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Title: Static and Dynamical Structural Investigations of Metal-Oxide Nanocrystals by Powder X-ray Diffraction: Colloidal Tungsten Oxide as a Case Study

Abstract

In this study, we have developed a general X-ray powder diffraction (XPD) methodology for the simultaneous structural and compositional characterization of inorganic nanomaterials. The approach is validated on colloidal tungsten oxide nanocrystals (WO3-x NCs), as a model polymorphic nanoscale material system. Rod-shaped WO3-x NCs with different crystal structure and stoichiometry are comparatively investigated under an inert atmosphere and after prolonged air exposure. An initial structural model for the as-synthesized NCs is preliminarily identified by means of Rietveld analysis against several reference crystal phases, followed by atomic pair distribution function (PDF) refinement of the best-matching candidates (static analysis). Subtle stoichiometry deviations from the corresponding bulk standards are revealed. NCs exposed to air at room temperature are monitored by XPD measurements at scheduled time intervals. The static PDF analysis is complemented with an investigation into the evolution of the WO3-x NC structure, performed by applying the modulation enhanced diffraction technique to the whole time series of XPD profiles (dynamical analysis). Prolonged contact with ambient air is found to cause an appreciable increase in the static disorder of the O atoms in the WO3-x NC lattice, rather than a variation in stoichiometry. Finally, the time behavior of such structural change is identified onmore » the basis of multivariate analysis.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [1]
  1. IC CNR-Institute of Crystallography, Bari (Italy)
  2. Universita del Salento, Lecce (Italy). Dipartimento di Matematica e Fisica E. De Giorgi"; Center for Biomolecular Nanotechnologies@UNILE Istituto Italiano di Tecnologia, Arnesano (Italy); CNR NANOTEC ”Institute of Nanotechnology c/o Campus Ecotekne, University of Salento, Lecce (Italy)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Department
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Photon Sciences
  5. Center for Biomolecular Nanotechnologies at UNILE, Istituto Italiano di Tecnologia, Arnesano (Italy)
  6. Universita del Salento, Lecce (Italy). Dipartimento di Matematica e Fisica E. De Giorgi; CNR NANOTEC Institute of Nanotechnology c/o Campus Ecotekne, University of Salento, Lecce (Italy)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1336039
Alternate Identifier(s):
OSTI ID: 1401172
Report Number(s):
BNL-112193-2016-JA
Journal ID: ISSN 1439-4235; R&D Project: CO009; KC0302010
Grant/Contract Number:  
SC0012704; AC02-98CH10886
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 17; Journal Issue: 5; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; colloids; nanoparticles; oxides; pair distribution; function; X-ray diffraction

