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Structural Evolution of Mixed-Addenda Keggin Polyoxometalate Anions with Atom-by-Atom Substitution

Journal Article · · The Journal of Physical Chemistry C
 [1];  [2];  [3];  [4];  [3];  [2];  [5]
  1. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Washington State University, Pullman, Richland, WA (United States)
  2. Universitat Rovira i Virgili, Tarragona (Spain)
  3. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  4. Northeast Normal University, Changchun (China)
  5. Purdue University, West Lafayette, IN (United States)
+ Show Author Affiliations
Polyoxometalates (POMs) are molecular metal oxides with distinctive electronic properties that make them promising materials for applications in energy, sensors, and memory devices. One of the most promising methods of tuning the stability, photochromic, redox, and electron-spin properties of POMs is through the substitution of the metal “addenda” atoms that, along with oxygen, constitute their cage-like structures. Because traditional synthesis methods typically produce a distribution of POMs, the isolation and characterization of multimetallic POMs with predetermined stoichiometry remains challenging. The presence of multiple energetically accessible isomers further complicates the experimental characterization and theoretical modeling of multimetallic POMs. Herein, we leverage the distinguishing mass-selection capabilities of ion soft landing to prepare stoichiometrically selected Keggin PMoxW12-xO40 3- (x = 0 – 6, 8, 10, and 12) POMs on self-assembled monolayer surfaces free of the solvent molecules and counterions that often confound characterization of complex species at interfaces. The structures of the supported POMs are characterized with atom-by-atom precision using in situ infrared (IR) reflection absorption spectroscopy complemented by detailed density functional theory calculations. Our joint experimental and theoretical results reveal an almost linear shift in the positions of the IR bands towards lower wavenumbers with an increase in the number of lighter molybdenum atoms compared to heavier W atoms in PMoxW12-xO40 3-. The theoretical calculations also indicate that numerous isomeric structures may be populated at the experimental conditions and, consequently, contribute to the overall IR spectra. In conclusion, our findings indicate that in addition to the number of substituted addenda atoms and the presence of multiple isomeric structures, interactions with the surface play an important role in determining the IR spectra and structure of supported bimetallic POMs.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
2585261
Report Number(s):
PNNL-SA--204680
Journal Information:
The Journal of Physical Chemistry C, Journal Name: The Journal of Physical Chemistry C Journal Issue: 4 Vol. 129; ISSN 1932-7455; ISSN 1932-7447
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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