Interest in layered transition metal dichalcogenides (TMDs) has proliferated due to their properties, making them promising materials for electrochemical applications. Despite this, almost exclusive attention has been placed on group 6 TMDs. Hitherto, there has been a lack of understanding of the electrochemical behaviour of group 4 TMDs, which could serve as promising materials for electrochemical applications with their semiconducting properties. In this work, we provide a first insight into the inherent electrochemistry of group 4 TMDs (i.e., TiS2, TiSe2, TiTe2, ZrS2, ZrSe2, ZrTe2, HfS2, HfSe2 and HfTe2) and their catalytic activities towards the hydrogen evolution reaction (HER). In particular, HfS2 is electrochemically inert within a wide potential range of -1.8 V to +1.8 V vs. Ag/AgCl and displays superior HER activity compared to the other group 4 TMDs, making it a promising candidate for electrochemical sensing applications. Towards the aim of tuning their HER catalytic properties, the materials are subjected to electrochemical treatment. Electrochemical activation towards the HER is displayed for ZrSe2 and HfSe2via both electrochemical oxidation and reduction, and TiTe2via electrochemical reduction. X-ray photoelectron spectroscopy (XPS) analysis points towards the importance of material purity in tuning the catalytic performances of group 4 TMDs. Such findings provide a foundational understanding of the electrochemistry of group 4 TMDs, which when applied appropriately can springboard this field of research towards achieving aims in electrochemical applications.
Bibliographical noteFunding Information:
M. P. acknowledges a Tier 2 grant (MOE2013-T2-1-056; ARC 35/13) from the Ministry of Education, Singapore. R. J. T. acknowledges financial support from the National Research Foundation (NRF), Prime Minister's Office, Singapore, under the CREATE programme, Singapore-MIT Alliance for Research and Technology (SMART) BioSystems and Micromechanics (BioSyM) IRG. Z. S. was supported by the Czech Science Foundation (GACR No. 16-05167S). The Acknowledgement of this manuscript was edited on 18.09.2016.
© The Royal Society of Chemistry
All Science Journal Classification (ASJC) codes
- Renewable Energy, Sustainability and the Environment
- Materials Science(all)