Predicting the Electrochemical Synthesis of 2D Materials from First Principles

Ashton, Michael; Trometer, Nicole; Mathew, Kiran; Suntivich, Jin; Freysoldt, Christoph; Sinnott, Susan B.; Hennig, Richard G.

doi:10.1021/acs.jpcc.8b10802

Cited by 40 publications

(43 citation statements)

References 60 publications

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“…No interlayer mixing of M and M atoms 24 and reproduced here (not shown), the stability region of the Cr-based o MXene increases to pH > 7 (Fig. 1(a)).…”

Section: Resultssupporting

confidence: 55%

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Prediction of Optimal Synthesis Conditions for the Formation of Ordered Double-Transition-Metal MXenes (o-MXenes)

Caffrey

2020

J. Phys. Chem. C

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o MXenes are a family of layered double-transition metal carbides and nitrides with a unique out-of-plane ordering of the two metal atoms. Their chemical versatility means they have novel applications in energy storage, catalysis and sensing devices. o MXenes are synthesized from their precursor o MAX phase materials using a chemical etching process, although yields are typically low. The optimal conditions necessary for the etching of MAX phase materials can be predicted using Pourbaix diagrams. Here, Pourbaix diagrams produced from rst-principles calculations are used to determine the conditions necessary to enhance the yields of o MXenes. In agreement with experiment, we show that high yields of (Mo, Ti) 2 CT x are possible, as the o MXene is stable relative to known competing ionic and molecular species in an aqueous solution across a wide range of pH and applied potentials. We show how the stability of the o MXene depends on the nature of the terminating groups and the presence of metal vacancies on the o MXene surface.

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“…No interlayer mixing of M and M atoms 24 and reproduced here (not shown), the stability region of the Cr-based o MXene increases to pH > 7 (Fig. 1(a)).…”

Section: Resultssupporting

confidence: 55%

“…They are also precursors to MXenes, their two-dimensional (2D) counterparts. 24 These are produced by selectively chemically etching the A elements from the parent MAX phase using, typically, an aqueous HF solution. The acid attacks the M-A bonds, forming A-F x compounds which diuse out.…”

Section: Introductionmentioning

confidence: 99%

Prediction of Optimal Synthesis Conditions for the Formation of Ordered Double-Transition-Metal MXenes (o-MXenes)

Caffrey

2020

J. Phys. Chem. C

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“…Clearly, the surface structure inferred from the calculations is at odds with the experimental data showing a mixture of all three types of terminations. The origin of this discrepancy is still unclear but can arise from ignoring the role of the solvent, 31 an improper treatment of the chemical potential of elements, 32 and absence of thermodynamic sampling. 33 Thus, the important questions still remain: how functional groups are distributed and how the composition depends on the experimental conditions.…”

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confidence: 99%

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

2019

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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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“…However, these methods could potentially introduce extra chemicals, and the influence of these chemicals on the subsequent HER activity is unknown. [82] [78] [Reprinted with permission from [78] . Copyright {2019} American Chemical Society.]…”

Section: Storage In Aqueous Colloidal Solutionsmentioning

confidence: 99%

Insights on the Corrosion and Degradation of MXenes as Electrocatalysts for Hydrogen Evolution Reaction

Liang

Liu

2022

ChemCatChem

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MXenes, known as the graphene-like two-dimensional transition metal carbides, carbonitrides, or nitrides, have been considered as promising electrocatalysts to replace benchmark Pt for hydrogen evolution reaction (HER). Despite the success in fabricating MXenes, their application in catalysis still faces great challenges. One critical drawback is the rapid corrosion and structural evolution of MXenes during storage and HER. In this work, the corrosion and structural evolution of various MXenes in air, aqueous colloidal solutions, and under HER conditions are reviewed. The degradation/structural mechanism of MXenes and effects of structural evolution on the HER activity are in dispute. Preliminary protocols are proposed for future MXene storage and design for HER application. This review provides valuable information to better prevent corrosion of MXenes before and after servicing as HER catalysts, and to interpret the obtained HER performance for MXenes in the view of corrosion/ structural evolution.

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Predicting the Electrochemical Synthesis of 2D Materials from First Principles

Cited by 40 publications

References 60 publications

Prediction of Optimal Synthesis Conditions for the Formation of Ordered Double-Transition-Metal MXenes (o-MXenes)

Prediction of Optimal Synthesis Conditions for the Formation of Ordered Double-Transition-Metal MXenes (o-MXenes)

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

Insights on the Corrosion and Degradation of MXenes as Electrocatalysts for Hydrogen Evolution Reaction

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