Stabilization of the redox polymer [Os(bipy)₂(PVP)₁₀Cl]Cl by in situ chemical cross‐linking

Abstract

The redox polymer [O~(bipy)~(P~TP),~CllCl, where bipy is 2,2'-bipyridyl and PLT is poly-4-vinylpyridine, has been physically stabilized by chemical cross-linking at various levels via the solid-state reaction with the cross-linking agents p-dibromobenzene, 1 ,j-dibromopentane, and 1 ,lo-dibromodecane. The stability of the resulting polymer films under the severe hydrodynamic conditions of thin-layer flow cells and at rotating disk electrodes (RDEs) was greatly increased compared to the uncross-linked polymer. The charge transport properties of the redox polymer were maintained or improved by cross-linking. The surface and Nernstian behavior of the cross-linked redox materials are not found to be substantially affected by cross-linking.

A Neutron Reflectivity Study of [ Os ( bipy ) 2 ( PVP ) 10Cl ] + Polymer Film Modified Electrodes: Effect of pH and Counterion

“…The second term is the film factor which accounts for the interference effects of neutrons reflected from the different interfaces of the film and is dependent on the scattering length density gradient [2] It is impossible to deconvolute the reflectivity profile into a scattering ].ength density profile due to a lack of phase information. This is seen as a region of unit reflectivity at small values of Q. Q. is related to the scattering length density change, (Nb), causing the total reflection by = 16'rrA(Nb) [4] In summary, the form of the reflectivity profile is dependent upon the film thickness and the scattering length densities. There are some model independent parameters which can be derived from a reflectivity profile, Reflection of neutrons from either interface of a thin film leads to constructive and destructive interference analogous to classical optics.…”

“…When a positive step in the scattering length density profile occurs, neutrons with momentum transfers below a critical value, Q, are totally reflected. This is seen as a region of unit reflectivity at small values of Q. Q. is related to the scattering length density change, (Nb), causing the total reflection by = 16'rrA(Nb) [4] In summary, the form of the reflectivity profile is dependent upon the film thickness and the scattering length densities. In some cases it can be used to directly obtain information on the film thickness and steps in Nb, but to obtain the complete Nb profile modeling must be used.…”