Citation Formats

Caliandro, Rocco, Sibillano, Teresa, Belviso, B. Danilo, Scarfiello, Riccardo, Hanson, Jonathan C., Dooryhee, Eric, Manca, Michele, Cozzoli, P. Davide, and Giannini, Cinzia. Static and Dynamical Structural Investigations of Metal-Oxide Nanocrystals by Powder X-ray Diffraction: Colloidal Tungsten Oxide as a Case Study. United States: N. p., 2016. Web. https://doi.org/10.1002/cphc.201501175.
Caliandro, Rocco, Sibillano, Teresa, Belviso, B. Danilo, Scarfiello, Riccardo, Hanson, Jonathan C., Dooryhee, Eric, Manca, Michele, Cozzoli, P. Davide, & Giannini, Cinzia. Static and Dynamical Structural Investigations of Metal-Oxide Nanocrystals by Powder X-ray Diffraction: Colloidal Tungsten Oxide as a Case Study. United States. https://doi.org/10.1002/cphc.201501175
Caliandro, Rocco, Sibillano, Teresa, Belviso, B. Danilo, Scarfiello, Riccardo, Hanson, Jonathan C., Dooryhee, Eric, Manca, Michele, Cozzoli, P. Davide, and Giannini, Cinzia. Tue . "Static and Dynamical Structural Investigations of Metal-Oxide Nanocrystals by Powder X-ray Diffraction: Colloidal Tungsten Oxide as a Case Study". United States. https://doi.org/10.1002/cphc.201501175. https://www.osti.gov/servlets/purl/1336039.
@article{osti_1336039,
title = {Static and Dynamical Structural Investigations of Metal-Oxide Nanocrystals by Powder X-ray Diffraction: Colloidal Tungsten Oxide as a Case Study},
author = {Caliandro, Rocco and Sibillano, Teresa and Belviso, B. Danilo and Scarfiello, Riccardo and Hanson, Jonathan C. and Dooryhee, Eric and Manca, Michele and Cozzoli, P. Davide and Giannini, Cinzia},
abstractNote = {In this study, we have developed a general X-ray powder diffraction (XPD) methodology for the simultaneous structural and compositional characterization of inorganic nanomaterials. The approach is validated on colloidal tungsten oxide nanocrystals (WO3-x NCs), as a model polymorphic nanoscale material system. Rod-shaped WO3-x NCs with different crystal structure and stoichiometry are comparatively investigated under an inert atmosphere and after prolonged air exposure. An initial structural model for the as-synthesized NCs is preliminarily identified by means of Rietveld analysis against several reference crystal phases, followed by atomic pair distribution function (PDF) refinement of the best-matching candidates (static analysis). Subtle stoichiometry deviations from the corresponding bulk standards are revealed. NCs exposed to air at room temperature are monitored by XPD measurements at scheduled time intervals. The static PDF analysis is complemented with an investigation into the evolution of the WO3-x NC structure, performed by applying the modulation enhanced diffraction technique to the whole time series of XPD profiles (dynamical analysis). Prolonged contact with ambient air is found to cause an appreciable increase in the static disorder of the O atoms in the WO3-x NC lattice, rather than a variation in stoichiometry. Finally, the time behavior of such structural change is identified on the basis of multivariate analysis.},
doi = {10.1002/cphc.201501175},
journal = {ChemPhysChem},
number = 5,
volume = 17,
place = {United States},
year = {2016},
month = {2}
}

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Works referenced in this record:

Nanostructured Oxides in Chemistry:  Characterization and Properties
journal, September 2004

  • Fernández-García, M.; Martínez-Arias, A.; Hanson, J. C.
  • Chemical Reviews, Vol. 104, Issue 9
  • DOI: 10.1021/cr030032f

Oxygen vacancies in transition metal and rare earth oxides: Current state of understanding and remaining challenges
journal, June 2007

  • Ganduglia-Pirovano, M. Verónica; Hofmann, Alexander; Sauer, Joachim
  • Surface Science Reports, Vol. 62, Issue 6
  • DOI: 10.1016/j.surfrep.2007.03.002

Morphology-dependent nanocatalysts: Rod-shaped oxides
journal, January 2014


Quantitative phase analysis by combining the Rietveld and the whole-pattern decomposition methods
journal, July 2002

  • Giannini, Cinzia; Guagliardi, Antonietta; Millini, Roberto
  • Journal of Applied Crystallography, Vol. 35, Issue 4
  • DOI: 10.1107/S0021889802008737

Determination of nanoparticle structure type, size and strain distribution from X-ray data for monatomic f.c.c.-derived non-crystallographic nanoclusters
journal, September 2003

  • Cervellino, Antonio; Giannini, Cinzia; Guagliardi, Antonietta
  • Journal of Applied Crystallography, Vol. 36, Issue 5
  • DOI: 10.1107/S0021889803013542

DEBUSSY : a Debye user system for nanocrystalline materials
journal, November 2010

  • Cervellino, Antonio; Giannini, Cinzia; Guagliardi, Antonietta
  • Journal of Applied Crystallography, Vol. 43, Issue 6
  • DOI: 10.1107/S0021889810041889

Nanoscale structural order from the atomic pair distribution function (PDF): There's plenty of room in the middle
journal, July 2008


