Vacancy Rich TiB2 Nanosheets Promote Electrochemical Ammonia Synthesis.

The ability to exfoliate transition metal diborides has led to a renewed interest in their prospect to be applied as catalysts for electrochemical reactions. This is due to an enhanced access to the unprecedented interfaces these nanomaterials offer. In this work, we show that nanosheets exfoliated from TiB2 exhibit vacancies that facilitate an excellent interface for catalyzing nitrogen reduction reaction (NRR). We found that these nanosheets demonstrate a high selectivity toward NH3 because of their abiity to preferentially chemisorb and activate N2. These nanosheets exhibit a superlative NH3 yield of 318 µg h-1 cm-2 at -0.2 V versus RHE with a faradaic efficiency of 57%. We also found how the relative ratios of Ti and B atoms in these nanosheets can affect the NH3 yield and faradaic efficiency. We supplement these results with DFT studies that indicate that it is the creation of frustrated Lewis pairs along with the Ti-B synergy that induces a push-and-pull effect; this in turn favors N2 activation and lowers the energy barrier for NRR. Furthermore, we explored B-exposed and Ti-exposed surfaces to understand how different surfaces affect the reaction yield and efficiency and found that Ti-exposed surfaces with boron divacancy have the highest propensity for NRR. The maiden insights presented in this study on the role of transition metal-boron synergy and interfaces present significant additions to the fast-expanding knowledge on nanoscaled metal borides.

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

Titanium diboride (TiB2) is a member of the AlB2-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 TiB2 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.

TiB2-Derived Nanosheets Enhance the Tensile Strength and Controlled Drug Release of Biopolymeric Films Used in Wound Healing.

Wound healing using an alginate-based biopolymeric film is one of the most preferred treatments. However, these films lack mechanical strength (elasticity and tensile strength), show higher initial burst release, and exhibit high vapor permeability. The present study reports the development of nanosheets derived from titanium diboride (10 nm) (NTB)-incorporated biopolymeric films (0.025, 0.05, and 0.1% w/v) using sodium alginate (SA) and carboxymethyl cellulose (CMC) to overcome the shortfalls. The surface properties of the film, nanosheet distribution within the film, and possible interactions with the film are explored by using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), Fourier transform infrared (FTIR), and X-ray diffraction (XRD). These analyses confirm that nanosheets are uniformly distributed in the film and introduce unevenness on the film's surface. The tensile strength of the nanosheet-incorporated film (0.1% NTB film) using UTM is found to be 24.30 MPa (six times higher compared to the blank film), equivalent to human skin. The water vapor transmission rate of the film is also found to be in the desired range (i.e., 2000-2500 g/m2 day). The biocompatibility of the NTB film is confirmed by the MTT assay test using NIH/3T3 cells and HEK 293 cells. Furthermore, the scratch assay shows that the developed films promote cell migration and proliferation. The antibacterial activity of the film is also demonstrated using a model drug, tetracycline hydrochloride (TCl). Besides, the film exhibits the sustained release of TCl and follows the Korsmeyer-Peppas model for drug release. Overall, the 0.1% w/v NTB film is easy to fabricate, biocompatible and shows superior mechanical properties.

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

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. TiB2 has been primarily investigated and applied in its bulk form. This perspective is, however, fast evolving with a number of efforts aimed at exfoliating TiB2. Here, we show that it is possible to delaminate TiB2 into ultrathin, minimally functionalized nanosheets with the aid of surfactants. These nanosheets exhibit crystalline nature and their chemical analysis reveals vacant sites within the nanosheets. These vacancies facilitate the chemisorption of N2 onto the TiB2 nanosheets under ambient conditions without the aid of any energy, this finding was unexpected. This remarkable activity of TiB2 nanosheets is attributed to vacancies and the Ti-B synergy, which enhance the adsorption and activation of N2. We obtained supplemental insights into the N2 adsorption by Density Functional Theory (DFT) studies, which reveal how charge transfer among Ti, B, and N2 results in N2 adsorption. The DFT studies also show that nanosheets having more vacancies result in increased adsorption when compared with nanosheets having less vacancies and bulk TiB2.

Hydrogen Storage in Partially Exfoliated Magnesium Diboride Multilayers.

Metal boride nanostructures have shown significant promise for hydrogen storage applications. However, the synthesis of nanoscale metal boride particles is challenging because of their high surface energy, strong inter- and intraplanar bonding, and difficult-to-control surface termination. Here, it is demonstrated that mechanochemical exfoliation of magnesium diboride in zirconia produces 3-4 nm ultrathin MgB2 nanosheets (multilayers) in high yield. High-pressure hydrogenation of these multilayers at 70 MPa and 330 °C followed by dehydrogenation at 390 °C reveals a hydrogen capacity of 5.1 wt%, which is ≈50 times larger than the capacity of bulk MgB2 under the same conditions. This enhancement is attributed to the creation of defective sites by ball-milling and incomplete Mg surface coverage in MgB2 multilayers, which disrupts the stable boron-boron ring structure. The density functional theory calculations indicate that the balance of Mg on the MgB2 nanosheet surface changes as the material hydrogenates, as it is energetically favorable to trade a small number of Mg vacancies in Mg(BH4 )2 for greater Mg coverage on the MgB2 surface. The exfoliation and creation of ultrathin layers is a promising new direction for 2D metal boride/borohydride research with the potential to achieve high-capacity reversible hydrogen storage at more moderate pressures and temperatures.

