Understanding coordination modification strategy on metal organic framework-based system for efficient water oxidation

[Display omitted] •The coordination environment modification strategy is introduced in MIL-59 MOFs.•Heterostructure within MIL-59(FeNi)/Co NSs is crucial for improved OER activity.•MIL-59(FeNi)/Co NSs can serve as efficient electrocatalysts towards OER.•DFT calculations prove favorable charge transfers between Co substrate and MIL-59. Rational modification of coordination environment on metal–organic frameworks (MOFs) have a strong impact on the performance of heterogeneous catalysis. Here, we demonstrate how tuning the surrounding environment on metals centers of MOFs can substantially enhance the oxygen evolution reaction (OER) efficiency. The MIL-59(FeNi)/Co NSs nano-heterostructure was formed by anchoring MIL-59(FeNi) MOFs on urchin-like Co nanosheet arrays. Metal-metal synergistic effect was validated to influence the coordination environment on MOFs, DFT calculations suggests that the charge transfer from the Co substrate to MIL-59 on a formed –COOCo geometry should be responsible for excellent activity. Acting as OER electrocatalyst, the MIL-59(FeNi)/Co NSs requires a low overpotential of 216 mV to arrive at 20 mA cm−2 and obtains a low Tafel slope value of 38.46 mV dec−1. The facile synthetic route and proposed strategy would arouse more attention to design and utilize high-performance metal-hybrid supported MOFs for highly efficient electrochemical processes.