skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO 2 to CO conversion via the reverse water-gas shift reaction

Abstract

Understanding how nano-dimensionality impacts iron oxide based catalysis is central to a wide range of applications. Here, we focus on hematite nanosheets, nanowires and nanoparticles as applied to catalyze the reverse water gas shift (RWGS) probe reaction. We introduce a novel approach to synthesize ultrathin (4–7 nm) hematite nanosheets using copper oxide nanosheets as a hard template and propose a reaction mechanism based on density functional theory (DFT) calculations. Hematite nanowires and nanoparticles were also synthesized and characterized. H2 temperature programmed reduction (H2-TPR) and RWGS reactions were performed to glean insights into the mechanism of CO2 conversion to CO over the iron oxide nanomaterials and were compared to H2 binding energy calculations based on density functional theory. While the nanosheets did exhibit high CO2 conversion, 28% at 510 °C, we found that the iron oxide nanowires had the highest CO2 conversion, reaching 50% at 750 °C under atmospheric pressure. No products besides CO and H2O were detected.

Authors:
ORCiD logo [1];  [1];  [2];  [1];  [3];  [1];  [1];  [2];  [1]
  1. Department of Chemical and Environmental Engineering; Yale University; New Haven; USA
  2. Department of Chemistry and Energy Sciences Institute; Yale University; New Haven; USA
  3. Department of Chemistry; Nankai University; Tianjin 300071; China
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE
OSTI Identifier:
1492968
Resource Type:
Journal Article
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 9; Journal Issue: 35; Journal ID: ISSN 2040-3364
Country of Publication:
United States
Language:
English

Citation Formats

Fishman, Zachary S., He, Yulian, Yang, Ke R., Lounsbury, Amanda W., Zhu, Junqing, Tran, Thanh Minh, Zimmerman, Julie B., Batista, Victor S., and Pfefferle, Lisa D. Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO 2 to CO conversion via the reverse water-gas shift reaction. United States: N. p., 2017. Web. doi:10.1039/c7nr03522e.
Fishman, Zachary S., He, Yulian, Yang, Ke R., Lounsbury, Amanda W., Zhu, Junqing, Tran, Thanh Minh, Zimmerman, Julie B., Batista, Victor S., & Pfefferle, Lisa D. Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO 2 to CO conversion via the reverse water-gas shift reaction. United States. doi:10.1039/c7nr03522e.
Fishman, Zachary S., He, Yulian, Yang, Ke R., Lounsbury, Amanda W., Zhu, Junqing, Tran, Thanh Minh, Zimmerman, Julie B., Batista, Victor S., and Pfefferle, Lisa D. Sun . "Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO 2 to CO conversion via the reverse water-gas shift reaction". United States. doi:10.1039/c7nr03522e.
@article{osti_1492968,
title = {Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO 2 to CO conversion via the reverse water-gas shift reaction},
author = {Fishman, Zachary S. and He, Yulian and Yang, Ke R. and Lounsbury, Amanda W. and Zhu, Junqing and Tran, Thanh Minh and Zimmerman, Julie B. and Batista, Victor S. and Pfefferle, Lisa D.},
abstractNote = {Understanding how nano-dimensionality impacts iron oxide based catalysis is central to a wide range of applications. Here, we focus on hematite nanosheets, nanowires and nanoparticles as applied to catalyze the reverse water gas shift (RWGS) probe reaction. We introduce a novel approach to synthesize ultrathin (4–7 nm) hematite nanosheets using copper oxide nanosheets as a hard template and propose a reaction mechanism based on density functional theory (DFT) calculations. Hematite nanowires and nanoparticles were also synthesized and characterized. H2 temperature programmed reduction (H2-TPR) and RWGS reactions were performed to glean insights into the mechanism of CO2 conversion to CO over the iron oxide nanomaterials and were compared to H2 binding energy calculations based on density functional theory. While the nanosheets did exhibit high CO2 conversion, 28% at 510 °C, we found that the iron oxide nanowires had the highest CO2 conversion, reaching 50% at 750 °C under atmospheric pressure. No products besides CO and H2O were detected.},
doi = {10.1039/c7nr03522e},
journal = {Nanoscale},
issn = {2040-3364},
number = 35,
volume = 9,
place = {United States},
year = {2017},
month = {1}
}

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Unique Lamellar Sodium/Potassium Iron Oxide Nanosheets: Facile Microwave-Assisted Synthesis and Magnetic and Electrochemical Properties
journal, September 2011

  • Wu, Liheng; Yao, Hongbin; Hu, Bo
  • Chemistry of Materials, Vol. 23, Issue 17
  • DOI: 10.1021/cm2013736

Role of Surface Cobalt Silicate in Single-Walled Carbon Nanotube Synthesis from Silica-Supported Cobalt Catalysts
journal, March 2010

