Bimetallic NiCo Metal-Organic Frameworks with High Stability and Performance Toward Electrocatalytic Oxidation of Urea in Seawater.

Abstract

The urea oxidation reaction (UOR) is an alternative anodic reaction for hydrogen generation via water splitting. The significance of UOR lies in both H2 production and the decontamination of urea-containing wastewater. Commercial electrocatalysts in this field are generally based on noble metals and show several limitations. Bimetal-organic frameworks (BMOFs) can be excellent candidates for the replacement of noble-metal-based catalysts beacuse of their promising features, such as a tunable structure, high surface area, and abundant sites for electrocatalysis. In this study, a series of nickel-cobalt BMOFs (Nix-Coy-BMOFs: x and y refer to a molar fraction of Ni and Co) were synthesized and applied as electrocatalysts in UOR. In particular, a Ni0.15Co0.85-MOF material with a structure similar to that of its parent Co-MOF, revealed exceptional electrocatalytic performance, as evidenced by low values of overpotential (1.33 V vs RHE at 10 mA cm-2), TOF (0.47 s-1), and Tafel slope (125 mV dec-1). At a 40 mA cm-2 current density, Ni0.15Co0.85-MOF also showed excellent stability during the 72 h tests. This performance of NiCo-BMOF can be assigned to the synergistic effect between Co and Ni, abundant active sites, porosity, and a tunable structure, all of which result in an increased reaction rate due to the acceleration of charge and mass transfers. Thus, the present work introduces an efficient noble-metal-free UOR for energy generation from urea-based wastewater.