PH-Dependent Distribution of Functional Groups on Titanium-Based MXenes

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openAccess

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Journal Title

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Volume Title

A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Date

2019-01-01

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Mcode

Degree programme

Language

en

Pages

9171−9181

Series

ACS Nano, Volume 13, issue 8

Abstract

MXenes are a new rapidly developing class of two-dimensional materials with suitable properties for a broad range of applications. It has been shown that during synthesis of these materials the surfaces are usually functionalized by O, OH, and F and further suggested that controlling the surface allows controlling the material properties. However, a proper understanding of the surface structure is still missing, with a significant discrepancy between computational and experimental studies. Experiments consistently show formation of surfaces with mixed terminations, whereas computational studies point toward pure terminated surfaces. Here, we explain the formation of mixed functionalization on the surface of titanium-based two-dimensional carbides, Ti2C and Ti3C2, using a multiscale modeling scheme. Our scheme is based on calculating Gibbs free energy of formation by a combination of electronic structure calculations with cluster expansion and Monte Carlo simulations. Our calculations show formation of mixtures of O, OH, and F on the surface with the composition depending on pH, temperature, and the work function. On the other hand, our results also suggest a limited stable range of compositions, which challenges the paradigm of a high tunability of MXene properties.

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Keywords

2D materials, density functional theory, functional group, multiscale simulation, MXene

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Citation

Ibragimova, R, Puska, M J & Komsa, H P 2019, ' PH-Dependent Distribution of Functional Groups on Titanium-Based MXenes ', ACS Nano, vol. 13, no. 8, pp. 9171−9181 . https://doi.org/10.1021/acsnano.9b03511