Unraveling the Role of Lithium in Enhancing the Hydrogen Evolution Activity of MoS2: Intercalation versus Adsorption

Molybdenum disulfide (MoS2) is a highly promising catalyst for the hydrogen evolution reaction (HER) to realize large-scale artificial photosynthesis. The metallic 1T'-MoS2 phase, which is stabilized via the adsorption or intercalation of small molecules or cations such as Li, shows exceptionally high HER activity, comparable to that of noble metals, but the effect of cation adsorption on HER performance has not yet been resolved. Here we investigate in detail the effect of Li adsorption and intercalation on the proton reduction properties of MoS2. By combining spectroscopy methods (infrared of adsorbed NO, Li-7 solid-state nuclear magnetic resonance, and X-ray photoemission and absorption) with catalytic activity measurements and theoretical modeling, we infer that the enhanced HER performance of LixMoS2 is predominantly due to the catalytic promotion of edge sites by Li.