Spontaneous doping of the basal plane of MoS2 single layers through oxygen substitution under ambient conditions

The chemical inertness of the defect-free basal plane confers environmental stability to MoS2 single layers, but it also limits their chemical versatility and catalytic activity. The stability of pristine MoS2 basal plane against oxidation under ambient conditions is a widely accepted assumption however, here we report single-atom-level structural investigations that reveal that oxygen atoms spontaneously incorporate into the basal plane of MoS2 single layers during ambient exposure. The use of scanning tunnelling microscopy reveals a slow oxygen-substitution reaction, during which individual sulfur atoms are replaced one by one by oxygen, giving rise to solid-solution-type 2D MoS2−xOx crystals. Oxygen substitution sites present all over the basal plane act as single-atom reaction centres, substantially increasing the catalytic activity of the entire MoS2 basal plane for the electrochemical H2 evolution reaction. MoS2 single layers spontaneously undergo a slow oxygen substitution reaction under ambient conditions giving rise to solid-solution-type 2D molybdenum oxy-sulfide crystals. The oxygen substitution sites of the 2D MoS2−xOx crystals act as efficient single-atom catalytic centres for the hydrogen evolution reaction.