New Simultaneous Exfoliation and Doping Process for Generating MX Nanosheets for Electrocatalytic Hydrogen Evolution Reaction.

Doping nonmetal atoms into layered transition metal dichalcogenide MX structures has emerged as a promising strategy for enhancing their catalytic activities for the hydrogen evolution reaction. In this study, we developed a new and efficient one-step approach that involves simultaneous plasma-induced doping and exfoliating of MX bulk into nanosheets-such as MoSe, WSe, MoS, and WS nanosheets-within a short time and at a low temperature (ca. 80 °C). Specifically, by utilizing active plasma that is generated with an asymmetric electrical field during the electrochemical reaction at the surface of the submerged cathode tip, we are able to achieve doping of nitrogen atoms, from the electrolytes, into the semiconducting 2H-MX structures during their exfoliation process from the bulk states, forming N-doped MX. We selected N-doped MoS nanosheets for demonstrating their catalytic hydrogen evolution potential. We modulated the electronic and transport properties of the MoS structure with the synergy of nitrogen doping and exfoliating for enhancing their catalytic activity. We found that the nitrogen concentration of 5.2 atom % at N-doped MoS nanosheets have an excellent catalytic hydrogen evolution reaction, where a low overpotential of 164 mV at a current density of 10 mA cm and a small Tafel slope of 71 dec mV-much lower than those of exfoliated MoS nanosheets (207 mV, 82 dec mV) and bulk MoS (602 mV, 198 dec mV)-as well as an extraordinary long-term stability of >25 h in 0.5 M HSO can be achieved.