TY - JOUR

T1 - Inversion of the photogalvanic effect of conductive polymers by porphyrin dopants

AU - Petrov, Alexey A.

AU - Lukyanov, Daniil A.

AU - Kopytko, Oleg A.

AU - Novoselova, Julia V.

AU - Alekseeva, Elena V.

AU - Levin, Oleg V.

N1 - Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzer. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/6/12

Y1 - 2021/6/12

N2 - Conductive polymers are widely used as active and auxiliary materials for organic pho-tovoltaic cells due to their easily tunable properties, high electronic conductivity, and light absorp-tion. 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 NiSa-lens exhibit cathodic photopolarization, doping with porphyrins inverts the polarization. As a re-sult, 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.

AB - Conductive polymers are widely used as active and auxiliary materials for organic pho-tovoltaic cells due to their easily tunable properties, high electronic conductivity, and light absorp-tion. 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 NiSa-lens exhibit cathodic photopolarization, doping with porphyrins inverts the polarization. As a re-sult, 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.

KW - Electrodeposition

KW - NiSalen

KW - Photocurrent

KW - Photovoltaics

KW - Porphyrin

KW - THIN-FILMS

KW - OXIDATION

KW - porphyrin

KW - COMPLEXES

KW - photocurrent

KW - NONAQUEOUS SOLUTIONS

KW - COUNTER ELECTRODES

KW - CONJUGATED POLYMERS

KW - SYSTEMS

KW - ENERGY-TRANSFER

KW - electrodeposition

KW - DERIVATIVES

KW - photovoltaics

KW - PHOTOELECTROCHEMICAL BEHAVIOR

UR - http://www.scopus.com/inward/record.url?scp=85107703831&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/be89b7f2-f816-3afd-8631-f883d08ef529/

U2 - 10.3390/catal11060729

DO - 10.3390/catal11060729

M3 - Article

AN - SCOPUS:85107703831

VL - 11

JO - Catalysts

JF - Catalysts

SN - 2073-4344

IS - 6

M1 - 729

ER -