Spontaneous dynamical disordering of borophenes in MgB2 and related metal borides.

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.

Processable dispersions of photocatalytically active nanosheets derived from titanium diboride: self assembly into hydrogels and paper-like macrostructures.

Titanium diboride (TiB2), a layered ceramic material, is well-known for its ultrahigh strength, wear resistance, and chemical inertness. In this work, we present a simple one-pot chemical approach that yields sheet-like nanostructures from TiB2. We serendipitously found that TiB2 crystals can undergo complete dissolution in a mild aqueous solution of H2O2 under ambient conditions. This unexpected dissolution of TiB2 is followed by non-classical recrystallization that results in nanostructures with sheet-like morphology exhibiting Ti-O and B-O functional groups. We show that this pathway can be used to obtain an aqueous dispersion of nanosheets with concentrations ≥3 mg mL-1. Interestingly, these nanosheets tend to transform into a hydrogel without the need of any additives. We found that the degree of gelation depends on the ratio of TiB2 to H2O2, which can be tuned to achieve gels with a shear modulus of 0.35 kPa. We also show this aqueous dispersion of nanosheets is processable and forms hierarchical paper-like macrostructures upon vacuum filtration. Such an ability to assemble into free-standing 3D structures would enable a leap to practical applications. We also show that the high surface area and presence of oxy-functional groups on these nanosheets endow them a superior photocatalytic activity to degrade organic pollutants. This exemplifies the rich potential that TiB2 offers upon nanoscaling. The results presented here not only add a novel material to the 2D flatland but also urge the scientific community to revisit the chemistry of metal borides, that have been traditionally considered as relatively inert ceramics.

Tuning the oscillatory dynamics of the Belousov-Zhabotinsky reaction using ruthenium nanoparticle decorated graphene.

The classic Belousov-Zhabotinsky (BZ) reaction, which involves transition metal catalysed redox reactions, represents a family of nonlinear chemical oscillators. Here, we show that it is possible to tune the oscillatory dynamics of the BZ reaction by using a hybrid 2D material, i.e., graphene-based nanosheets decorated with Ru nanoparticles. Specifically, we demonstrate that the frequency of chemical oscillations in a BZ reaction increases, by up to four-fold, when catalyzed by the Ru-graphene nanocomposite. We show that this observed behaviour is attributed to enhanced access to active catalytic sites on Ru nanoparticles, as well as the rapid shuttling of electrons facilitated by the highly conductive graphene platform. We further demonstrate that this enhancement of oscillations facilitated by the graphene platform can be simulated using the Oregonator model. Our numerical simulations reveal a strong correlation between the rate of charge transfer and the frequency of chemical oscillations. This ability of a 2D material, like graphene, to influence the dynamics of an oscillatory chemical reaction, as showcased in this work, is studied for the first time and opens up new avenues to tune the dynamics of chemical oscillators. We anticipate that these findings would enable us to design a variety of intrinsically powered biomimetic systems with controllable dynamic behavior.

Boron based nanosheets as reducing templates in aqueous solutions: towards novel nanohybrids with gold nanoparticles and graphene.

We show that nanosheets obtained by exfoliating magnesium diboride bear an intrinsic ability to elicit chemical reduction of quinone-based molecules. They also reduce gold salt into ultra-small gold nanoparticles and graphene oxide into reduced graphene oxide. These nanosheets subsequently interface with the partner nanomaterial in solution to form novel nanohybrids.

Introduction of Protonated Sites on Exfoliated, Large-Area Sheets of Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) sheets possess an exclusive set of properties, including wide energy band gap, high optical transparency, high dielectric breakdown strength, high thermal conductivity, UV cathodoluminescence, and pronounced thermochemical stability. However, functionalization of large h-BN layers has remained a challenge due to their chemical resistance and unavailable molecular-binding sites. Here we report on the protonation of h-BN via treatment with chlorosulfonic acid that not only exfoliates "large" h-BNs (up to 10 000 µm2) at high yields (∼23%) but also results in their covalent functionalization by introducing four forms of aminated nitrogen (N) sites within the h-BN lattice: sp2-delocalized and sp3-quaternary protonation on internal N sites (>N+═ and >NH+-) and pyridinic-like protonation on the edge N sites (═NH+- and -NH-). The presence of these groups transforms the chemically passive h-BN sheets to their chemically active form, which as demonstrated here can be used as scaffolds for forming composites with plasmonic gold nanoparticles and organic dye molecules. The dispersion of h-BNs exhibits an optical energy band gap of 5.74 eV and a zeta potential of ζ = +36.25 mV at pH = 6.1 (ζmax = +150 mV), confirming high dispersion stability. We envision that these two-dimensional nanomaterials with an atomically packed honeycomb lattice and high-energy band gap will evolve next-generation applications in controlled-UV emission, atomic-tunneling-barrier devices, ultrathin controlled-permeability membranes, and thermochemically resistive transparent coatings.

