Nitrogen adsorption <i>via</i> charge transfer on vacancies created during surfactant assisted exfoliation of TiB<sub>2</sub>

Rasyotra, Anshul; Thakur, Anupma; Mandalia, Raviraj; Ranganathan, Raghavan; Jasuja, Kabeer

doi:10.1039/d2nr06676a

Cited by 8 publications

(37 citation statements)

References 86 publications

(111 reference statements)

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“…This is possibly due to the disruption of bonds during milling, which leads to an exposed site of boron that reacts with atmospheric N 2 . We have observed a similar peak for TiB 2 nanosheets obtained via surfactant-assisted exfoliation in another work (Rasyotra et al ) by our research group . In that work, we have presented detailed insights about the chemisorption of N 2 on pristine TiB 2 nanosheets under ambient conditions, which is due to vacancies and the Ti–B synergy.…”

Section: Resultssupporting

confidence: 76%

“…We have observed a similar peak for TiB 2 nanosheets obtained via surfactant-assisted exfoliation in another work (Rasyotra et al) by our research group. 35 In that work, we have presented detailed insights about the chemisorption of N 2 on pristine TiB 2 nanosheets under ambient conditions, which is due to vacancies and the Ti−B synergy. The second and third daughter peaks correspond to the B−O bonds, which are possibly observed due to the interaction of zirconia balls (ZrO 2 ) with the boron atoms, forming an oxide layer over the material.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…23 Our group has recently developed an ultrasonication-assisted approach that uses surfactants to retain the native chemistry of TiB 2 upon exfoliation. 35 Although these methods result in nanosheets which are chemically unmodified, they are not scalable approaches as they involve ultrasonication. Furthermore, these approaches are associated with relatively low yields of nanosheets.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In 2021, Green and co-workers reported that TiB 2 (and several other borides) can be exfoliated without any chemical modification when these are ultrasonicated in organic solvents . Our group has recently developed an ultrasonication-assisted approach that uses surfactants to retain the native chemistry of TiB 2 upon exfoliation . Although these methods result in nanosheets which are chemically unmodified, they are not scalable approaches as they involve ultrasonication.…”

Section: Introductionmentioning

confidence: 99%

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Large-Scale Synthesis of Electrochemically Active Titanium Diboride-Based Nanosheets by High-Energy Ball Milling

et al. 2023

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AlB2-type layered metal diborides have sought renewed research attention in recent years on account of their ability to yield XBenestheir quasi-two-dimensional (2D) counterparts. These quasi-2D nanostructures present exciting avenues to utilize the rich science offered by metal diborides. While a range of approaches have been developed to exfoliate layered metal diborides, the ability to obtain XBenes in a scalable manner is in its incipient stagesthis is a critical bottleneck in translating their rich nanoscience into tangible technology. In this work, we present a scalable approach that employs high-energy ball milling to exfoliate titanium diboride (TiB2) into its quasi-2D counterparts at the gram scale. We first show that milling TiB2 crystals for an optimal duration (6 h) and at a specific balls-to-powder ratio (20:1) yields multi-layer-thick nanosheets (∼5–10 nm thick). Second, by using Rietveld refinement and Raman spectroscopy, we show that the chemical integrity of TiB2 is retained to a large extent upon exfoliationthere is an associated formation of defects within the crystal structure of TiB2 that evolve with milling. Finally, we show that upon milling, the native electrochemical activity of TiB2 is enhanced by several folds. This ability to obtain nanosheets of TiB2 in a scalable manner using a high-energy ball mill bridges a critical missing link in the fast-growing science on nanoscaling AlB2-type metal borides.

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Section: Resultssupporting

confidence: 76%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Large-Scale Synthesis of Electrochemically Active Titanium Diboride-Based Nanosheets by High-Energy Ball Milling

et al. 2023

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“…Our research efforts over the past few years have been directed toward deriving nanosheets from TiB 2 in both functionalized and minimally functionalized forms. We have shown that nanosheets from TiB 2 can be derived by dissolution and recrystallization, 16 cosolvent-assisted exfoliation, 23 surfactant-assisted exfoliation, 36 and, very recently, mechanical exfoliation. 37 Among these methods, dissolution and recrystallization was our first attempt at exfoliating TiB 2 .…”

Section: ■ Introductionmentioning

confidence: 99%

Insights into the Unanticipated Chemical Reactivity of Functionalized Nanosheets Derived from TiB₂

Chakrabarty,

Jasuja

2023

Inorg. Chem.

