Herein, a side chain engineered polythiophene copolymer based organic semiconductor polymer (OSP) with pendant aldehyde groups was synthesized by a combination of Grignard Metathesis (GRIM) polymerization and post-synthetic modifications. The...

We report the synthesis and electrocatalytic activity of poly(3‐hexylthiophene) stabilized nickel oxide nanoparticles (P3HT@NiO NPs). Employing semiconducting P3HT as a stabilizing agent produced well dispersed P3HT@NiO NPs with uniform size distribution (2.5 ± 1.2 nm). For comparison, NiO NPs stabilized with the small molecule 3‐hexylthiophene (3HT@NiO NPs) were also synthesized and characterized as reference material. The physiochemical properties of the developed hybrid P3HT@NiO were fully characterized using UV/Vis absorption spectroscopy, fluorescence spectroscopy, high resolution transmission electron microscopy (HRTEM) and X‐ray photoelectron spectroscopy (XPS). The electrocatalytic activities of the developed semiconducting polymer‐stabilized NPs were evaluated for the oxygen evolution reaction (OER) of water splitting. Our work reveals the electronic communication between P3HT and NiO NPs and demonstrates that P3HT@NiO NPs exhibit superior catalytic activity with an overpotential of 310 mV when compared to the reference 3HT@NiO NPs which exhibited an overpotential 560 mV. These results suggest that the heteroatom‐containing π‐conjugated semiconducting polymers can be employed as electrocatalytic performance enhancing and stabilizing ligands for the synthesis of ultrafine metal‐based NPs as efficient electrocatalytic platforms.