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A Self‐Improved Water‐Oxidation Catalyst: Is One Site Really Enough?
Author(s) -
López Isidoro,
Ertem Mehmed Z.,
Maji Somnath,
BenetBuchholz Jordi,
Keidel Anke,
Kuhlmann Uwe,
Hildebrandt Peter,
Cramer Christopher J.,
Batista Victor S.,
Llobet Antoni
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201307509
Subject(s) - catalysis , homogeneous , chemistry , homogeneous catalysis , transition metal , kinetic energy , redox , chemical engineering , process (computing) , turnover number , catalytic oxidation , materials science , combinatorial chemistry , inorganic chemistry , organic chemistry , thermodynamics , computer science , physics , quantum mechanics , engineering , operating system
The homogeneous catalysis of water oxidation by transition‐metal complexes has experienced spectacular development over the last five years. Practical energy‐conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water‐oxidation catalyst that is generated by self‐assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water‐oxidation catalyst that does not decompose over extended periods of time.