Remedy for Collapse of ZIF Derived Carbon: Micro-Pore Filled Synthesis to Improve ORR Catalytic Property

Zeolitic imidazolate framework (ZIF) derived carbons deliver outstanding performance as oxygen reduction reaction (ORR) catalysts. However, their electrocatalytic activities are limited due to unavoidable collapse of ZIFs upon pyrolysis, which results in degradation of porosity, sintering of metals and loss of active sites. In this work, a micro-pore filling strategy was employed to strength the architecture of ZIF by using size matched cyanamide molecules as fillers. The cyanamide with high nitrogen content shows a triple effect in stabilizing the carbonaceous skeleton, preserving of metal containing active sites and improving the conductivity of matrix. Therefore, the as-prepared Fe, Co co-doped ZIF derived carbon (FeCo@NC-N) delivers a significantly improved electrochemical activity for ORR than its unfilled counterpart, with half-wave potential upshifted by 30 mV (0.84 V vs RHE). Besides, a promoted power density of home-assembled zinc-air battery is obtained when FeCo@NC-N is applied as cathode catalyst. This work demonstrates a reliable approach to mitigate framework collapse of metal organic framework (MOF), thus may open a new way for fabrication of MOF based catalysts with increased loading of pores and active sites.