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X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.5b11465· OSTI ID:1240563
 [1];  [2];  [1];  [1];  [1];  [3];  [3];  [4];  [4];  [4];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  2. Univ. of Tennessee, Knoxville, TN (United States). Department of Physics and Astronomy, Joint Institute of Neutron Science
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science
+ Show Author Affiliations
A typical type of core-shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo72Fe30}. Small angle X-ray scattering is used to study the structural features and stability of the core-shell structures in aqueous solutions. Time-resolved small angle X-ray scattering is applied to monitor the synthetic reactions and a three-stage formation mechanism is proposed to describe the synthesis of the core-shell polyoxometalates based on the monitoring results. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core-shell structures and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures. A typical type of core shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo72Fe30}. Small-angle X-ray scattering is used to study the structural features and stability of the core shell structures in aqueous solutions. Time-resolved small-angle X-ray scattering is applied to monitor the synthetic reactions, and a three-stage formation mechanism is proposed to describe the synthesis of the core shell polyoxometalates based on the monitoring results. New protocols have been developed by fitting the X-ray data with custom physical models, which provide more convincing, objective, and completed data interpretation. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core shell structures, and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Spallation Neutron Source
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357
OSTI ID:
1240563
Alternate ID(s):
OSTI ID: 1340274
OSTI ID: 1245207
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 8 Vol. 138; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Poly(ethylene glycol) nanocomposites of sub-nanometer metal oxide clusters for dynamic semi-solid proton conductive electrolytes journal January 2019
Jenseits von Ladungsausgleich: Gegenkationen in der Polyoxometallat‐Chemie journal October 2019
Beyond Charge Balance: Counter‐Cations in Polyoxometalate Chemistry journal January 2020
A General Approach to Access Morphologies of Polyoxometalates in Solution by Using SAXS: An Ab Initio Modeling Protocol journal April 2018
Unprecedented Halide‐Ion Binding and Catalytic Activity of Nanoscale Anionic Metal Oxide Clusters journal July 2019
Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry journal January 2019
The applications of small-angle X-ray scattering in studying nano-scaled polyoxometalate clusters in solutions journal April 2018
Polyoxometalates as components of supramolecular assemblies journal January 2019
Two new Keggin-type polyoxometalate-based organic-inorganic hybrid compounds with metal ions and chelate ligands journal February 2017
Two copper(II)-bbtz modified Keggin and β -octamolybdate compounds captured in one-pot under hydrothermal conditions journal February 2017
Scattering functions of carved-ellipsoid-shaped particles journal February 2019
Scattering functions of carved-ellipsoid-shaped particles text January 2019
A series of Keggin- and Wells-Dawson-polyoxometalate-based compounds constructed from oxygen-functional imidazole derivatives journal February 2019
Polyoxometalates as components of supramolecular assemblies text January 2019
Catalytic Growth of Carbon Nanotubes by Direct Liquid Injection CVD Using the Nanocluster [HxPMo12O40⊂H4Mo72Fe30(O2CMe)15O254(H2O)98-y(EtOH)y] journal March 2018
Two new Keggin-type polyoxometalate-based organic-inorganic hybrid compounds with metal ions and chelate ligands text January 2017
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