Understanding the Effect of Second Metal on CoM (M = Ni, Cu, Zn) Metal–Organic Frameworks for Electrocatalytic Oxygen Evolution Reaction

Co-based bimetallic metal-organic frameworks (MOFs) have emerged as a kind of promising electrocatalyst for oxygen evolution reaction (OER). However, most of present works for Co-based bimetallic MOFs are still in try-and-wrong stage, while the OER performance trend and the underlying structure-function relationship remain unclear. To address this challenge, Co-based MOFs on carbon cloth (CC) (CoM MOFs/CC, M = Zn, Ni, and Cu) are prepared through a room-temperature method, and their structure and OER performance are compared systematically. Based on the results of overpotential and Tafel slope, the order of OER activity is ordered in the decreasing sequence: CoZn MOF > CoNi MOF > CoCu MOF > Co MOF. Spectroscopic studies clearly show that the better OER performance of CoM MOFs results from the higher oxidation state of Co, which is related to the choice of second metal. Theoretical calculations indicate that CoZn MOFs possess strengthened adsorption for O-containing intermediate, and lower energy barrier towards OER. This study figures out the effect of second metal on the OER performance of Co-based bimetallic MOFs and suggests that tuning the electronic structure of the metal site can be an effective strategy for other MOFs-based OER catalysts.