Unveiling Active Sites for the Hydrogen Evolution Reaction on Monolayer MoS2

Abstract

Here, the hydrogen evolution reaction (HER) activities at the edge and basal-plane sites of monolayer molybdenum disulfide (MoS₂) synthesized by chemical vapor deposition (CVD) are studied using a local probe method enabled by selected-area lithography. Reaction windows are opened by e-beam lithography at sites of interest on poly(methyl methacrylate) (PMMA)-covered monolayer MoS₂ triangles. The HER properties of MoS₂ edge sites are obtained by subtraction of the activity of the basal-plane sites from results containing both basal-plane and edge sites. The catalytic performances in terms of turnover frequencies (TOFs) are calculated based on the estimated number of active sites on the selected areas. The TOFs follow a descending order of 3.8 ± 1.6, 1.6 ± 1.2, 0.008 ± 0.002, and 1.9 ± 0.8 × 10⁻⁴ s⁻¹, found for 1T′-, 2H-MoS₂ edges, and 1T′-, 2H-MoS₂ basal planes, respectively. Edge sites of both 2H- and 1T′-MoS₂ are proved to have comparable activities to platinum (≈1–10 s⁻¹). When fitted into the HER volcano plot, the MoS₂ active sites follow a trend distinct from conventional metals, implying a possible difference in the reaction mechanism between transition-metal dichalcogenides (TMDs) and metal catalysts.

Utilizing an on-chip electrochemical device, which is capable of measuring the hydrogen-evolution performance on the designated location of monolayer MoS₂, the catalytic activities of the basal-plane and edge sites of both 2H and 1T′-MoS₂ are identified. The activities of the MoS₂ active sites follow a unique trend in the volcano plot.

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