Layered Platinum Dichalcogenides (PtS₂, PtSe₂, and PtTe₂) Electrocatalysis: Monotonic Dependence on the Chalcogen Size

Presently, research in layered transition metal dichalcogenides (TMDs) for numerous electrochemical applications have largely focused on Group 6 TMDs, especially MoS₂ and WS₂, whereas TMDs belonging to other groups are relatively unexplored. This work unravels the electrochemistry of Group 10 TMDs: specifically PtS₂, PtSe₂, and PtTe₂. Here, the inherent electroactivities of these Pt dichalcogenides and the effectiveness of electrochemical activation on their charge transfer and electrocatalytic properties are thoroughly examined. By performing density functional theory (DFT) calculations, the electrochemical and electrocatalytic behaviors of the Pt dichalcogenides are elucidated. The charge transfer and electrocatalytic attributes of the Pt dichalcogenides are strongly associated with their electronic structures. In terms of charge transfer, electrochemical activation has been successful for all Pt dichalcogenides as evident in the faster heterogeneous electron transfer (HET) rates observed in electrochemically reduced Pt dichalcogenides. Interestingly, the hydrogen evolution reaction (HER) performance of the Pt dichalcogenides adheres to a trend of PtTe₂ > PtSe₂ > PtS₂ whereby the HER catalytic property increases down the chalcogen group. Importantly, the DFT study shows this correlation to their electronic property in which PtS₂ is semiconducting, PtSe₂is semimetallic, and PtTe₂ is metallic. Furthermore, Pt dichalcogenides are effectively activated for HER. Distinct electronic structures of Pt dichalcogenides account for their different responses to electrochemical activation. Among all activated Pt dichalcogenides, PtS₂ shows most accentuated improvement as a HER electrocatalyst with an exceptional 50% decline in HER overpotential. Knowledge on Pt dichalcogenides provides valuable insights in the field of TMD electrochemistry, in particular, for the currently underrepresented Group 10 TMDs.