Distal Synergistic Effect in Bimetal–Organic Framework for Superior Catalytic Water Oxidation
Umashis Bhoi, Subhasmita Ray, Sujit Bhand, Pranay Ninawe, Debashree Roy, Shammi Rana, Kartick Tarafder, Nirmalya Ballav
Abstract
Metal–organic frameworks (MOFs) are emerging as promising electro-catalysts for the oxygen evolution reaction (OER). The bimetallic design strategy was further adopted in MOFs to elevate the OER performance by a synergistic effect. The proximal metal–oxygen–metal bonding configuration with typical 3 d π –2 p π –3 d π interaction was apparently essential for an effective electronic coupling between the metal centers. Here, we report an example of distal synergy in a bimetal–organic framework exhibiting a better OER activity than the monometallic counterparts, as well as the conventional proximal synergy. To achieve a current density of 10 mA·cm –2, our electrodeposited bimetallic MOF, Co–Ni(TCNQ) 2 (H 2 O) 2 (TCNQ = 7,7,8,8-tetracyanoquinodimethane), on a glassy-carbon electrode required an overpotential value of 220 mV. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations revealed distinctive electronic coupling between the Co(II)-3 d 7 and Ni(II)-3 d 8 centers, despite being 9 Å apart, leading to an overall charge delocalization in the structure via TCNQ.