Development of transition metal phosphine complexes as electrocatalysts for CO2 and CO reduction

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Abstract

[Pd(triphosphine)(solvent)](BF4)2 complexes have been developed as catalysts for the electrochemical reduction of CO2 to CO. A variety of structural features of these complexes have been varied to determine their effects on the mechanism, rates, and decomposition products of these catalysts. The structural features varied included substituents on the triphosphine ligand, the size of the chelate bite, and donor atoms of the tridentate ligand. Bimetallic catalysts containing two [Pd(triphosphine)(solvent)] units have been prepared and characterized that exhibit a cooperative interaction during CO2 reduction with large rate enhancements compared to their monomeric analogs. As a first step in developing electrocatalysts capable of reducing CO, electrochemically generated hydrides of Ni and Pd have been shown to transfer their hydride ligands to coordinated CO to form formyl complexes.

Original languageEnglish
Pages (from-to)307-325
Number of pages19
JournalComments on Inorganic Chemistry
Volume19
Issue number5
Publication statusPublished - 1997

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phosphine
Electrocatalysts
Carbon Monoxide
Metal complexes
Transition metals
Ligands
Hydrides
Catalysts
Decomposition
Atoms

Keywords

  • Carbon dioxide reduction
  • Cooperative effects
  • Electrocatalysis
  • Formyl complexes
  • Metal phosphine complexes

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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abstract = "[Pd(triphosphine)(solvent)](BF4)2 complexes have been developed as catalysts for the electrochemical reduction of CO2 to CO. A variety of structural features of these complexes have been varied to determine their effects on the mechanism, rates, and decomposition products of these catalysts. The structural features varied included substituents on the triphosphine ligand, the size of the chelate bite, and donor atoms of the tridentate ligand. Bimetallic catalysts containing two [Pd(triphosphine)(solvent)] units have been prepared and characterized that exhibit a cooperative interaction during CO2 reduction with large rate enhancements compared to their monomeric analogs. As a first step in developing electrocatalysts capable of reducing CO, electrochemically generated hydrides of Ni and Pd have been shown to transfer their hydride ligands to coordinated CO to form formyl complexes.",
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T1 - Development of transition metal phosphine complexes as electrocatalysts for CO2 and CO reduction

AU - Dubois, Daniel L.

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AB - [Pd(triphosphine)(solvent)](BF4)2 complexes have been developed as catalysts for the electrochemical reduction of CO2 to CO. A variety of structural features of these complexes have been varied to determine their effects on the mechanism, rates, and decomposition products of these catalysts. The structural features varied included substituents on the triphosphine ligand, the size of the chelate bite, and donor atoms of the tridentate ligand. Bimetallic catalysts containing two [Pd(triphosphine)(solvent)] units have been prepared and characterized that exhibit a cooperative interaction during CO2 reduction with large rate enhancements compared to their monomeric analogs. As a first step in developing electrocatalysts capable of reducing CO, electrochemically generated hydrides of Ni and Pd have been shown to transfer their hydride ligands to coordinated CO to form formyl complexes.

KW - Carbon dioxide reduction

KW - Cooperative effects

KW - Electrocatalysis

KW - Formyl complexes

KW - Metal phosphine complexes

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