Volume 215, 2019

Photoinduced hole transfer from tris(bipyridine)ruthenium dye to a high-valent iron-based water oxidation catalyst

Abstract

An efficient water oxidation system is a prerequisite for developing solar energy conversion devices. Using advanced time-resolved spectroscopy, we study the initial catalytic relevant electron transfer events in the light-driven water oxidation system utilizing [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) as a light harvester, persulfate as a sacrificial electron acceptor, and a high-valent iron clathrochelate complex as a catalyst. Upon irradiation by visible light, the excited state of the ruthenium dye is quenched by persulfate to afford a [Ru(bpy)3]3+/SO4˙ pair, showing a cage escape yield up to 75%. This is followed by the subsequent fast hole transfer from [Ru(bpy)3]3+ to the FeIV catalyst to give the long-lived FeV intermediate in aqueous solution. In the presence of excess photosensitizer, this process exhibits pseudo-first order kinetics with respect to the catalyst with a rate constant of 3.2(1) × 1010 s−1. Consequently, efficient hole scavenging activity of the high-valent iron complex is proposed to explain its high catalytic performance for water oxidation.

Graphical abstract: Photoinduced hole transfer from tris(bipyridine)ruthenium dye to a high-valent iron-based water oxidation catalyst

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
05 Nov 2018
Accepted
19 Dec 2018
First published
05 Apr 2019
This article is Open Access
Creative Commons BY license

Faraday Discuss., 2019,215, 162-174

Photoinduced hole transfer from tris(bipyridine)ruthenium dye to a high-valent iron-based water oxidation catalyst

S. I. Shylin, Mariia V. Pavliuk, L. D’Amario, I. O. Fritsky and G. Berggren, Faraday Discuss., 2019, 215, 162 DOI: 10.1039/C8FD00167G

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