates". United States. https://doi.org/10.1039/c6dt00204h. https://www.osti.gov/servlets/purl/1464133.
@article{osti_1464133,
title = {Hydrothermal synthesis and characterization under dynamic conditions of cobalt oxide nanoparticles supported over magnesium oxide nano-plates},
author = {Alayoglu, Selim and Rosenberg, Daniel J. and Ahmed, Musahid},
abstractNote = {Here, a nano-catalyst comprised of oxidized Co NPs supported on MgO nano-plates was synthesized via a hydrothermal co-precipitation strategy and calcination in O2 and subsequently in H2 at 250 °C. Spectro-microscopy characterization was performed by scanning transmission electron microscopy, electron energy loss spectroscopy and scanning X-ray transmission microscopy. Surface measurements under H2 and H2 + CO atmospheres were obtained by ambient pressure X-ray photoelectron spectroscopy and in situ X-ray absorption spectroscopy in the 225–480 °C range. These measurements at the atomic and microscopic levels demonstrated that the oxidized Co nanoparticles uniformly decorated the MgO nano-plates. The surfaces are enriched with Co, and with a mixture of Co(OH)2 and CoO under H2 and H2 + CO atmospheres. Under a H2 atmosphere, the outermost surfaces were composed of (lattice) O2-, CO32- and OH-. No inorganic carbonates were observed in the bulk. Chemisorbed CO, likely on the oxidized Co surfaces, was observed at the expense of O2- under 300 mTorr H2 + CO (2:1) at 225 °C. Gas phase CO2 was detected under 32 Torr H2 + CO (2:1) at 225 °C upon prolonged reaction time, and was attributed to a surface chemical reaction between O2- and chemisorbed CO. Furthermore, sp3 like carbon species were detected on the otherwise carbon free surface in H2 + CO, which remained on the surface under the subsequent reaction conditions. The formation of sp3 like hydrocarbons was ascribed to a surface catalytic reaction between the chemisorbed CO and OH- as the apparent hydrogen source.},
doi = {10.1039/c6dt00204h},
journal = {Dalton Transactions},
number = 24,
volume = 45,
place = {United States},
year = {Mon Mar 07 00:00:00 EST 2016},
month = {Mon Mar 07 00:00:00 EST 2016}
}

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Works referenced in this record:

NO 2 Adsorption on Ultrathin θ-Al 2 O 3 Films:  Formation of Nitrite and Nitrate Species
journal, August 2005

  • Ozensoy, Emrah; Peden, Charles H. F.; Szanyi, János
  • The Journal of Physical Chemistry B, Vol. 109, Issue 33
  • DOI: 10.1021/jp052053e

Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103
journal, January 1985


Cobalt Particle Size Effects in the Fischer−Tropsch Reaction Studied with Carbon Nanofiber Supported Catalysts
journal, March 2006

  • Bezemer, G. Leendert; Bitter, Johannes H.; Kuipers, Herman P. C. E.
  • Journal of the American Chemical Society, Vol. 128, Issue 12
  • DOI: 10.1021/ja058282w

Synthesis of monodisperse cobalt nanocrystals and their assembly into magnetic superlattices (invited)
journal, April 1999

  • Sun, Shouheng; Murray, C. B.
  • Journal of Applied Physics, Vol. 85, Issue 8
  • DOI: 10.1063/1.370357

On the Origin of the Cobalt Particle Size Effects in Fischer−Tropsch Catalysis
journal, April 2009

  • den Breejen, J. P.; Radstake, P. B.; Bezemer, G. L.
  • Journal of the American Chemical Society, Vol. 131, Issue 20
  • DOI: 10.1021/ja901006x

Deactivation of cobalt based Fischer–Tropsch catalysts: A review
journal, September 2010


Synthesis of higher alcohols with cobalt and copper based model catalysts: effect of the alkaline metals
journal, February 2001


High-performance hybrid oxide catalyst of manganese and cobalt for low-pressure methanol synthesis
journal, March 2015

  • Li, Cheng-Shiuan; Melaet, Gérôme; Ralston, Walter T.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7538

Nanoscale Magnesium Hydroxide and Magnesium Oxide Powders:  Control over Size, Shape, and Structure via Hydrothermal Synthesis
journal, February 2001

