Water exchange reactivity and stability of cobalt polyoxometalates under catalytically relevant pH conditions: Insight into water oxidation catalysis

Journal article
(Original article)


Publication Details

Author(s): Lieb D, Zahl A, Wilson EF, Streb C, Nye L, Meyer K, Ivanovic-Burmazovic I
Journal: Inorganic Chemistry
Publisher: American Chemical Society
Publication year: 2011
Volume: 50
Journal issue: 18
Pages range: 9053-9058
ISSN: 0020-1669


Abstract


Water exchange on a molecular, purely inorganic cobalt-based water oxidation catalyst, [Co (H O) (α-P W O ) ] (1), in the catalytically relevant pH region (pH 6-10) is studied using O-NMR spectroscopy and ultrahigh-resolution electrospray ionization mass spectrometry. The results are compared with those of the inactive [Co (H O) Si W O ] (2), which is stable in the same pH region. The results obtained provide mechanistic details of the elementary reaction step related to the water oxidation on homogeneous metal oxide catalysts under catalytically relevant conditions. It is shown that the structural integrity of 1 and 2 is maintained, no deprotonation of the aqua ligands on the Co(II) centers occurs, and the water exchange does not undergo any mechanistic changeover at the catalytic pH conditions. We have demonstrated that the water exchange process is influenced by the cluster environment surrounding the water binding sites and is fast enough to not be rate-limiting for the water oxidation catalysis. © 2011 American Chemical Society.



FAU Authors / FAU Editors

Ivanovic-Burmazovic, Ivana Prof. Dr.
Lehrstuhl für Bioanorganische Chemie
Lieb, Dominik Dr.
Sonderforschungsbereich 583 Redoxative Metallkomplexe - Reaktivitätssteuerung durch molekulare Architekturen (Sprecher: Prof.Dr.Kisch)
Meyer, Karsten Prof. Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Nye, Leanne
Sonderforschungsbereich 583 Redoxative Metallkomplexe - Reaktivitätssteuerung durch molekulare Architekturen (Sprecher: Prof.Dr.Kisch)
Streb, Carsten Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Zahl, Achim Dr.
Lehrstuhl für Bioanorganische Chemie


How to cite

APA:
Lieb, D., Zahl, A., Wilson, E.F., Streb, C., Nye, L., Meyer, K., & Ivanovic-Burmazovic, I. (2011). Water exchange reactivity and stability of cobalt polyoxometalates under catalytically relevant pH conditions: Insight into water oxidation catalysis. Inorganic Chemistry, 50(18), 9053-9058. https://dx.doi.org/10.1021/ic201243n

MLA:
Lieb, Dominik, et al. "Water exchange reactivity and stability of cobalt polyoxometalates under catalytically relevant pH conditions: Insight into water oxidation catalysis." Inorganic Chemistry 50.18 (2011): 9053-9058.

BibTeX: 

Last updated on 2019-11-04 at 21:50