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

doi:10.1002/cctc.201402134

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

14 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 language	English
Pages (from-to)	2345-2353
Number of pages	9
Journal	ChemCatChem
Volume	6
Issue number	8
DOIs	https://doi.org/10.1002/cctc.201402134
Publication status	Published - 2014
Externally published	Yes

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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10.1002/cctc.201402134

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

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.",

keywords = "electron transfer, heterogeneous catalysis, platinum, redox chemistry, solvent effects",

author = "Jinzhen Lu and Abrahams, {Brendan F.} and {Winther Jensen}, Bjorn and Martin, {Lisandra L.} and Bond, {Alan M.}",

year = "2014",

doi = "10.1002/cctc.201402134",

language = "English",

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T1 - Super-efficient platinum catalyst derived from a semiconducting, DMF solvate

T2 - Structural, spectroscopic, electrochemical, and catalytic characterization

AU - Lu, Jinzhen

AU - Abrahams, Brendan F.

AU - Winther Jensen, Bjorn

AU - Martin, Lisandra L.

AU - Bond, Alan M.

PY - 2014

Y1 - 2014

N2 - 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.

AB - 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.

KW - electron transfer

KW - heterogeneous catalysis

KW - platinum

KW - redox chemistry

KW - solvent effects

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

Abstract

Keywords

ASJC Scopus subject areas

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