Empowering the Water Oxidation Activity of the Bimetallic Metal-Organic Framework by Annexing Gold Nanoparticles over the Catalytic Surface.

Electrocatalytic water splitting to an anodic oxygen evolution reaction (OER) and a cathodic hydrogen evolution reaction (HER) is believed to be the most important application for sustainable hydrogen generation. Being a four-electron, four-proton transfer process, the OER plays the main obstacle for the same. Therefore, designing an effective electrocatalyst to minimize the activation energy barrier for the OER is a research topic of prime importance. The metal-organic framework (MOF) with a highly porous network is considered an appropriate candidate for the OER in alkaline conditions. Apart from several MOFs, the bimetallic one has an advantageous electrocatalytic performance due to the synergistic electronic interaction between two metal ions. However, most bimetallic MOFs have an obstacle to electrocatalytic application due to their low conductive nature, and therefore, they possess a barrier for charge transfer kinetics at the interface. Surface functionalization via various nanoparticles (NPs) is believed to be the most effective strategy for nullifying the conductive issue. In this work, we have designed a CoNi-based bimetallic MOF that was surface-functionalized by Au NPs (Au@CoNi-Bpy-BTC) for the OER under alkaline conditions. Au@CoNi-Bpy-BTC required an overpotential of just 330 mV, which is 56 mV lower as compared to the pristine MOF. Impedance analysis confirms an improved conductivity and charge transfer at the interface, where Au@CoNi-Bpy-BTC possesses a lower R ct value than CoNi-Bpy-BTC materials. Moreover, the Au-decorated MOF shows an 8.5 times increase in the TOF value compared to the pristine MOF. Therefore, this noble strategy toward the surface functionalization of MOFs via noble metal NPs is believed to be the most effective strategy for developing effective electrocatalysts for electrocatalytic application in energy-related fields. Overall, this report displays an exceptional correlation between the decorated NPs over the MOF surface, which can regulate the OER activity, as confirmed by experimental analysis.