On the Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts
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WangVanVoorhis10a.pdf
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Author(s)
Wang, Lee-Ping
Wu, Qin
Van Voorhis, Troy
Alternative Title
Acid-Base Mechanism for Ruthenium Water Oxidation Catalysts
Date Issued
April 2010
Journal
Inorganic Chemistry
Publisher
American Chemical Society
Citation
Wang, Lee-Ping, Qin Wu, and Troy Van Voorhis. “Acid−Base Mechanism for Ruthenium Water Oxidation Catalysts.” Inorganic Chemistry 49.10 (2010): 4543–4553.
Version
Author's final manuscript
Abstract
We present a detailed theoretical study of the pathway for water oxidation in synthetic ruthenium-based catalysts. As a first step, we consider a recently discovered single center catalyst, where experimental observations suggest a purely single-center mechanism. We find low activation energies (<5 kcal/mol) for each rearrangement in the catalytic cycle. In the crucial step of O−O bond formation, a solvent water acts as a Lewis base and attacks a highly oxidized RuV=O. Armed with the structures and energetics of the single-center catalyst, we proceed to consider a representative Ru-dimer which was designed to form O2 via coupling between the two centers. We discover a mechanism that proceeds in analogous fashion to the monomer case, with all the most significant steps occurring at a single catalytic center within the dimer. This acid−base mechanism suggests a new set of strategies for the rational design of multicenter catalysts: rather than coordinating the relative orientations of the subunits, one can focus on coordinating solvation-shell water molecules or tuning redox potentials.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ic100075k