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Titanium diboride (TiB 2 ) is a member of the AlB 2 -type layered metal boride family; the materials of this family are receiving renewed research interest owing to their amenability to nanoscaling. Earlier, we showed that TiB 2 can be nanoscaled to yield quasi 2D nanostructures following a dissolution− recrystallization approach. This approach yielded nanosheets that were chemically functionalized with oxy-functional groups. Also, these nanosheets could inherently form a gel-like substance. In this work, we show that these functionalized nanosheets can interact with ascorbic acid in a way that first imparts a characteristic orange hue to the original yellowish nanosheet dispersion. Second, this interaction results in the loss of gel-like behavior of the nanosheet dispersion. We utilize several spectroscopic techniques such as UV−visible, FT-IR, NMR, EPR, XPS, and XANES to unravel this unexplored chemical interaction. The findings show that both titania as well as oxy-boron species react with ascorbic acid, leading to a profound modification of the nanosheets. This modification results in an augmented electrochemical response, implying that the modified nanosheets can be used in novel applications. This study is therefore a step toward gaining an even deeper understanding of the chemical opportunities that these nanoscaled borides can provide.

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Defect Engineering of Hexagonal MAB Phase Ti₂InB₂ as Anode of Lithium‐Ion Battery with Excellent Cycling Stability

Shen,

Shi,

et al. 2024

Advanced Science

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Hexagonal MAB phases （h‐MAB） have attracted attention due to their potential to exfoliate into MBenes, similar to MXenes, which are predicted to be promising for Li‐ion battery applications. However, the high cost of synthesizing MBenes poses challenges for their use in batteries. This study presents a novel approach where a simple ball‐milling treatment is employed to enhance the purity of the h‐MAB phase Ti2InB2 and introduce significant indium defects, resulting in improved conductivity and the creation of abundant active sites. The synthesized Ti2InB2 with indium defects (VIn‐Ti2InB2) exhibits excellent electrochemical properties, particularly exceptional long‐cycle stability at current densities of 5 A g−1 (5000 cycles, average capacity decay of 0.0018%) and 10 A g−1 (15 000 cycles, average capacity decay of 0.093%). The charge storage mechanism of VIn‐Ti2InB2, involving a dual redox reaction, is proposed, where defects promote the In‐Li alloy reaction and a redox reaction with Li in the TiB layer. Finally, a Li‐ion full cell demonstrates cycling stability at 0.5 A g−1 after 350 cycles. This work presents the first accessible and scalable application of VIn‐Ti2InB2 as a Li‐ion anode, unlocking a wealth of possibilities for sustainable electrochemical applications of h‐MAB phases.

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Nitrogen adsorption via charge transfer on vacancies created during surfactant assisted exfoliation of TiB₂

Abstract: Titanium diboride (TiB2), a layered ceramic material, comprised of titanium atoms sandwiched in between honeycomb planes of boron atoms, exhibits a promising structure to utilize the rich chemistry offered by the synergy of titanium and boron.

Cited by 8 publications

References 86 publications

Large-Scale Synthesis of Electrochemically Active Titanium Diboride-Based Nanosheets by High-Energy Ball Milling

Large-Scale Synthesis of Electrochemically Active Titanium Diboride-Based Nanosheets by High-Energy Ball Milling

Insights into the Unanticipated Chemical Reactivity of Functionalized Nanosheets Derived from TiB₂

Defect Engineering of Hexagonal MAB Phase Ti₂InB₂ as Anode of Lithium‐Ion Battery with Excellent Cycling Stability

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Nitrogen adsorption via charge transfer on vacancies created during surfactant assisted exfoliation of TiB2

Abstract: Titanium diboride (TiB2), a layered ceramic material, comprised of titanium atoms sandwiched in between honeycomb planes of boron atoms, exhibits a promising structure to utilize the rich chemistry offered by the synergy of titanium and boron.

Cited by 8 publications

References 86 publications

Large-Scale Synthesis of Electrochemically Active Titanium Diboride-Based Nanosheets by High-Energy Ball Milling

Large-Scale Synthesis of Electrochemically Active Titanium Diboride-Based Nanosheets by High-Energy Ball Milling

Insights into the Unanticipated Chemical Reactivity of Functionalized Nanosheets Derived from TiB2

Defect Engineering of Hexagonal MAB Phase Ti2InB2 as Anode of Lithium‐Ion Battery with Excellent Cycling Stability

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Product

Resources

About

Nitrogen adsorption via charge transfer on vacancies created during surfactant assisted exfoliation of TiB₂

Insights into the Unanticipated Chemical Reactivity of Functionalized Nanosheets Derived from TiB₂

Defect Engineering of Hexagonal MAB Phase Ti₂InB₂ as Anode of Lithium‐Ion Battery with Excellent Cycling Stability