Heptanuclear brucite disk with cyanide bridges in a cocrystal and tracking its pyrolysis to an efficient oxygen evolution electrode.

The development of efficient oxygen evolution reaction (OER) catalysts is still lacking in exploration of the mechanism of controlled pyrolysis of precursors among new material platforms. Here, a novel Co-based coordination molecular cluster has been first introduced as precursor to obtain metallic cobalt core shelled by N-doped carbon (Co@NC) structure which operates as an oxygen evolution electrode. Specifically, a new cocrystal compound, [Co(μ-CN)(mmimp)] [CoClN(CN)]·3CHOH (Co, mmimp = 2-methoxy-6-((methylimino)-methyl)phenol), was isolated consisting of Brucite disks of cobalt where the usual bridging μ-OH is replaced by μ-CN produced by the in-situ decomposition of dicyanamide (N≡C-N-C≡N). The cobalt atoms are bonded through the nitrogen atom of the cyanide. Remarkably, time dependent thermogravimetric-mass spectrometry (TG-MS) analysis was utilized to track its pyrolysis process. It allowed us to propose a possible formation process of the Co@NC structure from Co. Interestingly, an extremely superior OER electrode is optimized for Co@NC-600 having the lowest overpotential of 257 mV at 10 mA/cm in 1 mol/L KOH solution. The present study pins down the importance of clusters of transition metals on realizing distinct nanostructures operating as highly efficient OER electrocatalyst.