Tuning the Basal Plane Functionalization of Two-Dimensional Metal Carbides (MXenes) To Control Hydrogen Evolution Activity
2017; American Chemical Society; Volume: 1; Issue: 1 Linguagem: Inglês
10.1021/acsaem.7b00054
ISSN2574-0962
AutoresAlbertus D. Handoko, Kurt Fredrickson, Babak Anasori, Kurt W. Convey, Luke R. Johnson, Yury Gogotsi, Aleksandra Vojvodić, Zhi Wei Seh,
Tópico(s)Advanced Photocatalysis Techniques
ResumoHydrogen evolution reaction (HER) via electrocatalysis is one method of enabling sustainable production of molecular hydrogen as a clean and promising energy carrier. Previous theoretical and experimental results have shown that some two-dimensional (2D) transition metal carbides (MXenes) can be effective electrocatalysts for the HER, based on the assumption that they are functionalized entirely with oxygen or hydroxyl groups on the basal plane. However, it is known that MXenes can contain other basal plane functionalities, e.g., fluorine, due to the synthesis process, yet the influence of fluorine termination on their HER activity remains unexplored. In this paper, we investigate the role and effect of basal plane functionalization (Tx) on the HER activity of 5 different MXenes using a combination of experimental and theoretical approaches. We first studied Ti3C2Tx produced by different fluorine-containing etchants and found that those with higher fluorine coverage on the basal plane exhibited lower HER activity. We then controllably prepared Mo2CTx with very low basal plane fluorine coverage, achieving a geometric current density of −10 mA cm–2 at 189 mV overpotential in acid. More importantly, our results indicate that the oxygen groups on the basal planes of Mo2CTx are catalytically active toward the HER, unlike in the case of widely studied 2H-phase transition metal dichalcogenides such as MoS2, in which only the edge sites are active. These results pave the way for the rational design of 2D materials for either the HER, when minimal overpotential is desired, or for energy storage, when maximum voltage window is needed.
Referência(s)