Interfacial electronic structure modulations of Au@CuS with defective Ni-doped CoS2 facilitates the electroreduction of N2 into NH3

The nitrogen reduction reaction (NRR) offers a sustainable pathway for ammonia production. However, its effectiveness is hindered by the selective adsorption of nitrogen and the subsequent occurrence of the hydrogen evolution reaction. In this work, a novel and efficient NRR catalyst, Au@CuS heterostructured nanoparticles supported on carbon-coated Ni-doped CoS2 hollow nanocages (Au@CuS/Ni-CoS2/C), was designed and synthesized to enhance the conversion of N2 to NH3 under ambient conditions. The defective Ni-CoS2@C nanocages not only provide a larger surface area for the loading of Au@CuS nanoparticles but also improve conductivity and promote synergistic effects among different components within catalyst. Both experimental investigations and density functional theory (DFT) calculations reveal that the integration of Au and CuS leads to unique inorganic donor–acceptor couplings with electron enriched in Au nanoparticles due to the higher work function of Au compared to CuS. This electron enrichment expedites the adsorption and dissociation of N2 molecules over the electron-rich Au active sites, thereby significantly optimizing the adsorption of intermediates and catalyzing subsequent hydrogenation reduction processes. Benefiting from these synergistic advantages, the resulting Au@CuS/Ni-CoS2/C catalyst exhibited high NRR electrocatalytic activity with an NH3 yield of 25.61 µg h−1 mg−1cat. and a Faraday efficiency of 14.99 % at –0.3 V (vs. reversible hydrogen electrode, RHE), surpassing those of Au@CuS, Ni-CoS2/C, and Au/Ni-CoS2/C. This work presents a new strategy for precisely adjusting the valence state of Au species, thereby facilitating the production of valuable ammonia through NRR.