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Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b05882· OSTI ID:1324096
 [1];  [2];  [3];  [1];  [1];  [3];  [4];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Inst. Max Von Laue Paul Langevin, Grenoble (France)
+ Show Author Affiliations

A 2.9 nm molybdenum oxide cluster {Mo132} (Formula: [MoVI72MoV60O372(CH3COO)30(H2O)72]42-) can be obtained by reducing ammonium molybdate with hydrazine sulfate in weakly acidic CH3COOH/CH3COO- buffers. This reaction has been monitored by time-resolved UV-Vis, 1H-NMR, small angle X-ray/neutron scattering, and X-ray absorption near edge structure spectroscopy. The growth of {Mo132} cluster shows a typical sigmoid curve, suggesting a multi-step assembly mechanism for this reaction. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {MoV2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {MoV2(acetate)} reaches a critical value, it triggers the assembly of MoV and MoVI species into {Mo132} clusters. Parameters such as the type and amount of reducing agent, the pH, the type of cation, and the type of organic ligand in the reaction buffer, have been studied for the roles they play in the formation of the target clusters.Understanding the formation mechanism of giant molecular clusters is essential for rational design and synthesis of cluster-based nanomaterials with required morphologies and functionalities. Here, typical synthetic reactions of a 2.9 nm spherical molybdenum oxide cluster, {Mo132} (formula: [MoVI72MoV60O372(CH3COO)30(H2O)72]42), with systematically varied reaction parameters have been fully explored to determine the morphologies and concentration of products, reduction of metal centers, and chemical environments of the organic ligands. The growth of these clusters shows a typical sigmoid curve, suggesting a general multistep self-assembly mechanism for the formation of giant molecular clusters. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {MoV2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {MoV2(acetate)} reaches a critical value, it triggers the co-assembly of MoV and MoVI species into the giant clusters.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357
OSTI ID:
1324096
Alternate ID(s):
OSTI ID: 1368099
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 33 Vol. 138; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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{Nb 288 O 768 (OH) 48 (CO 3 ) 12 }: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms journal June 2018
Unprecedented Halide‐Ion Binding and Catalytic Activity of Nanoscale Anionic Metal Oxide Clusters journal July 2019
The applications of small-angle X-ray scattering in studying nano-scaled polyoxometalate clusters in solutions journal April 2018
Improved peroxidase-mimic property: Sustainable, high-efficiency interfacial catalysis with H2O2 on the surface of vesicles of hexavanadate-organic hybrid surfactants journal February 2018
Synthesis of polyoxometalate clusters using carbohydrates as reducing agents leads to isomer-selection journal January 2019
Scattering functions of carved-ellipsoid-shaped particles journal February 2019
Scattering functions of carved-ellipsoid-shaped particles text January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY