A Mononuclear CoII Coordination Complex Locked in a Confined Space and Acting as an Electrochemical Water‐Oxidation Catalyst: A “Ship‐in‐a‐Bottle” Approach |
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Authors: | Paulami Manna Dr. Joyashish Debgupta Dr. Suranjana Bose Prof. Samar K. Das |
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Affiliation: | School of Chemistry, University of Hyderabad, Hyderabad, India |
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Abstract: | 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 [{Co3(μ3‐OH)(BTB)2(dpe)2} {Co(H2O)4(DMF)2}0.5]n?n H2O ( 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 CoII complex {Co(H2O)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. |
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Keywords: | electrocatalyst metal– organic frameworks cobalt complexes oxygen evolution water oxidation |
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