Applications of pair distribution function methods to contemporary problems in materials chemistry
journal, January 2011

  • Young, Callum A.; Goodwin, Andrew L.
  • Journal of Materials Chemistry, Vol. 21, Issue 18
  • DOI: 10.1039/c0jm04415f

Size, Shape, and Internal Atomic Ordering of Nanocrystals by Atomic Pair Distribution Functions: A Comparative Study of γ-Fe 2 O 3 Nanosized Spheres and Tetrapods
journal, October 2009

  • Petkov, Valeri; Cozzoli, P. Davide; Buonsanti, Raffaella
  • Journal of the American Chemical Society, Vol. 131, Issue 40
  • DOI: 10.1021/ja9067589

Kinematic diffraction on a structure with periodically varying scattering function
journal, May 2011

  • Chernyshov, Dmitry; van Beek, Wouter; Emerich, Hermann
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 67, Issue 4
  • DOI: 10.1107/S0108767311010695

Untangling diffraction intensity: modulation enhanced diffraction on ZrO 2 powder
journal, June 2012

  • van Beek, Wouter; Emerich, Hermann; Urakawa, Atsushi
  • Journal of Applied Crystallography, Vol. 45, Issue 4
  • DOI: 10.1107/S0021889812018109

Patterson selectivity by modulation-enhanced diffraction
journal, May 2012

  • Caliandro, Rocco; Chernyshov, Dmitry; Emerich, Hermann
  • Journal of Applied Crystallography, Vol. 45, Issue 3
  • DOI: 10.1107/S0021889812011569

Chemical selectivity in structure determination by the time dependent analysis of in situ XRPD data: a clear view of Xe thermal behavior inside a MFI zeolite
journal, January 2015

  • Palin, Luca; Caliandro, Rocco; Viterbo, Davide
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 26
  • DOI: 10.1039/C5CP02522B

Tailored multivariate analysis for modulated enhanced diffraction
journal, October 2015

  • Caliandro, Rocco; Guccione, Pietro; Nico, Giovanni
  • Journal of Applied Crystallography, Vol. 48, Issue 6
  • DOI: 10.1107/S1600576715017070

Single-Crystalline Tungsten Oxide Quantum Dots for Fast Pseudocapacitor and Electrochromic Applications
journal, April 2014


Highly Flexible Sub-1 nm Tungsten Oxide Nanobelts as Efficient Desulfurization Catalysts
journal, August 2014


Tungsten Oxide Nanorods: An Efficient Nanoplatform for Tumor CT Imaging and Photothermal Therapy
journal, January 2014

  • Zhou, Zhiguo; Kong, Bin; Yu, Chao
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep03653

Length and Diameter Control of Ultrathin Nanowires of Substoichiometric Tungsten Oxide with Insights into the Growth Mechanism
journal, September 2012

  • Moshofsky, Brian; Mokari, Taleb
  • Chemistry of Materials, Vol. 25, Issue 8
  • DOI: 10.1021/cm302015z

Tunable Localized Surface Plasmon Resonances in Tungsten Oxide Nanocrystals
journal, February 2012

  • Manthiram, Karthish; Alivisatos, A. Paul
  • Journal of the American Chemical Society, Vol. 134, Issue 9
  • DOI: 10.1021/ja211363w

WO 3 Nanoparticles in the 5−30 nm Range by Solvothermal Synthesis under Microwave or Resistive Heating
journal, November 2009

  • Le Houx, N.; Pourroy, G.; Camerel, F.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 1
  • DOI: 10.1021/jp908669u

In Situ One-Pot Synthesis of 1-Dimensional Transition Metal Oxide Nanocrystals
journal, March 2005

  • Seo, Jung-wook; Jun, Young-wook; Ko, Seung Jin
  • The Journal of Physical Chemistry B, Vol. 109, Issue 12
  • DOI: 10.1021/jp0501291

Growth and Assembly of Crystalline Tungsten Oxide Nanostructures Assisted by Bioligation
journal, November 2005

