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

Abstract 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 (Ni 3 C) coated with a graphitic shell and deposited on a carbon platform. Our findings underscore the prominent role of nickel species, including Ni 0 , Ni 2+ , and Ni 3+ , 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 cm 2 , and a turnover frequency (TOF) value of 52.8 s −1 , surpassing RuO 2 . 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 Ni 8 O 8 (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 H 2 O 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.