Gd-Doped Ni-Oxychloride Nanoclusters: New Nanoscale Electrocatalysts for High-Performance Water Oxidation through Surface and Structural Modification

Oxygen evolution reaction (OER) is a bottleneck process in the water-splitting module for sustainable and clean energy production. Transition metal-based electrocatalysts can be effective as water-splitting catalytic materials because of their appropriate redox properties and natural abundance, but the slow kinetics because of strong adsorption and consequently slow desorption of intermediates on the active sites of catalysts severely hamper the dynamics of the released molecular oxygen and thus remains a formidable challenge. Herein, we report the development of structurally and surface-modified PA-Gd-Ni(OH)2Cl (partially alkylated gadolinium-doped nickel oxychloride) nanoclusters (NCs, size ≤ 3 nm) for enhanced and stable OER catalysis at low overpotential and high turnover frequency. The ameliorated catalytic performance was achieved by controlling the surface coverage of these NCs with hydrophobic ligands and through the incorporation of electronegative atoms to facilitate easy adsorption/desorption of intermediates on the catalyst surface, thus improving the liberation of O2. Such a surface and structural modification and uniform distribution at the nanoscale length are indeed worth considering to selectively tune the catalytic potential and further modernize the electrode materials for the challenging OER process.