  • Polleux, Julien; Pinna, Nicola; Antonietti, Markus
  • Journal of the American Chemical Society, Vol. 127, Issue 44
  • DOI: 10.1021/ja0544915

Electrochromics for smart windows: thin films of tungsten oxide and nickel oxide, and devices based on these
journal, January 2007

  • Niklasson, Gunnar A.; Granqvist, Claes G.
  • Journal of Materials Chemistry, Vol. 17, Issue 2, p. 127-156
  • DOI: 10.1039/B612174H

Nanostructured Tungsten Oxide - Properties, Synthesis, and Applications
journal, May 2011

  • Zheng, Haidong; Ou, Jian Zhen; Strano, Michael S.
  • Advanced Functional Materials, Vol. 21, Issue 12
  • DOI: 10.1002/adfm.201002477

Tungsten Oxides for Photocatalysis, Electrochemistry, and Phototherapy
journal, August 2015


Nanostructure-based WO3 photoanodes for photoelectrochemical water splitting
journal, January 2012

  • Liu, Xien; Wang, Fengying; Wang, Qing
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 22
  • DOI: 10.1039/c2cp40976c

Nanostructured photoelectrodes based on WO 3 : applications to photooxidation of aqueous electrolytes
journal, January 2013

  • Bignozzi, Carlo Alberto; Caramori, Stefano; Cristino, Vito
  • Chem. Soc. Rev., Vol. 42, Issue 6
  • DOI: 10.1039/C2CS35373C

New materials for tunable plasmonic colloidal nanocrystals
journal, January 2014

  • Comin, Alberto; Manna, Liberato
  • Chem. Soc. Rev., Vol. 43, Issue 11
  • DOI: 10.1039/C3CS60265F

Synthesis and Optical Properties of Colloidal Tungsten Oxide Nanorods
journal, March 2003

  • Lee, Kwangyeol; Seo, Won Seok; Park, Joon T.
  • Journal of the American Chemical Society, Vol. 125, Issue 12
  • DOI: 10.1021/ja034011e

Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408

Chemical Selectivity in Diffraction by Statistical Analysis of in situ XRPD Data
journal, August 2014

  • Milanesio, Marco; Palin, Luca; Viterbo, Davide
  • Acta Crystallographica Section A Foundations and Advances, Vol. 70, Issue a1
  • DOI: 10.1107/S2053273314085283

Quanto : a Rietveld program for quantitative phase analysis of polycrystalline mixtures
journal, May 2001

  • Altomare, Angela; Burla, Maria Cristina; Giacovazzo, Carmelo
  • Journal of Applied Crystallography, Vol. 34, Issue 3
  • DOI: 10.1107/S0021889801002904

A profile refinement method for nuclear and magnetic structures
journal, June 1969


Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993


PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions
journal, March 2013


PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals
journal, July 2007


RootProf : software for multivariate analysis of unidimensional profiles
journal, May 2014

  • Caliandro, Rocco; Belviso, Danilo Benny
  • Journal of Applied Crystallography, Vol. 47, Issue 3
  • DOI: 10.1107/S1600576714005895

SIR2011 : a new package for crystal structure determination and refinement
journal, February 2012

  • Burla, Maria Cristina; Caliandro, Rocco; Camalli, Mercedes
  • Journal of Applied Crystallography, Vol. 45, Issue 2
  • DOI: 10.1107/S0021889812001124

    Works referencing / citing this record:

    Principal component analysis for automatic extraction of solid-state kinetics from combined in situ experiments
    journal, January 2018

    • Guccione, Pietro; Palin, Luca; Belviso, Benny Danilo
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 29
    • DOI: 10.1039/c8cp02481b

    X-ray Diffraction: A Powerful Technique for the Multiple-Length-Scale Structural Analysis of Nanomaterials
    journal, August 2016

    • Giannini, Cinzia; Ladisa, Massimo; Altamura, Davide
    • Crystals, Vol. 6, Issue 8
    • DOI: 10.3390/cryst6080087