  • Li, Nan; Wang, Xiaoming; Derrouiche, Salim
  • ACS Nano, Vol. 4, Issue 3
  • DOI: 10.1021/nn901812t

Fischer-Tropsch synthesis over reduced and unreduced iron oxide catalysts
journal, January 1986


Projector augmented-wave method
journal, December 1994


Facile synthesis of ultrathin magnetic iron oxide nanoplates by Schikorr reaction
journal, January 2013


Hematite (α-Fe 2 O 3 ) with Various Morphologies: Ionic Liquid-Assisted Synthesis, Formation Mechanism, and Properties
journal, October 2009

  • Lian, Jiabiao; Duan, Xiaochuan; Ma, Jianmin
  • ACS Nano, Vol. 3, Issue 11
  • DOI: 10.1021/nn900941e

Adsorption of arsenite and arsenate on amorphous iron hydroxide
journal, January 1982


Ultrasmall Fe 3 O 4 Nanoparticle/MoS 2 Nanosheet Composites with Superior Performances for Lithium Ion Batteries
journal, December 2013


Controlled Soft-Template Synthesis of Ultrathin C@FeS Nanosheets with High-Li-Storage Performance
journal, May 2012


Adsorption of arsenite on amorphous iron hydroxide from dilute aqueous solution
journal, February 1980

  • Pierce, Matthew L.; Moore, Carleton B.
  • Environmental Science & Technology, Vol. 14, Issue 2
  • DOI: 10.1021/es60162a011

Insights for size-dependent reactivity of hematite nanomineral surfaces through Cu2+ sorption
journal, August 2006

  • Madden, Andrew S.; Hochella, Michael F.; Luxton, Todd P.
  • Geochimica et Cosmochimica Acta, Vol. 70, Issue 16
  • DOI: 10.1016/j.gca.2006.06.1366

Layered Double Hydroxide-based Nanomaterials as Highly Efficient Catalysts and Adsorbents
journal, August 2014


Oxide nanotubes prepared using carbon nanotubes as templates
journal, March 1997

  • Satishkumar, B. C.; Govindaraj, A.; Vogl, Erasmus M.
  • Journal of Materials Research, Vol. 12, Issue 3
  • DOI: 10.1557/JMR.1997.0089

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Hydrogenation of carbon dioxide over alumina supported Fe-K catalysts
journal, January 1996

  • Choi, Pyoung Ho; Jun, Ki-Won; Lee, Soo-Jae
  • Catalysis Letters, Vol. 40, Issue 1-2
  • DOI: 10.1007/BF00807467

Kinetics of reverse water gas shift (RWGS) reaction on metal disulfide catalysts
journal, October 1997

  • Osaki, Toshihiko; Narita, Norichika; Horiuchi, Tatsuro
  • Journal of Molecular Catalysis A: Chemical, Vol. 125, Issue 1
  • DOI: 10.1016/S1381-1169(97)00080-0

High-yield synthesis and magnetic property of hematite nanorhombohedras through a facile solution route
journal, October 2007


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

On the activation energies of the forward and reverse water-gas shift reaction
journal, January 1995


Recent advances in nanoparticle synthesis with reversed micelles
journal, December 2006

  • Eastoe, Julian; Hollamby, Martin J.; Hudson, Laura
  • Advances in Colloid and Interface Science, Vol. 128-130
  • DOI: 10.1016/j.cis.2006.11.009

Band-Gap Energy as a Descriptor of Catalytic Activity for Propene Oxidation over Mixed Metal Oxide Catalysts
journal, September 2014

  • Getsoian, Andrew “Bean”; Zhai, Zheng; Bell, Alexis T.
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja5051555

Light-Induced Water Splitting with Hematite: Improved Nanostructure and Iridium Oxide Catalysis
journal, August 2010

  • Tilley, S. David; Cornuz, Maurin; Sivula, Kevin
  • Angewandte Chemie, Vol. 122, Issue 36
  • DOI: 10.1002/ange.201003110

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Hard template synthesis of crystalline mesoporous anatase TiO2 for photocatalytic hydrogen evolution
journal, January 2010

  • Zhang, Zhenyu; Zuo, Fan; Feng, Pingyun
  • Journal of Materials Chemistry, Vol. 20, Issue 11
  • DOI: 10.1039/b921157h

Arsenate and Chromate Retention Mechanisms on Goethite. 1. Surface Structure
journal, February 1997

  • Fendorf, Scott; Eick, Matthew J.; Grossl, Paul
  • Environmental Science & Technology, Vol. 31, Issue 2
  • DOI: 10.1021/es950653t

Investigation of multiplet splitting of Fe 2p XPS spectra and bonding in iron compounds
journal, January 2004

  • Grosvenor, A. P.; Kobe, B. A.; Biesinger, M. C.
  • Surface and Interface Analysis, Vol. 36, Issue 12
  • DOI: 10.1002/sia.1984