  • Ding, Yi; Zhang, Guangtao; Wu, Hao
  • Chemistry of Materials, Vol. 13, Issue 2
  • DOI: 10.1021/cm000607e

A template-free, thermal decomposition method to synthesize mesoporous MgO with a nanocrystalline framework and its application in carbon dioxide adsorption
journal, January 2010

  • Bian, Shao-Wei; Baltrusaitis, Jonas; Galhotra, Pragati
  • Journal of Materials Chemistry, Vol. 20, Issue 39, p. 8705-8710
  • DOI: 10.1039/c0jm01261k

Molecular Rulers for Scaling Down Nanostructures
journal, February 2001


In Situ Surface and Reaction Probe Studies with Model Nanoparticle Catalysts
journal, September 2012

  • Alayoglu, Selim; Krier, James M.; Michalak, William D.
  • ACS Catalysis, Vol. 2, Issue 11
  • DOI: 10.1021/cs3004903

Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles
journal, November 2008


A high pressure, high temperature infrared study of CO hydrogenation over Rh/ZrO2
journal, February 1996


Study of mixed steam and CO2 reforming of CH4 to syngas on MgO-supported metals
journal, December 1994


Au/MgO catalysts modified with ascorbic acid for low temperature CO oxidation
journal, February 2002


XPS and AFM investigations of annealing induced surface modifications of MgO single crystals
journal, March 2002


Design, synthesis, and use of cobalt-based Fischer-Tropsch synthesis catalysts
journal, November 1997


Hydrothermal synthetic strategies of inorganic semiconducting nanostructures
journal, January 2013

  • Shi, Weidong; Song, Shuyan; Zhang, Hongjie
  • Chemical Society Reviews, Vol. 42, Issue 13
  • DOI: 10.1039/c3cs60012b

Calculations of electron inelastic mean free paths. IX. Data for 41 elemental solids over the 50 eV to 30 keV range
journal, February 2011

  • Tanuma, S.; Powell, C. J.; Penn, D. R.
  • Surface and Interface Analysis, Vol. 43, Issue 3
  • DOI: 10.1002/sia.3522

Nano-MgO: novel preparation and application as support of Ni catalyst for CO2 reforming of methane
journal, July 2001


XPS Study of MgO Nanopowders Obtained by Different Preparation Procedures
journal, December 2006

  • Khairallah, Fares; Glisenti, Antonella
  • Surface Science Spectra, Vol. 13, Issue 1
  • DOI: 10.1116/11.20060601

Evidence of Highly Active Cobalt Oxide Catalyst for the Fischer–Tropsch Synthesis and CO 2 Hydrogenation
journal, January 2014

  • Melaet, Gérôme; Ralston, Walter T.; Li, Cheng-Shiuan
  • Journal of the American Chemical Society, Vol. 136, Issue 6
  • DOI: 10.1021/ja412447q

Synthesis, characterization and reactivity study of nanoscale magnesium oxide
journal, September 2007


Molecular Factors of Catalytic Selectivity
journal, November 2008

  • Somorjai, Gabor A.; Park, Jeong Y.
  • Angewandte Chemie International Edition, Vol. 47, Issue 48
  • DOI: 10.1002/anie.200803181

Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO
journal, July 2011

  • Balaraman, Ekambaram; Gunanathan, Chidambaram; Zhang, Jing
  • Nature Chemistry, Vol. 3, Issue 8
  • DOI: 10.1038/nchem.1089

Magnesium K -edge XANES spectroscopy of geological standards
journal, July 2013

  • Yoshimura, Toshihiro; Tamenori, Yusuke; Iwasaki, Nozomu
  • Journal of Synchrotron Radiation, Vol. 20, Issue 5
  • DOI: 10.1107/S0909049513016099

Oxidation of magnesium
journal, January 2002

  • Fournier, V.; Marcus, P.; Olefjord, I.
  • Surface and Interface Analysis, Vol. 34, Issue 1
  • DOI: 10.1002/sia.1346

Size-Controlled Model Co Nanoparticle Catalysts for CO 2 Hydrogenation: Synthesis, Characterization, and Catalytic Reactions
journal, May 2012

  • Iablokov, Viacheslav; Beaumont, Simon K.; Alayoglu, Selim
  • Nano Letters, Vol. 12, Issue 6
  • DOI: 10.1021/nl300973b