What factors control O2 binding and release thermodynamics in mononuclear ruthenium water oxidation catalysts? A theoretical exploration

Guiling Zhang; Kejuan Chen; Hui Chen; Jiannian Yao; Sason Shaik

doi:10.1021/ic3028644

What factors control O₂ binding and release thermodynamics in mononuclear ruthenium water oxidation catalysts? A theoretical exploration

Guiling Zhang, Kejuan Chen, Hui Chen^*, Jiannian Yao, Sason Shaik

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

19 Scopus citations

Abstract

Mononuclear Ru-based water oxidation catalysts (WOCs) constitute an important class of WOCs for water splitting. This work constitutes a systematic study of Ru-O₂ complexes of mononuclear ruthenium WOCs, with a focus on the thermodynamics of water-assisted O₂ release in various electronic states and conformations. Our extensive DFT study reveals several factors that affect the O₂ release thermodynamics: (1) steric effect from the ligand sphere of Ru; (2) trans effect of ligands trans to O ₂; (3) oxygen cis coordinating effect; (4) carbon coordinating effect; and (5) Ru coordination strength. Some of these effects could selectively stabilize/destabilize some states/conformations of the Ru-O ₂ complexes relative to Ru-OH₂ complexes, and affect thereby the O₂ release thermodynamics. The identification and rationalization of factors for O₂ release thermodynamics, as in this work, could be helpful toward a better understanding of this final step of the ruthenium-catalyzed water oxidation.

Original language	English
Pages (from-to)	5088-5096
Number of pages	9
Journal	Inorganic Chemistry
Volume	52
Issue number	9
DOIs	https://doi.org/10.1021/ic3028644
State	Published - 6 May 2013

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title = "What factors control O2 binding and release thermodynamics in mononuclear ruthenium water oxidation catalysts? A theoretical exploration",

abstract = "Mononuclear Ru-based water oxidation catalysts (WOCs) constitute an important class of WOCs for water splitting. This work constitutes a systematic study of Ru-O2 complexes of mononuclear ruthenium WOCs, with a focus on the thermodynamics of water-assisted O2 release in various electronic states and conformations. Our extensive DFT study reveals several factors that affect the O2 release thermodynamics: (1) steric effect from the ligand sphere of Ru; (2) trans effect of ligands trans to O 2; (3) oxygen cis coordinating effect; (4) carbon coordinating effect; and (5) Ru coordination strength. Some of these effects could selectively stabilize/destabilize some states/conformations of the Ru-O 2 complexes relative to Ru-OH2 complexes, and affect thereby the O2 release thermodynamics. The identification and rationalization of factors for O2 release thermodynamics, as in this work, could be helpful toward a better understanding of this final step of the ruthenium-catalyzed water oxidation.",

author = "Guiling Zhang and Kejuan Chen and Hui Chen and Jiannian Yao and Sason Shaik",

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AU - Zhang, Guiling

AU - Chen, Kejuan

AU - Chen, Hui

AU - Yao, Jiannian

AU - Shaik, Sason

PY - 2013/5/6

Y1 - 2013/5/6

N2 - Mononuclear Ru-based water oxidation catalysts (WOCs) constitute an important class of WOCs for water splitting. This work constitutes a systematic study of Ru-O2 complexes of mononuclear ruthenium WOCs, with a focus on the thermodynamics of water-assisted O2 release in various electronic states and conformations. Our extensive DFT study reveals several factors that affect the O2 release thermodynamics: (1) steric effect from the ligand sphere of Ru; (2) trans effect of ligands trans to O 2; (3) oxygen cis coordinating effect; (4) carbon coordinating effect; and (5) Ru coordination strength. Some of these effects could selectively stabilize/destabilize some states/conformations of the Ru-O 2 complexes relative to Ru-OH2 complexes, and affect thereby the O2 release thermodynamics. The identification and rationalization of factors for O2 release thermodynamics, as in this work, could be helpful toward a better understanding of this final step of the ruthenium-catalyzed water oxidation.

AB - Mononuclear Ru-based water oxidation catalysts (WOCs) constitute an important class of WOCs for water splitting. This work constitutes a systematic study of Ru-O2 complexes of mononuclear ruthenium WOCs, with a focus on the thermodynamics of water-assisted O2 release in various electronic states and conformations. Our extensive DFT study reveals several factors that affect the O2 release thermodynamics: (1) steric effect from the ligand sphere of Ru; (2) trans effect of ligands trans to O 2; (3) oxygen cis coordinating effect; (4) carbon coordinating effect; and (5) Ru coordination strength. Some of these effects could selectively stabilize/destabilize some states/conformations of the Ru-O 2 complexes relative to Ru-OH2 complexes, and affect thereby the O2 release thermodynamics. The identification and rationalization of factors for O2 release thermodynamics, as in this work, could be helpful toward a better understanding of this final step of the ruthenium-catalyzed water oxidation.

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What factors control O₂ binding and release thermodynamics in mononuclear ruthenium water oxidation catalysts? A theoretical exploration

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