Optical absorption spectrum of hematite, αFe2O3 near IR to UV
journal, January 1980

  • Marusak, L. A.; Messier, R.; White, William B.
  • Journal of Physics and Chemistry of Solids, Vol. 41, Issue 9
  • DOI: 10.1016/0022-3697(80)90105-5

Large-Scale Soft Colloidal Template Synthesis of 1.4 nm Thick CdSe Nanosheets
journal, September 2009


Band-gap measurements of bulk and nanoscale hematite by soft x-ray spectroscopy
journal, January 2009


Template-Controlled Synthesis of Wire-Like Cadmium Sulfide Nanoparticle Assemblies within Core−Shell Cylindrical Polymer Brushes
journal, February 2004

  • Zhang, Mingfu; Drechsler, Markus; Müller, Axel H. E.
  • Chemistry of Materials, Vol. 16, Issue 3
  • DOI: 10.1021/cm034760v

Highly oriented Ge-doped hematite nanosheet arrays for photoelectrochemical water oxidation
journal, October 2014


Mechanism of M Ferrites (M = Cu and Ni) in the CO 2 Decomposition Reaction
journal, April 2001

  • Shin, Hyun-Chang; Choi, Seung-Chul; Jung, Kwang-Deog
  • Chemistry of Materials, Vol. 13, Issue 4
  • DOI: 10.1021/cm000658b

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Solar Water Splitting: Progress Using Hematite (α-Fe2O3) Photoelectrodes
journal, March 2011

  • Sivula, Kevin; Le Formal, Florian; Grätzel, Michael
  • ChemSusChem, Vol. 4, Issue 4
  • DOI: 10.1002/cssc.201000416

FTIR analysis of well-defined α-Fe2O3 particles
journal, March 1998

  • Wang, Yinsheng; Muramatsu, Atsushi; Sugimoto, Tadao
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 134, Issue 3
  • DOI: 10.1016/S0927-7757(97)00102-7

Simultaneous determination of composition and thickness of thin iron-oxide films from XPS Fe 2p spectra
journal, July 1996


Silicon-doped hematite nanosheets with superlattice structure
journal, January 2011

  • Liu, Jun; Liang, Changhao; Zhang, Hemin
  • Chemical Communications, Vol. 47, Issue 28
  • DOI: 10.1039/c1cc12513c

Ultrathin nanosheets of feroxyhyte: a new two-dimensional material with robust ferromagnetic behavior
journal, January 2014


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Ge-doped hematite nanosheets with tunable doping level, structure and improved photoelectrochemical performance
journal, May 2013


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Fundamental Role of Oxygen Stoichiometry in Controlling the Band Gap and Reactivity of Cupric Oxide Nanosheets
journal, August 2016

  • Fishman, Zachary S.; Rudshteyn, Benjamin; He, Yulian
  • Journal of the American Chemical Society, Vol. 138, Issue 34
  • DOI: 10.1021/jacs.6b05332

Hydrothermal fabrication of various morphological α-Fe2O3 nanoparticles modified by surfactants
journal, November 2004


Carbon dioxide hydrogenation over iron containing catalysts
journal, September 1994


Influence of point defects on the performance of InVO<sub>4</sub> photoanodes
journal, January 2011

  • van de Krol, Roel
  • Journal of Photonics for Energy, Vol. 1, Issue 1
  • DOI: 10.1117/1.3564926

The Big Problem of Small Particles:  A Comparison of Methods for Determination of Particle Size in Nanocrystalline Anatase Powders
journal, May 2005

  • Weibel, A.; Bouchet, R.; Boulc', F.
  • Chemistry of Materials, Vol. 17, Issue 9
  • DOI: 10.1021/cm0403762

In situ XPS analysis of various iron oxide films grown by NO 2 -assisted molecular-beam epitaxy
journal, January 1999


Synthesis of Platinum Nanowire Networks Using a Soft Template
journal, December 2007

  • Song, Yujiang; Garcia, Robert M.; Dorin, Rachel M.
  • Nano Letters, Vol. 7, Issue 12
  • DOI: 10.1021/nl0719123

Synthesis and characterization of silver nanoparticle and graphene oxide nanosheet composites as a bactericidal agent for water disinfection
journal, August 2011


Synthesis of Pure Boron Single-Wall Nanotubes
journal, April 2004

  • Ciuparu, Dragos; Klie, Robert F.; Zhu, Yimei
  • The Journal of Physical Chemistry B, Vol. 108, Issue 13
  • DOI: 10.1021/jp049301b

Redox Equilibria in Flooded Soils: i. the iron Hydroxide Systems
journal, January 1967


An XPS study of the adsorption of chromate on goethite (α-FeOOH)
journal, March 1997