A Mononuclear Co II Coordination Complex Locked in a Confined Space and Acting as an Electrochemical Water‐Oxidation Catalyst: A “Ship‐in‐a‐Bottle” Approach

• Published in: Angewandte Chemie International Edition Vol. 55; no. 7; pp. 2425 - 2430
• Main Authors: Manna, Paulami, Debgupta, Joyashish, Bose, Suranjana, Das, Samar K.
• Format: Journal Article
• Language: English
• Published: 12.02.2016
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201509643

Preparing efficient and robust water oxidation catalyst (WOC) with inexpensive materials remains a crucial challenge in artificial photosynthesis and for renewable energy. Existing heterogeneous WOCs are mostly metal oxides/hydroxides immobilized on solid supports. Herein we report a newly synthesized and structurally characterized metal–organic hybrid compound [{Co 3 (μ 3 ‐OH)(BTB) 2 (dpe) 2 } {Co(H 2 O) 4 (DMF) 2 } 0.5 ] n ⋅ n  H 2 O ( Co‐WOC‐1 ) as an effective and stable water‐oxidation electrocatalyst in an alkaline medium. In the crystal structure of Co‐WOC‐1 , a mononuclear Co II complex {Co(H 2 O) 4 (DMF) 2 } 2+ is encapsulated in the void space of a 3D framework structure and this translationally rigid complex cation is responsible for a remarkable electrocatalytic WO activity, with a catalytic turnover frequency (TOF) of 0.05 s −1 at an overpotential of 390 mV (vs. NHE) in 0.1  m KOH along with prolonged stability. This host–guest system can be described as a “ship‐in‐a‐bottle”, and is a new class of heterogeneous WOC.