Interfacial Engineering of CuCo₂S₄/g-C₃N₄ Hybrid Nanorods for Efficient Oxygen Evolution Reaction

Abstract

Altering the morphology of electrochemically active nanostructured materials could fundamentally influence their subsequent catalytic as well as oxygen evolution reaction (OER) performance. Enhanced OER activity for mixed-metal spinel-type sulfide (CuCo₂S₄) nanorods is generally done by blending the material that has high conductive supports together with those having a high surface volume ratio, for example, graphitic carbon nitrides (g-C₃N₄). Here, we report a noble-metal-free CuCo₂S₄ nanorod-based electrocatalyst appropriate for basic OER and neutral media, through a simple one-step thermal decomposition approach from its molecular precursors pyrrolidine dithiocarbamate-copper(II), Cu[PDTC]₂, and pyrrolidine dithiocarbamate-cobalt(II), Co[PDTC]₂ complexes. Transmission electron microscopy (TEM) images as well as X-ray diffraction (XRD) patterns suggest that as-synthesized CuCo₂S₄ nanorods are highly crystalline in nature and are connected on the g-C₃N₄ support. Attenuated total reflectance-Fourier-transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy studies affirm the successful formation of bonds that bridge (Co-N/S-C) at the interface of CuCo₂S₄ nanorods and g-C₃N₄. The kinetics of the reaction are expedited, as these bridging bonds function as an electron transport chain, empowering OER electrocatalytically under a low overpotential (242 mV) of a current density at 10 mA cm^-2 under basic conditions, resulting in very high durability. Moreover, CuCo₂S₄/g-C₃N₄ composite nanorods exhibit a high catalytic activity of OER under a neutral medium at an overpotential of 406 mV and a current density of 10 mA cm^-2.