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ACS Appl Mater Interfaces. 2018 Nov 7;10(44):37948-37954. doi: 10.1021/acsami.8b11041. Epub 2018 Oct 23.

Architecture of Biomimetic Water Oxidation Catalyst with Mn4CaO5 Clusterlike Structure Unit.

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State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry , Jilin University , Changchun 130012 , China.
Inner Mongolia Key Laboratory of Carbon Nanomaterials, Nano Innovation Institute (NII), College of Chemistry and Chemical Engineering , Inner Mongolia University for the Nationalities (IMUN) , Tongliao 028000 , People's Republic of China.


Mn4CaO5 cluster in green plant is considered as the ideal structure for water oxidation catalysis. However, this structure is difficult to be constructed in heterogeneous catalyst because of its distorted spatial structure and unique electronic state. Herein, we report the synthesis of two-dimensional biomimetic Ca-Mn-O catalyst with Mn4CaO5 clusterlike structure through ultrasonic-assisted reduction treatment toward Ca-birnessite. The synergistic effect between ultrasonic and reduction successfully reduced the Mn oxidation state in Ca-birnessite without breaking the structure of MnO2 monolayers, forming a regular two-dimensional structure with Mn4CaO5 cubanelike structure unit for the first time. The biomimetic catalyst shows a superior water oxidation activity (turnover frequency = 3.43 s-1), which is the best in manganese-based heterogeneous catalyst to date. This work provides a new strategy for the precise synthesis of specific structure and exhibits a great prospect of biomimic in heterogeneous catalyst.


Ca-birnessite; architecture; biomimetic; water oxidation


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