Formation and reactivity of surface-bound high oxidation state Ruthenium-oxo complexes.
Abstract
Ruthenium polypyridyl oxalate complexes are precursors to high oxidation state species that can catalyze the oxidation of a variety of substrates. Covalent attachment of these reactive species to surfaces such at ZrO{sub 2} or TiO{sub 2} inhibit catalyst deactivation and provide supports from which to build electrocatalytic and photoelectrocatalytic devices. Unfortunately, few details of the effects of surface binding on reactivity are available in the literature. To this end, precursors such as, Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4})(H{sub 2}O) and (C{sub 2}O{sub 4})(H{sub 2}O{sub 3}Ptpy)Ru-O-Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4}) (tpy is terpyridine) have been synthesized and attached to TiO{sub 2}. Quantitative surface binding studies were carried out and acid catalyzed solvolysis was used to form the aqua species. The complexes were oxidized with Ce(IV) to their high-valent analogs and their reactivity toward selected substrates was tested. These studies not only provide information about the effects of surface binding on the reactivity of metal oxides but also have implications for the development of light-driven catalysts.
- Authors:
-
- Brooks J.
- Dana M.
- Jon R.
- Thomas J.
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 977823
- Report Number(s):
- LA-UR-04-5852
TRN: US201012%%551
- Resource Type:
- Conference
- Resource Relation:
- Conference: Submitted to: 228th Meeting Of The American Chemical Society, August 2004, Philadelphia
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CATALYSTS; DEACTIVATION; OXALATES; RUTHENIUM COMPLEXES; SOLVOLYSIS; VALENCE; CATALYST SUPPORTS; PRECURSOR; SYNTHESIS; TITANIUM OXIDES; OXIDATION
Citation Formats
Hornstein, B J, Dattelbaum, D M, Schoonover, J R, and Meyer, T J. Formation and reactivity of surface-bound high oxidation state Ruthenium-oxo complexes.. United States: N. p., 2004.
Web.
Hornstein, B J, Dattelbaum, D M, Schoonover, J R, & Meyer, T J. Formation and reactivity of surface-bound high oxidation state Ruthenium-oxo complexes.. United States.
Hornstein, B J, Dattelbaum, D M, Schoonover, J R, and Meyer, T J. 2004.
"Formation and reactivity of surface-bound high oxidation state Ruthenium-oxo complexes.". United States. https://www.osti.gov/servlets/purl/977823.
@article{osti_977823,
title = {Formation and reactivity of surface-bound high oxidation state Ruthenium-oxo complexes.},
author = {Hornstein, B J and Dattelbaum, D M and Schoonover, J R and Meyer, T J},
abstractNote = {Ruthenium polypyridyl oxalate complexes are precursors to high oxidation state species that can catalyze the oxidation of a variety of substrates. Covalent attachment of these reactive species to surfaces such at ZrO{sub 2} or TiO{sub 2} inhibit catalyst deactivation and provide supports from which to build electrocatalytic and photoelectrocatalytic devices. Unfortunately, few details of the effects of surface binding on reactivity are available in the literature. To this end, precursors such as, Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4})(H{sub 2}O) and (C{sub 2}O{sub 4})(H{sub 2}O{sub 3}Ptpy)Ru-O-Ru(H{sub 2}O{sub 3}Ptpy)(C{sub 2}O{sub 4}) (tpy is terpyridine) have been synthesized and attached to TiO{sub 2}. Quantitative surface binding studies were carried out and acid catalyzed solvolysis was used to form the aqua species. The complexes were oxidized with Ce(IV) to their high-valent analogs and their reactivity toward selected substrates was tested. These studies not only provide information about the effects of surface binding on the reactivity of metal oxides but also have implications for the development of light-driven catalysts.},
doi = {},
url = {https://www.osti.gov/biblio/977823},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Jan 01 00:00:00 EST 2004},
month = {Thu Jan 01 00:00:00 EST 2004}
}