Issue 42, 2012
From the journal:

Dalton Transactions

A nickel containing polyoxometalate water oxidation catalyst†‡

Guibo Zhu,a   Elliot N. Glass,a   Chongchao Zhao,a   Hongjin Lv,a   James W. Vickers,a   Yurii V. Geletii,a   Djamaladdin G. Musaev,b   Jie Songa  and  Craig L. Hill*a  

* Corresponding authors

a Department of Chemistry, Emory University, Atlanta, GA 30322, USA
E-mail: chill@emory.edu
Fax: +1 404-727-6076
Tel: +1 404-727-6611

b Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, GA 30322, USA

Abstract

A new pentanickel silicotungstate complex, K10H2[Ni5(OH)6(OH2)3(Si2W18O66)]·34H2O (KH-1), has been synthesized and characterized by X-ray crystallography and several other methods. Dynamic light scattering, kinetics and other experiments confirm that 1 in the presence of [Ru(bpy)3]2+ (the photosensitizer for light-driven water oxidations) and [Ru(bpy)3]3+ (the oxidant in the dark water oxidations) exists in an equilibrium between solution (soluble) and a [Ru(bpy)3]n+-1 complex (minimally soluble) form. This new pentanickel polyoxometalate catalyzes efficient water oxidation in both the dark and on irradiation with 455 nm LED light with 1.0 mM [Ru(bpy)3]2+ photosensitizer and 5.0 mM Na2S2O8, sacrificial electron acceptor. Four lines of evidence indicate that 1 in this solution ⇌ Ru(bpy)3]n+-1 complex equilibrium remains molecular and does not decompose to nickel hydroxide particles.

Graphical abstract: A nickel containing polyoxometalate water oxidation catalyst

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Article information

DOI
https://doi.org/10.1039/C2DT30331K
Article type
Paper
Submitted
14 Feb 2012
Accepted
17 Jul 2012
First published
17 Jul 2012

Dalton Trans., 2012,41, 13043-13049

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A nickel containing polyoxometalate water oxidation catalyst

G. Zhu, E. N. Glass, C. Zhao, H. Lv, J. W. Vickers, Y. V. Geletii, D. G. Musaev, J. Song and C. L. Hill, Dalton Trans., 2012, 41, 13043 DOI: 10.1039/C2DT30331K

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