Molecular Triad Containing a TEMPO Catalyst Grafted on Mesoporous Indium Tin Oxide as a Photoelectrocatalytic Anode for Visible Light-Driven Alcohol Oxidation.

Photoelectrochemical cells based on semiconductors are among the most studied methods of artificial photosynthesis. This study concerns the immobilization, on a mesoporous conducting indium tin oxide electrode (nano-ITO), of a molecular triad (NDADI-P-Ru-TEMPO) composed of a ruthenium tris-bipyridine complex (Ru) as photosensitizer, connected at one end to 2,2,6,6-tetramethyl-1-piperidine N-oxyl (TEMPO) as alcohol oxidation catalyst and at the other end to the electron acceptor naphthalenedicarboxyanhydride dicarboximide (NDADI). Light irradiation of NDADI-P-Ru-TEMPO grafted to nano-ITO in a pH 10 carbonate buffer effects selective oxidation of para-methoxybenzyl alcohol (MeO-BA) to para-methoxybenzaldehyde with a TON of approximately 150 after 1 h of photolysis at a bias of 0.4 V vs. SCE. The faradaic efficiency is found to be of 80±5 %. The photophysical study indicates that photoinduced electron transfer from the Ru complex to NDADI is a slow process and must compete with direct electron injection into ITO to have a better performing system. This work sheds light on some of the important ways to design more efficient molecular systems for the preparation of photoelectrocatalytic cells based on catalyst-dye-acceptor arrays immobilized on conducting electrodes.