Structural and Morphological Conversion between Two Co-Based MOFs for Enhanced Water Oxidation.

Abstract

The rapid development of suitable and cheap water oxidation catalysts is of great significance in energy conversion and storage. In this context, herein we have synthesized two different types of metal-organic frameworks (MOFs, denoted as BMM-11 and BMM-12) constructed from the same metal salts (cobalt nitrate) and organic linkers (H4BPTC) at the similar solvothermal conditions. Interestingly, we learned that both crystalline materials can be conveniently converted into each other by a single-crystal-to-single-crystal transformation method at their corresponding synthetic conditions. Meanwhile, we applied them directly as electrocatalysts into OER application where the pure BMM-11 and BMM-12 can achieve a stable current density of 10 mA cm-2 with an overpotential of 0.362 and 0.393 V, respectively, during which MOF degradation unexpectedly occurs. After electrolysis, the following microscopic, spectroscopic, as well as electrochemical measurements confirm that these initial MOF precursors are rapidly transformed into the mixed phases of CoOxHy species consisting of CoOOH and Co(OH)2, which are essentially active components for OER performance. Finally, we have also considered other strategies to improve MOF-derived composites in oxygen evolution activity, including bimetallic doping and physical grinding strategy. The approach described here can further be extended to other cobalt-based MOFs-derived electrocatalysts for water splitting.