A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals

Qiushi Yin; Jeffrey Miles Tan; Claire Besson; Yurii V. Geletii; Djamaladdin G. Musaev; Aleksey E. Kuznetsov; Zhen Luo; Ken I. Hardcastle; Craig L. Hill

doi:10.1126/science.1185372

A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals

Qiushi Yin
, Jeffrey Miles Tan
, Claire Besson
, Yurii V. Geletii
, Djamaladdin G. Musaev
, Aleksey E. Kuznetsov
, Zhen Luo
, Ken I. Hardcastle
, Craig L. Hill

Chemistry

Binghamton University

Emory University

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

1363 Scopus citations

Abstract

Traditional homogeneous water oxidation catalysts are plagued by instability under the reaction conditions. We report that the complex [Co ₄(H₂O)₂(PW₉O₃₄) ₂]^10-, comprising a Co₄O₄ core stabilized by oxidatively resistant polytungstate ligands, is a hydrolytically and oxidatively stable homogeneous water oxidation catalyst that self-assembles in water from salts of earth-abundant elements (Co, W, and P). With [Ru(bpy)₃]³⁺ (bpy is 2,2'-bipyridine) as the oxidant, we observe catalytic turnover frequencies for O₂ production ≥5 s ^-1 at pH = 8. The rate's pH sensitivity reflects the pH dependence of the four-electron O₂-H₂O couple. Extensive spectroscopic, electrochemical, and inhibition studies firmly indicate that [Co ₄(H₂O)₂(PW₉O₃₄) ₂]^10- is stable under catalytic turnover conditions: Neither hydrated cobalt ions nor cobalt hydroxide/oxide particles form in situ.

Original language	English
Pages (from-to)	342-345
Number of pages	4
Journal	Science
Volume	328
Issue number	5976
DOIs	https://doi.org/10.1126/science.1185372
State	Published - Apr 16 2010

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@article{d0163c6432b14df1964c4bd704961266,

title = "A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals",

abstract = "Traditional homogeneous water oxidation catalysts are plagued by instability under the reaction conditions. We report that the complex [Co 4(H2O)2(PW9O34) 2]10-, comprising a Co4O4 core stabilized by oxidatively resistant polytungstate ligands, is a hydrolytically and oxidatively stable homogeneous water oxidation catalyst that self-assembles in water from salts of earth-abundant elements (Co, W, and P). With [Ru(bpy)3]3+ (bpy is 2,2'-bipyridine) as the oxidant, we observe catalytic turnover frequencies for O2 production ≥5 s -1 at pH = 8. The rate's pH sensitivity reflects the pH dependence of the four-electron O2-H2O couple. Extensive spectroscopic, electrochemical, and inhibition studies firmly indicate that [Co 4(H2O)2(PW9O34) 2]10- is stable under catalytic turnover conditions: Neither hydrated cobalt ions nor cobalt hydroxide/oxide particles form in situ.",

author = "Qiushi Yin and Tan, \{Jeffrey Miles\} and Claire Besson and Geletii, \{Yurii V.\} and Musaev, \{Djamaladdin G.\} and Kuznetsov, \{Aleksey E.\} and Zhen Luo and Hardcastle, \{Ken I.\} and Hill, \{Craig L.\}",

year = "2010",

month = apr,

day = "16",

doi = "10.1126/science.1185372",

language = "English",

volume = "328",

pages = "342--345",

journal = "Science",

issn = "0036-8075",

number = "5976",

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TY - JOUR

T1 - A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals

AU - Yin, Qiushi

AU - Tan, Jeffrey Miles

AU - Besson, Claire

AU - Geletii, Yurii V.

AU - Musaev, Djamaladdin G.

AU - Kuznetsov, Aleksey E.

AU - Luo, Zhen

AU - Hardcastle, Ken I.

AU - Hill, Craig L.

PY - 2010/4/16

Y1 - 2010/4/16

N2 - Traditional homogeneous water oxidation catalysts are plagued by instability under the reaction conditions. We report that the complex [Co 4(H2O)2(PW9O34) 2]10-, comprising a Co4O4 core stabilized by oxidatively resistant polytungstate ligands, is a hydrolytically and oxidatively stable homogeneous water oxidation catalyst that self-assembles in water from salts of earth-abundant elements (Co, W, and P). With [Ru(bpy)3]3+ (bpy is 2,2'-bipyridine) as the oxidant, we observe catalytic turnover frequencies for O2 production ≥5 s -1 at pH = 8. The rate's pH sensitivity reflects the pH dependence of the four-electron O2-H2O couple. Extensive spectroscopic, electrochemical, and inhibition studies firmly indicate that [Co 4(H2O)2(PW9O34) 2]10- is stable under catalytic turnover conditions: Neither hydrated cobalt ions nor cobalt hydroxide/oxide particles form in situ.

AB - Traditional homogeneous water oxidation catalysts are plagued by instability under the reaction conditions. We report that the complex [Co 4(H2O)2(PW9O34) 2]10-, comprising a Co4O4 core stabilized by oxidatively resistant polytungstate ligands, is a hydrolytically and oxidatively stable homogeneous water oxidation catalyst that self-assembles in water from salts of earth-abundant elements (Co, W, and P). With [Ru(bpy)3]3+ (bpy is 2,2'-bipyridine) as the oxidant, we observe catalytic turnover frequencies for O2 production ≥5 s -1 at pH = 8. The rate's pH sensitivity reflects the pH dependence of the four-electron O2-H2O couple. Extensive spectroscopic, electrochemical, and inhibition studies firmly indicate that [Co 4(H2O)2(PW9O34) 2]10- is stable under catalytic turnover conditions: Neither hydrated cobalt ions nor cobalt hydroxide/oxide particles form in situ.

UR - https://www.scopus.com/pages/publications/77951187670

U2 - 10.1126/science.1185372

DO - 10.1126/science.1185372

M3 - Article

SN - 0036-8075

VL - 328

SP - 342

EP - 345

JO - Science

JF - Science

IS - 5976

ER -

A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals

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