Design of an inherently-stable water oxidation catalyst.

Abstract:

:While molecular water-oxidation catalysts are remarkably rapid, oxidative and hydrolytic processes in water can convert their active transition metals to colloidal metal oxides or hydroxides that, while quite reactive, are insoluble or susceptible to precipitation. In response, we propose using oxidatively-inert ligands to harness the metal oxides themselves. This approach is demonstrated by covalently attaching entirely inorganic oxo-donor ligands (polyoxometalates) to 3-nm hematite cores, giving soluble anionic structures, highly resistant to aggregation, yet thermodynamically stable to oxidation and hydrolysis. Using orthoperiodate (at pH 8), and no added photosensitizers, the hematite-core complex catalyzes visible-light driven water oxidation for seven days (7600 turnovers) with no decrease in activity, far exceeding the documented lifetimes of molecular catalysts under turnover conditions in water. As such, a fundamental limitation of molecular complexes is entirely bypassed by using coordination chemistry to harness a transition-metal oxide as the reactive center of an inherently stable, homogeneous water-oxidation catalyst.

journal_name

Nat Commun

journal_title

Nature communications

authors

Chakraborty B,Gan-Or G,Raula M,Gadot E,Weinstock IA

doi

10.1038/s41467-018-07281-z

subject

Has Abstract

pub_date

2018-11-20 00:00:00

pages

4896

issue

1

issn

2041-1723

pii

10.1038/s41467-018-07281-z

journal_volume

9

pub_type

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