Synthesis and electrocatalysis of ordered carbonaceous frameworks from Ni porphyrin with four ethynyl groups

Ordered carbonaceous frameworks (OCFs) are carbon materials possessing three-dimensional ordered structures with regularly-aligned single-atomic metal species. OCFs are characterized by well-defined chemical structures like organic-based frameworks together with high thermal/chemical stability and electrical conductivity, making them an interesting platform for electrocatalytic applications. OCFs are synthesized by a simple thermal treatment of metalloporphyrin crystals with polymerizable moieties, but the reported precursors have been limited to only four types. Herein, we report two new types of Ni porphyrin precursors which can be converted into OCFs. The comprehensive structural analysis of resulting OCFs, including PXRD, TEM, HAADF-STEM, Ni K-edge XAFS and N 2 adsorption measurement, demonstrated that Ni-N 4 coordination units, namely single-atomic Ni sites, are regularly immobilized in the microporous carbon framework. There is a general tendency in which the higher the number of ethynyl moieties, the more the microporosity developed in the resulting OCFs. Furthermore, single-atomic Ni species catalyze electrochemical hydrogen evolution reaction even without any conductive additives. • New types of ordered carbonaceous frameworks (OCFs) were successfully synthesized by rational design of precursor molecules. • Single-atomic Ni species were regularly aligned with Ni-N 4 coordination units in microporous carbonaceous frameworks. • The porosity of resulting OCFs were enhanced by increasing the number of ethynyl moieties in precursor molecules. • The OCFs with the Ni-N 4 coordination units accelerate the electrochemical alkaline hydrogen evolution reaction (HER).