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.

Homoleptic Ni(ii) dithiocarbamate complexes as pre-catalysts for the electrocatalytic oxygen evolution reaction

“…Electro-catalysts prepared from first row transition metals, e.g. cobalt, 6 copper, [7][8][9][10] iron, 11,12 and manganese, 13 have attracted tremendous attention due to their economic viability and high abundance. 14 The Earth abundant and biologically important nickel metal in the development of electrocatalysts for water oxidation has also been investigated.…”

Graphitic Carbon Nitride Composites with MoO3-Decorated Co3O4 Nanorods as Catalysts for Oxygen and Hydrogen Evolution

“…The N 1s high-resolution XPS spectrum shown in Figure f is deconvoluted into two peaks. The peaks at binding energies 398.38 and 400.26 eV of the N 1s core level are assigned to sp 2 -hybridized pyridine nitrogen C–NC and C–NH 2 functional groups, respectively. − The rigorous analysis of XRD, TEM, and XPS results concludes that the Co 3 O 4 /MoO 3 /g-C 3 N 4 composite nanorods were successfully synthesized.…”

Mechanism of Iron Integration into LiMn1.5Ni0.5O4 for the Electrocatalytic Oxygen Evolution Reaction

“…Moreover, there is a shift of primary peaks of O 1s toward a higher binding energy with expanding applied current densities, indicating that water reacts with the active site of Fe. 5,44 To comprehend the origin of the remarkable change in the electronic alteration and electrical conductivity caused by Fe doping in LiMn 1.5 Ni 0.5 O 4 , we have collected X-ray absorption near edge structure (XANES). The normalized XANES spectra at Mn K-edge are shown in panels a−c of Figure 5 along with those of Mn metal, MnO (Mn 2+ ), Mn 2 O 3 (Mn 3+ ), and MnO 2 (Mn 4+ ) standards.…”