Ni-based compounds in multiwalled graphitic shell for electrocatalytic oxygen evolution reactions

Here, we report a general strategy for designing a metal/carbon system, via a facile and environmentally friendly one-step approach, from metal acetate as an active electrocatalyst in oxygen evolution reaction (OER) during water decomposition. As a demonstration, a nanostructured Ni/C composite induced from nickel acetate is revealed in great detail. The resulting material is composed of: metallic nickel (Ni), nickel(II) oxide (NiO), and nickel carbide (Ni₃C) coated with a graphitic shell and deposited on a carbon platform. Our findings underscore the prominent role of nickel species, including Ni⁰, Ni²⁺, and Ni³⁺, in driving the catalytic activity. Notably, the catalyst exhibits an overpotential of 170 mV, a Tafel slope of 49 mV·dec⁻¹, an electrocatalytic surface area (ECSA) of 964.7 cm², and a turnover frequency (TOF) value of 52.8 s⁻¹, surpassing RuO₂. The Raman spectra also suggest a graphitic "self-healing" phenomenon post-OER, attributed to the reduction of oxygen-containing groups. Carbon in the system (i) facilitates electron transfer, (ii) allows homogeneous distribution of Ni nanoparticles avoiding their agglomeration, and (iii) promotes durability of the electrocatalyst by serving as a protective barrier, shielding the core metal compounds. What is more, density functional theory (DFT) calculations allowed to optimized geometry of the model cluster Ni₈O₈(OH)₈ describing two different sites on the β-NiOOH surface (001) and two different intermediates, (i)L-OOH and (ii)L-OOH. This facilitated to propose the reaction mechanisms involving both hydroxide ions and water molecules as reducers. Therefore, the chemisorption of OH⁻ and H₂O molecules at the NiOOH active center accompanied by bond breakage and the formation of a lattice hydroperoxide as an important intermediate is presumed. What is more, the proposed fabrication method for electroactive metal/carbon composites was validated with an iron and iron/nickel mixture.