Mechanistic Analysis of Water Oxidation Catalyst cis-[Ru(bpy)2(H2O)2]2+: Effect of Dimerization

Erdman, Darren; Pineda-Galvan, Yuliana; Pushkar, Yulia

doi:10.3390/catal7020039

Mechanistic Analysis of Water Oxidation Catalyst cis-[Ru(bpy)2(H2O)2]2+: Effect of Dimerization

Journal Article · Tue Jan 24 23:00:00 EST 2017 · Catalysts

DOI:https://doi.org/10.3390/catal7020039· OSTI ID:2370601

Erdman, Darren; Pineda-Galvan, Yuliana; Pushkar, Yulia

While the catalytic activity of some Ru-based polypyridine complexes in water oxidation is well established, the relationship between their chemical structure and activity is less known. In this work, the single site Ru complex [Ru(bpy)2(H2O)2]2+ (bpy = 2,2′-bipyridine)—which can exist as either a cis isomer or a trans isomer—is investigated. While a difference in the catalytic activity of these two isomers is well established, with cis-[Ru(bpy)2(H2O)2]2+ being much more active, no mechanistic explanation of this fact has been presented. The oxygen evolving capability of both isomers at multiple concentrations has been investigated, with cis-[Ru(bpy)2(H2O)2]2+ showing a second-order dependence of O2 evolution activity with increased catalyst concentration. Measurement of the electron paramagnetic resonance (EPR) spectrum of cis-[Ru(bpy)2(H2O)2]2+, shortly after oxidation with CeIV, showed the presence of a signal matching that of cis,cis-[RuIII(bpy)2(H2O)ORuIV(bpy)2(OH)]4+, also known as “blue dimer”. The formation of dimers is a concentration-dependent process, which could serve to explain the greater than first order increase in catalytic activity. The trans isomer showed a first-order dependence of O2 evolution on catalyst concentration. Behavior of [Ru(bpy)2(H2O)2]2+ isomers is compared with other Ru-based catalysts, in particular [Ru(tpy)(bpy)(H2O)]2+ (tpy = 2,2′;6,2′′-terpyridine).

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Sponsoring Organization:: USDOE

OSTI ID:: 2370601

Alternate ID(s):: OSTI ID: 1358441

Journal Information:: Catalysts, Journal Name: Catalysts Journal Issue: 2 Vol. 7; ISSN CATACJ; ISSN 2073-4344

Publisher:: MDPI AGCopyright Statement

Country of Publication:: Switzerland

Language:: English

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