Development of 3D interconnected carbon materials derived from Zn-MOF-74@carbon nanofiber web as an efficient metal-free electrocatalyst for oxygen reduction

A novel 3D interconnected web-like carbon material with high electrocatalytic activities toward oxygen reduction reaction (ORR) has been developed for the first time via direct carbonization of a composite (Zn-MOF-74@CNFs) comprising Zn-MOF-74s grown on carbon nanofibers (CNFs) web. The hexagonal pillar shaped Zn-MOF-74s with a diameter which ranges from 300 to 600 nm grow along the CNFs web by solvothermal method. After carbonization of Zn-MOF-74@CNFs, effective interconnections promoting electron transfer are successfully formed between carbonized Zn-MOF-74 (C-Zn-MOF-74) and on CNFs as well as C-Zn-MOF-74 themselves. The extraordinary 3D structure thus fabricated significantly improves the electrocatalytic activity toward ORR. The calculated electron transfers number (n) values for carbonized Zn-MOF-74@CNFs (C-Zn-MOF-74@CNFs) are nearly 4 at potentials ranging from 0.4 to 0.6 V (vs. reversible hydrogen electrode), demonstrating that the ORR process occurs dominantly through a direct four-electron pathway. Tafel slope of C-Zn-MOF-74@CNFs at low over-potential are lower than those from C-Zn-MOF-74 and even commercial Pt/C. Durability is also found to exceed that of commercial Pt/C. This study provides a novel 3D interconnected carbon material as a non-metal ORR electrocatalyst and design strategy for a large-area, self-standing and binder-free carbon-based electrochemical electrode.