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Title: Molecular water-oxidation catalyst derived from ruthenium diaqua bis(2,2'-bipyridyl-5,5'-dicarboxylic acid)

Abstract

Controlled-potential electrolysis of cis-Ru/sup II/L/sub 2/(OH/sub 2/)/sub 2//sup 2 +/ (where L is 2,2'-bipyridyl-5,5'-dicarboxylic acid) in 0.5 M H/sub 2/SO/sub 4/ solutions leads to the formation of a relatively durable and active molecular water-oxidation catalyst. Detailed analyses by UV-visible absorption spectrophotometry, resonance Raman spectrophotometry, electrochemical measurements, HPLC, and elemental analysis indicate that the water-oxidation catalyst is an oxo-bridged dimer, L/sub 2/(H/sub 2/O)Ru-O-Ru(OH/sub 2/)L/sub 2/. The synthesis, spectrophotometric, and redox properties of the monomeric and dimeric ruthenium complexes have been characterized. The effectiveness of the oxo-bridged complex as a water-oxidation catalyst has been evaluated by electrochemical and spectrophotometric analyses and by determination of oxygen production. This newly discovered homogeneous catalyst is highly effective in mediating the thermal and visible-light-induced generation of oxygen from water. A comparison is made between the monomer and dimer and various analogues of the complexes. The presence of the COOH groups at the 5,5' positions of the bipyridyl ligands correlates with the unusual and favorable properties of cis-RuL/sub 2/(OH/sub 2/)/sub 2/ and L/sub 2/(OH/sub 2/)Ru-O-Ru(OH/sub 2/)L/sub 2/. Dimeric ruthenium complexes of similar structure are also formed during the thermolysis and photolysis of Ru(II) tris(2,2'-bipyridyl-5,5'-dicarboxylic acid), RuL/sub 3//sup 2 +/, in 0.5 M H/sub 2/SO/sub 4/ solutions containingmore » peroxodisulfate.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Ecole Polytechnique Federale, Lausanne, Switzerland
OSTI Identifier:
5571418
DOE Contract Number:  
AC02-83CH10093; AC06-83ER13111
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 109:22
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BIPYRIDINES; CATALYTIC EFFECTS; CHEMICAL PREPARATION; CARBOXYLIC ACIDS; OXYGEN; PRODUCTION; RUTHENIUM COMPLEXES; WATER; OXIDATION; PHOTOCHEMICAL REACTIONS; CATALYSIS; CATALYSTS; ELECTROCHEMISTRY; EXPERIMENTAL DATA; REDOX REACTIONS; SPECTROPHOTOMETRY; AZINES; CHEMICAL REACTIONS; CHEMISTRY; COMPLEXES; DATA; ELEMENTS; HETEROCYCLIC COMPOUNDS; HYDROGEN COMPOUNDS; INFORMATION; NONMETALS; NUMERICAL DATA; ORGANIC ACIDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; OXYGEN COMPOUNDS; PYRIDINES; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400500* - Photochemistry

Citation Formats

Rotzinger, F P, Munavalli, S, Comte, P, Hurst, J K, Gratzel, M, Pern, F, and Frank, A J. Molecular water-oxidation catalyst derived from ruthenium diaqua bis(2,2'-bipyridyl-5,5'-dicarboxylic acid). United States: N. p., 1987. Web. doi:10.1021/ja00256a010.
Rotzinger, F P, Munavalli, S, Comte, P, Hurst, J K, Gratzel, M, Pern, F, & Frank, A J. Molecular water-oxidation catalyst derived from ruthenium diaqua bis(2,2'-bipyridyl-5,5'-dicarboxylic acid). United States. https://doi.org/10.1021/ja00256a010
Rotzinger, F P, Munavalli, S, Comte, P, Hurst, J K, Gratzel, M, Pern, F, and Frank, A J. 1987. "Molecular water-oxidation catalyst derived from ruthenium diaqua bis(2,2'-bipyridyl-5,5'-dicarboxylic acid)". United States. https://doi.org/10.1021/ja00256a010.
@article{osti_5571418,
title = {Molecular water-oxidation catalyst derived from ruthenium diaqua bis(2,2'-bipyridyl-5,5'-dicarboxylic acid)},
author = {Rotzinger, F P and Munavalli, S and Comte, P and Hurst, J K and Gratzel, M and Pern, F and Frank, A J},
abstractNote = {Controlled-potential electrolysis of cis-Ru/sup II/L/sub 2/(OH/sub 2/)/sub 2//sup 2 +/ (where L is 2,2'-bipyridyl-5,5'-dicarboxylic acid) in 0.5 M H/sub 2/SO/sub 4/ solutions leads to the formation of a relatively durable and active molecular water-oxidation catalyst. Detailed analyses by UV-visible absorption spectrophotometry, resonance Raman spectrophotometry, electrochemical measurements, HPLC, and elemental analysis indicate that the water-oxidation catalyst is an oxo-bridged dimer, L/sub 2/(H/sub 2/O)Ru-O-Ru(OH/sub 2/)L/sub 2/. The synthesis, spectrophotometric, and redox properties of the monomeric and dimeric ruthenium complexes have been characterized. The effectiveness of the oxo-bridged complex as a water-oxidation catalyst has been evaluated by electrochemical and spectrophotometric analyses and by determination of oxygen production. This newly discovered homogeneous catalyst is highly effective in mediating the thermal and visible-light-induced generation of oxygen from water. A comparison is made between the monomer and dimer and various analogues of the complexes. The presence of the COOH groups at the 5,5' positions of the bipyridyl ligands correlates with the unusual and favorable properties of cis-RuL/sub 2/(OH/sub 2/)/sub 2/ and L/sub 2/(OH/sub 2/)Ru-O-Ru(OH/sub 2/)L/sub 2/. Dimeric ruthenium complexes of similar structure are also formed during the thermolysis and photolysis of Ru(II) tris(2,2'-bipyridyl-5,5'-dicarboxylic acid), RuL/sub 3//sup 2 +/, in 0.5 M H/sub 2/SO/sub 4/ solutions containing peroxodisulfate.},
doi = {10.1021/ja00256a010},
url = {https://www.osti.gov/biblio/5571418}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 109:22,
place = {United States},
year = {Wed Oct 28 00:00:00 EST 1987},
month = {Wed Oct 28 00:00:00 EST 1987}
}