- An Electrode-Supported Oxidation Catalyst Based on Ruthenium(IV). pH "Encapsulation" in a Polymer Film
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The known oxidative catalytic behavior of ions (bpy)2(py)RuO2+ (bpy is 2,2'-bipyridine; py is pyridine) and (trpy)(bpy)RuO2+ (trpy is 2,2',2''-terpyridine) has been successfully transferred to electrode surfaces.The electrodes were chemically modified by deposition of thin polymeric films containing the (bpy)2(H2O)RuII group bound to poly-4-vinylpyridine.Upon oxidation to RuIV on the surface, catalytic oxidation currents are observed for the modified electrodes in the presence of 2-propanol, p-toluic acid, and the xylenes with an added surfactant.The effective catalytic lifetimes of the films are limited (>30 turnovers per redox site) by a competing reaction within the polymer film which changes the nature of the redox sites.An unusual pH effect has been observed in the polymer films.Below pH 4, potentials measured by cyclic voltammetry for the bound III(py)(*)>2+/II(py)(*)>2+ and IV(py)(*)>2+/III(py)(*)>2+ couples change with pH as expected.Above pH 4, where the unbound pyridyl groups in the polymer become deprotonated, up to pH 9.2 the redox couples no longer respond to pH changes in the bulk solution.The difference in the pH behavior between the polymer in solution and on the electrode surface has allowed us to observe the deposition process by cyclic voltammetry.In acid solution, the polymer film is open and large amounts of ferri- or ferrocyanide ions can be incorporated reversibly into the films by ion exchange.Over a longer time period, the cyano ions are permanently bound in the films, apparently by the formation of a cyano-bridged Fe-Ru dimer.
- Samuels, George J.,Meyer, Thomas J.
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- MICROPOROUS COORDINATION COMPLEX AND METHOD OF MAKING THE SAME
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Disclosed herein is a three-dimensional coordination complex that includes a plurality of inorganic centers; a plurality of a first bis(bidentate) linker; and a plurality of a second bis(bidentate) linker, where the first and the second bis(bidentate) linkers are have different lengths, and the bidentate binding sites on each linker face in opposite directions on an axis.
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Paragraph 0065
(2014/09/03)
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- Novel Electrocatalytic Procedure for the Oxidation of Alcohols, Aldehydes, Cyclic Ketones, and C-H Bonds Adjacent to Olefinic or Aromatic Groups
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A novel electrocatalytic procedure is described for the oxidation of primary and secondary alcohols, cyclic ketones, and C-H bonds adjacent to aromatic or olefinic groups.The procedure involves the use of the RuIVoxidant 2+ (trpy is 2,2',2''-terpyridine; bpy is 2,2'-bipyridine) in water at pH 6.8 or in dimethyl sulfone-water mixtures and is based on a electrochemical "shuttle" mechanism in which the RuIV complex is regenerated by electrochemical oxidation of II(trpy)(bpy)(H2O)>2+.
- Thompson, Mark S.,Giovani, Wagner F. De,Moyer, Bruce A.,Meyer, Thomas J.
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p. 4972 - 4977
(2007/10/02)
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