Stability of 2H- and 1T-MoS2 in the presence of aqueous oxidants and its protection by a carbon shell

Abstract

Two-dimensional molybdenum disulfide (MoS₂) is emerging as a catalyst for energy and environmental applications. Recent studies have suggested the stability of MoS₂ is questionable when exposed to oxidizing conditions found in water and air. In this study, the aqueous stability of 2H- and 1T-MoS₂ and 2H-MoS₂ protected with a carbon shell was evaluated in the presence of model oxidants (O₂, NO₂⁻, BrO₃⁻). The MoS₂ electrocatalytic performance and stability was characterized using linear sweep voltammetry and chronoamperometry. In the presence of dissolved oxygen (DO) only, 2H- and 1T-MoS₂ were relatively stable, with SO₄²⁻ formation of only 2.5% and 3.1%, respectively. The presence of NO₂⁻ resulted in drastically different results, with SO₄²⁻ formations of 11% and 14% for 2H- and 1T-MoS₂, respectively. When NO₂⁻ was present without DO, the 2H- and 1T-MoS₂ remained relatively stable with SO₄²⁻ formations of only 4.2% and 3.3%, respectively. Similar results were observed when BrO₃⁻ was used as an oxidant. Collectively, these results indicate that the oxidation of 2H- and 1T-MoS₂ can be severe in the presence of these aqueous oxidants but that DO is also required. To investigate the ability of a capping agent to protect the MoS₂ from oxidation, a carbon shell was added to 2H–MoS₂. In a batch suspension in the presence of DO and NO₂⁻, the 2H–MoS₂ with the carbon shell exhibited good stability with no oxidation observed. The activity of 2H–MoS₂ electrodes was then evaluated for the hydrogen evolution reaction by a Tafel analysis. The carbon shell improved the activity of 2H–MoS₂ with a decrease in the Tafel slope from 451 to 371 mV dec⁻¹. The electrode stability, characterized by chronopotentiometry, was also enhanced for the 2H–MoS₂ coated with a carbon shell, with no marked degradation in current density observed over the reaction period. Because of the instability exhibited by unprotected MoS₂, it will only be a useful catalyst if measures are taken to protect the surface from oxidation. Further, given the propensity of MoS₂ to undergo oxidation in aqueous solutions, caution should be used when describing it as a true catalyst for reduction reactions (e.g., H₂ evolution), unless proven otherwise.