Sulfur-doped graphene anchoring of ultrafine Au25 nanoclusters for electrocatalysis

The biggest challenge of exploring the catalytic properties under-coordinated nanoclusters is issue stability. We demonstrate herein that chemical dopants on sulfur-doped graphene (S-G) can be utilized to stabilize ultrafine (sub-2 nm) Au25(PET)18 clusters enable stable nitrogen reduction reaction (NRR) without significant structural degradation. Au25@S-G exhibits an ammonia yield rate $$27.5\,{\rm{\mu }}{{\rm{g}}_{{\rm{N}}{{\rm{H}}_3}}} \cdot {\rm{m}}{{\rm{g}}_{{\rm{Au}}}}^{ - 1} {{\rm{h}}^{ 1}}$$ at −0.5 V with faradic efficiency 2.3%. More importantly, anchored preserve ∼ 80% NRR activity after four days continuous operation, a improvement over 15% remaining production for loaded undoped tested under same conditions. Isotope labeling experiments confirmed was direct product N2 feeding gas instead other contaminations. Ex-situ X-ray photoelectron spectroscopy and absorption near-edge post-reaction catalysts reveal sulfur dopant plays critical role in stabilizing state coordination environment Au atoms clusters. Further ReaxFF molecular dynamics (RMD) simulation strong interaction between (NCs) S-G. This substrate-anchoring process could serve as effective strategy study nanoclusters’ electrocatalytic behavior while minimizing destruction surface motif harsh electrochemical