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Title: Mediated electrochemical reduction of CO/sub 2/. Preparation and comparison of an isoelectronic series of complexes

Abstract

The preparation and characterization of complexes of the type (M(triphos)L)(BF/sub 4/)/sub 2/ are described (for M = Ni, L is P(OMe)/sub 3/ and PEt/sub 3/; for M = Pd, L is CH/sub 3/CN, P(OMe)/sub 3/, PEt/sub 3/, P(CH/sub 2/OH)/sub 3/, and PPh/sub 3/; for M = Pt, L is PEt/sub 3/; triphos is PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/). On the basis of cyclic voltammetry and bulk electrolysis experiments, the Pd complexes are shown to catalyze the electrochemical reduction of CO/sub 2/ to CO in acidic acetonitrile solutions. The analogous Ni and Pt complexes are not catalysts for CO/sub 2/ reduction under the same conditions. Kinetic studies have been carried out on (Pd(triphos)(PEt/sub 3/))(BF/sub 4/)/sub 2/ and a mechanism for the reduction of CO/sub 2/ is proposed.

Authors:
;
Publication Date:
Research Org.:
Solar Energy Research Institute, Golden, CO
OSTI Identifier:
7101109
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 109:1
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 01 COAL, LIGNITE, AND PEAT; 54 ENVIRONMENTAL SCIENCES; 14 SOLAR ENERGY; CARBON DIOXIDE; REDUCTION; CARBON MONOXIDE; PRODUCTION; CATALYSTS; PERFORMANCE; NICKEL COMPLEXES; CATALYTIC EFFECTS; CHEMICAL PREPARATION; CHEMICAL PROPERTIES; ORGANIC COMPOUNDS; PALLADIUM COMPLEXES; PHOSPHORUS COMPLEXES; PLATINUM COMPLEXES; CATALYSIS; CHEMICAL REACTION KINETICS; ELECTROCHEMISTRY; ELECTROLYSIS; EXPERIMENTAL DATA; LIGANDS; VOLTAMETRY; CARBON COMPOUNDS; CARBON OXIDES; CHALCOGENIDES; CHEMICAL REACTIONS; CHEMISTRY; COMPLEXES; DATA; INFORMATION; KINETICS; LYSIS; NUMERICAL DATA; OXIDES; OXYGEN COMPOUNDS; REACTION KINETICS; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400400* - Electrochemistry; 010408 - Coal, Lignite, & Peat- C1 Processes- (1987-); 500100 - Environment, Atmospheric- Basic Studies- (-1989); 142000 - Solar Energy- Heat Storage- (1980-)

Citation Formats

DuBois, D L, and Miedaner, A. Mediated electrochemical reduction of CO/sub 2/. Preparation and comparison of an isoelectronic series of complexes. United States: N. p., 1987. Web. doi:10.1021/ja00235a019.
DuBois, D L, & Miedaner, A. Mediated electrochemical reduction of CO/sub 2/. Preparation and comparison of an isoelectronic series of complexes. United States. https://doi.org/10.1021/ja00235a019
DuBois, D L, and Miedaner, A. 1987. "Mediated electrochemical reduction of CO/sub 2/. Preparation and comparison of an isoelectronic series of complexes". United States. https://doi.org/10.1021/ja00235a019.
@article{osti_7101109,
title = {Mediated electrochemical reduction of CO/sub 2/. Preparation and comparison of an isoelectronic series of complexes},
author = {DuBois, D L and Miedaner, A},
abstractNote = {The preparation and characterization of complexes of the type (M(triphos)L)(BF/sub 4/)/sub 2/ are described (for M = Ni, L is P(OMe)/sub 3/ and PEt/sub 3/; for M = Pd, L is CH/sub 3/CN, P(OMe)/sub 3/, PEt/sub 3/, P(CH/sub 2/OH)/sub 3/, and PPh/sub 3/; for M = Pt, L is PEt/sub 3/; triphos is PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/). On the basis of cyclic voltammetry and bulk electrolysis experiments, the Pd complexes are shown to catalyze the electrochemical reduction of CO/sub 2/ to CO in acidic acetonitrile solutions. The analogous Ni and Pt complexes are not catalysts for CO/sub 2/ reduction under the same conditions. Kinetic studies have been carried out on (Pd(triphos)(PEt/sub 3/))(BF/sub 4/)/sub 2/ and a mechanism for the reduction of CO/sub 2/ is proposed.},
doi = {10.1021/ja00235a019},
url = {https://www.osti.gov/biblio/7101109}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 109:1,
place = {United States},
year = {Wed Jan 07 00:00:00 EST 1987},
month = {Wed Jan 07 00:00:00 EST 1987}
}