Layered Platinum Dichalcogenides (PtS2, PtSe2, and PtTe2) Electrocatalysis: Monotonic Dependence on the Chalcogen Size. (15th March 2016)

• Record Type: Journal Article
• Authors: Chia, Xinyi; Adriano, Ambrosi; Lazar, Petr; Sofer, Zdeněk; Luxa, Jan; Pumera, Martin
• Is Part Of: Advanced functional materials. Volume 26:Number 24(2016)
• Page Start: 4306
• Page End: 4318
• Publication Date: 2016-03-15
• Subjects: density functional theory -- electrochemistry -- hydrogen evolution -- noble transition metal dichalcogenides -- platinum dichalcogenides; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.201505402
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract : 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, PtSe2 is 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. Abstract : Noble transition metal dichalcogenides (TMDs) such as layered PtS2, PtSe2, and PtTe2 are studied for their charge transfer and electrocatalytic hydrogen evolution reaction (HER) properties. These properties correlate to their electronic structures, and trends down the chalcogen group are explored. Electrochemical activation is effective for all platinum dichalcogenides. Amidst all activated materials, PtS2 showcases most enhanced HER efficiency.