Abstract
Conductive polymers are widely used as active and auxiliary materials for organic photovoltaic cells due to their easily tunable properties, high electronic conductivity, and light absorption. Several conductive polymers show the cathodic photogalvanic effect in pristine state. Recently, photoelectrochemical oxygen reduction has been demonstrated for nickel complexes of Salen-type ligands. Herein, we report an unexpected inversion of the photogalvanic effect caused by doping of the NiSalen polymers with anionic porphyrins. The observed effect was studied by means of UV-Vis spectroscopy, cyclic voltammetry and chopped light chronoamperometry. While pristine NiSalens exhibit cathodic photopolarization, doping with porphyrins inverts the polarization. As a result, photoelectrochemical oxidation of the ascorbate proceeds smoothly on the NiSalen electrode doped with zinc porphyrins. The highest photocurrents were observed on NiSalen polymer with o-phenylene imine bridge, doped with anionic zinc porphyrin. Assuming this, porphyrin serves both as a catalytic center for the oxidation of ascorbate and an internal electron donor, facilitating the photoinduced charge transport and anodic depolarization.
Highlights
Conductive polymers (CP) are a unique class of materials, which combine the benefits of organic materials and electronic conductors
One of the main applications of the CPs is in photovoltaics, where they are used as donor phase [19,20,21] and hole transporting layer [22] materials in organic photovoltaic devices or counter electrode materials for dye-sensitized solar cells (DSSC) [23,24]
An intrinsic photogalvanic effect is known for polythiophene CPs, which indicates the potential of these materials as active layers in DSSC-type architectures [25,26]
Summary
Conductive polymers (CP) are a unique class of materials, which combine the benefits of organic materials and electronic conductors. An increase of the photocurrent was observed with increasing polymer orderliness and rigidity as well as decreasing dopant mobility [29]. Based on this knowledge, recently, the photogalvanic effect on highly rigid NiSalen-type conductive polymers has been discovered [30] and implemented for the photoelectrochemical oxygen reaction reduction reaction (ORR) cell to produce hydrogen peroxide [31]
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