Co-solvent exfoliation of layered titanium diboride into few-layer-thick nanosheets

Patidar, Rishabh; Gunda, Harini; Varma, Akash; Gawas, Ramchandra; Das, Saroj Kumar

doi:10.1016/j.ceramint.2020.07.336

Cited by 19 publications

(32 citation statements)

References 33 publications

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“…It is important to note that the predictions in Fig. 7 assume a stoichiometric surface; other boron patterns may be favored under different reaction conditions 38 , 39 . Nevertheless, we assert that disordering should be observable within certain ranges of boron chemical potential.…”

Section: Resultsmentioning

confidence: 99%

Spontaneous dynamical disordering of borophenes in MgB2 and related metal borides

Gunda

Ray

et al. 2021

Nat Commun

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Layered boron compounds have attracted significant interest in applications from energy storage to electronic materials to device applications, owing in part to a diversity of surface properties tied to specific arrangements of boron atoms. Here we report the energy landscape for surface atomic configurations of MgB2 by combining first-principles calculations, global optimization, material synthesis and characterization. We demonstrate that contrary to previous assumptions, multiple disordered reconstructions are thermodynamically preferred and kinetically accessible within exposed B surfaces in MgB2 and other layered metal diborides at low boron chemical potentials. Such a dynamic environment and intrinsic disordering of the B surface atoms present new opportunities to realize a diverse set of 2D boron structures. We validated the predicted surface disorder by characterizing exfoliated boron-terminated MgB2 nanosheets. We further discuss application-relevant implications, with a particular view towards understanding the impact of boron surface heterogeneity on hydrogen storage performance.

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Section: Resultsmentioning

confidence: 99%

Spontaneous dynamical disordering of borophenes in MgB2 and related metal borides

Gunda

Ray

et al. 2021

Nat Commun

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“…However, recently, Patidar et al demonstrated an empirical approach for identifying an optimal medium for exfoliating TiB 2 using cosolvents (IPA/H 2 O). This method resulted in minimally functionalized TiB 2 nanosheets with good structural integrity . Recently, Gilliam et al provided maiden insights on the liquid-phase exfoliation efficiency of quasi-2D metal diboride nanosheets using Hansen solubility parameters .…”

Section: Synthesis Of Metal-boride-derived 2d Nanostructuresmentioning

confidence: 99%

“…This is attributed to the multicentered bonding nature of boron, which leads to a rich variety of metal-boride properties. Several metal borides have been predicted to exist in 2D forms, some of which have also been experimentally realized (as represented in Figure a). − During the past few years, several top-down and bottom-up approaches have been proposed and developed to realize the 2D forms of metal borides, − adding a new facet to the rich science of these materials. For example, the enhanced accessibility to surface active sites in planar forms endows a state-of-the-art catalytic activity to metal-boride-derived 2D nanomaterials. − These nanostructures are also finding applications in areas not conventionally envisaged for such materials, such as hydrogen generation, rechargeable energy storage, and sensors. − Recently, several computational studies have also sought to explain the effect of two-dimensionality on their electronic and thermal transport properties. ,,,,− …”

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confidence: 99%

“…This method resulted in minimally functionalized TiB 2 nanosheets with good structural integrity. 46 Recently, Gilliam et al provided maiden insights on the liquid-phase exfoliation efficiency of quasi-2D metal diboride nanosheets using Hansen solubility parameters. 136 Researchers have used various exfoliation techniques such as ultrasonication, chelation, dissolution− recrystallization, chemical intercalation, and microwave-assisted exfoliation for the AlB 2 -type borides in media such as aqueous, acidic, organic solvents, and in surfactant solutions (Figures 3a−e).…”

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Progress, Challenges, and Opportunities in the Synthesis, Characterization, and Application of Metal-Boride-Derived Two-Dimensional Nanostructures

Gunda

Klebanoff

Sharma

et al. 2021

ACS Materials Lett.

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Two-dimensional (2D) metal-boride-derived nanostructures have been a focus of intense research for the past decade, with an emphasis on new synthetic approaches, as well as on the exploration of possible applications in next-generation advanced materials and devices. Their unusual mechanical, electronic, optical, and chemical properties, arising from low dimensionality, present a new paradigm to the science of metal borides that has traditionally focused on their bulk properties. This Perspective discusses the current state of research on metalboride-derived 2D nanostructures, highlights challenges that must be overcome, and identifies future opportunities to fully utilize their potential.

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“…Although one study predicted and demonstrated the successful cosolvent exfoliation of titanium diboride (TiB 2 ) by calculating its surface tension components and comparing them with various solvents, the work still did not directly examine the exfoliation efficiency of the material in a survey of individual solvents. 20 Such broad experimental solvent studies are important for understanding fundamental surface interactions that LPE 2D nanomaterials have with their environment during and after exfoliation, and also provide useful predictive abilities for choosing effective solvents to enhance scalability for research and industrial endeavors.…”

Section: ■ Introductionmentioning

confidence: 99%

Evaluating the Exfoliation Efficiency of Quasi-2D Metal Diboride Nanosheets Using Hansen Solubility Parameters

et al. 2021

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Non-van der Waals (non-vdW) solids are emerging sources of two-dimensional (2D) nanosheets that can be produced via liquid-phase exfoliation (LPE), and are beginning to expand our understanding of 2D and quasi-2D materials. Recently, nanosheets formed by LPE processing of bulk metal diborides, a diverse family of layered non-vdW ceramic materials, have been reported. However, detailed knowledge of the exfoliation efficiency of these nanomaterials is lacking, and is important for their effective solution-phase processing and for understanding their fundamental surface chemistry, since they have significant differences from more conventional nanosheets produced from layered vdW compounds. Here in this paper we use Hansen solubility theory to investigate nanosheets of the metal borides CrB2 and MgB2 derived from LPE. By preparing dispersions in 33 different solvents, we determine Hansen solubility parameters (δ D, δ P, δ H) for both these metal diborides. We find that they exhibit notably higher δ P and δ H values compared to conventional vdW materials such as graphene and MoS2, likely as a result of the types of bonds broken in such materials from exfoliation which allows for more favorable interactions with more polar and hydrogen-bonding solvents. We apply the solubility parameters to identify cosolvent blends suitable for CrB2 and MgB2 that produce dispersions with concentrations that match or exceed those of the top-performing individual solvents for each material and that have markedly higher stability compared to the constituent solvents of the blends alone. This work provides insight into the exfoliation effectiveness of different solvents for preparation of nanosheets from metal diborides and non-vdW materials in general. Such knowledge will be crucial for developing liquid-phase exfoliation strategies for incorporating these materials in applications such as nanocomposites, inks, and coatings.

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Co-solvent exfoliation of layered titanium diboride into few-layer-thick nanosheets

Cited by 19 publications

References 33 publications

Spontaneous dynamical disordering of borophenes in MgB2 and related metal borides

Spontaneous dynamical disordering of borophenes in MgB2 and related metal borides

Progress, Challenges, and Opportunities in the Synthesis, Characterization, and Application of Metal-Boride-Derived Two-Dimensional Nanostructures

Evaluating the Exfoliation Efficiency of Quasi-2D Metal Diboride Nanosheets Using Hansen Solubility Parameters

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