Super-efficient platinum catalyst derived from a semiconducting, DMF solvate: Structural, spectroscopic, electrochemical, and catalytic characterization

Jinzhen Lu, Brendan F. Abrahams, Bjorn Winther Jensen, Lisandra L. Martin, Alan M. Bond

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The reaction of [(NH3)4Pt](NO3) 2 with LiTCNQF4 (TCNQF4=2,3,5,6-tetrafluoro-7, 7,8,8-tetracyanoquinodimethane) in dimethylformamide gives the product [(NH 3)4Pt](TCNQF4)2·(DMF) 4 (1). Subtle changes in the solvent conditions, however, result in a different product, [(NH3)4Pt](TCNQF4) 2·Et2O·(CH3OH)4/3 (2). Both 1 and 2 have been characterized by X-ray crystallography, vibrational (FTIR, Raman) and UV/vis spectroscopy, thermogravimetric analysis and electrochemistry. Single crystals of 1 indicate the presence of 3D networks supported by hydrogen bonding, whereas the structural analysis of 2 indicates a 2D layered network, which consists of alternating TCNQF4 - and [(NH3)4Pt]2+ layers. The conductivity of a single crystal of 1 at room temperature lies in the semiconducting range (≈2.5×10-6 Scm-1). Unexpectedly, 1 was found to exhibit an exceptionally high catalytic activity for the electron transfer reaction between ferricyanide and thiosulfate ions in aqueous media. Our analysis indicates that the DMF solvates were removed prior to the catalytic reaction, but no other changes that occur in the chemical composition were found. Thus, the active catalyst is [(NH3)4Pt](TCNQF 4)2 (3) rather than the starting material 1.

Original languageEnglish
Pages (from-to)2345-2353
Number of pages9
JournalChemCatChem
Volume6
Issue number8
DOIs
Publication statusPublished - 2014
Externally publishedYes

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Keywords

  • electron transfer
  • heterogeneous catalysis
  • platinum
  • redox chemistry
  • solvent effects

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Catalysis

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