Redox-active ligands enhance oxygen evolution reaction activity: Regulating the spin state of ferric ions and accelerating electron transfer.

Metal-organic frameworks (MOFs) are considered as one of the most promising catalysts for oxygen evolution reaction (OER). However, only a few have introduced redox-active ligands into MOFs and explored their role in the OER process. In this work, we synthesized FeNi DHBQ/NF using the redox-active ligand 2,5-dihydroxy-1,4-benzoquinone (DHBQ), which exhibited excellent redox activity and required only 207 and 242 mV overpotentials to achieve current densities of 10 and 100 mA cm. Our research confirms that (i) the doping of Fe leads to the formation of Ni → O → Fe electron transfer channels in the MOFs and stronger electron transfer, attributed to the stronger d-π conjugation between the metal center and the ligand and reduced the d-orbital crystal field splitting energy of Fe; (ii) the rate determination step (RDS) in the OER process of the catalyst is the formation of O*, while Fe and redox-active ligands effectively regulate the adsorption energy of oxygen-containing intermediates, reducing the energy barrier of the RDS; (iii) the redox-active ligands can act as "electron reservoirs" in the electrochemical process, making Ni more readily oxidized to Ni or even Ni at low potentials, which is beneficial to the subsequent OER process.