Simple, Green, and High-Yield Production of Boron-Based Nanostructures with Diverse Morphologies by Dissolution and Recrystallization of Layered Magnesium Diboride Crystals in Water.

Layered metal diborides that contain metal atoms sandwiched between boron honeycomb planes offer a rich opportunity to access graphenic forms of boron. We recently demonstrated that magnesium diboride (MgB2 ) could be exfoliated by ultrasonication in water to yield boron-based nanosheets. However, knowledge of the fate of metal boride crystals in aqueous phases is still in its incipient stages. This work presents our preliminary findings on the discovery that MgB2 crystals can undergo dissolution in water under ambient conditions to result in precursors (prenucleation clusters) that, upon aging, undergo nonclassical crystallization preferentially growing in lateral directions by two-dimensional (2D) oriented attachment. We show that this recrystallization can be utilized as an avenue to obtain a high yield (≈92 %) of boron-based nanostructures, including nanodots, nanograins, nanoflakes, and nanosheets. These nanostructures comprise boron honeycomb planes chemically modified with hydride and oxy functional groups, which results in an overall negative charge on their surfaces. This ability of MgB2 crystals to yield prenucleation clusters that can self-seed to form nanostructures comprising chemically modified boron honeycomb planes presents a new facet to the physicochemical interaction of MgB2 with water. These findings also open newer avenues to obtain boron-based nanostructures with tunable morphologies by varying the chemical milieu during recrystallization.

Retained Carrier-Mobility and Enhanced Plasmonic-Photovoltaics of Graphene via ring-centered η6 Functionalization and Nanointerfacing.

Binding graphene with auxiliary nanoparticles for plasmonics, photovoltaics, and/or optoelectronics, while retaining the trigonal-planar bonding of sp2 hybridized carbons to maintain its carrier-mobility, has remained a challenge. The conventional nanoparticle-incorporation route for graphene is to create nucleation/attachment sites via "carbon-centered" covalent functionalization, which changes the local hybridization of carbon atoms from trigonal-planar sp2 to tetrahedral sp3. This disrupts the lattice planarity of graphene, thus dramatically deteriorating its mobility and innate superior properties. Here, we show large-area, vapor-phase, "ring-centered" hexahapto (η6) functionalization of graphene to create nucleation-sites for silver nanoparticles (AgNPs) without disrupting its sp2 character. This is achieved by the grafting of chromium tricarbonyl [Cr(CO)3] with all six carbon atoms (sigma-bonding) in the benzenoid ring on graphene to form an (η6-graphene)Cr(CO)3 complex. This nondestructive functionalization preserves the lattice continuum with a retention in charge carrier mobility (9% increase at 10 K); with AgNPs attached on graphene/n-Si solar cells, we report an ∼11-fold plasmonic-enhancement in the power conversion efficiency (1.24%).

Aqueous dispersions of few-layer-thick chemically modified magnesium diboride nanosheets by ultrasonication assisted exfoliation.

The discovery of graphene has led to a rising interest in seeking quasi two-dimensional allotropes of several elements and inorganic compounds. Boron, carbon's neighbour in the periodic table, presents a curious case in its ability to be structured as graphene. Although it cannot independently constitute a honeycomb planar structure, it forms a graphenic arrangement in association with electron-donor elements. This is exemplified in magnesium diboride (MgB2): an inorganic layered compound comprising boron honeycomb planes alternated by Mg atoms. Till date, MgB2 has been primarily researched for its superconducting properties; it hasn't been explored for the possibility of its exfoliation. Here we show that ultrasonication of MgB2 in water results in its exfoliation to yield few-layer-thick Mg-deficient hydroxyl-functionalized nanosheets. The hydroxyl groups enable an electrostatically stabilized aqueous dispersion and create a heterogeneity leading to an excitation wavelength dependent photoluminescence. These chemically modified MgB2 nanosheets exhibit an extremely small absorption coefficient of 2.9 ml mg(-1) cm(-1) compared to graphene and its analogs. This ability to exfoliate MgB2 to yield nanosheets with a chemically modified lattice and properties distinct from the parent material presents a fundamentally new perspective to the science of MgB2 and forms a first foundational step towards exfoliating metal borides.

Covalent functionalization of dipole-modulating molecules on trilayer graphene: an avenue for graphene-interfaced molecular machines.

The molecular dipole moment plays a significant role in governing important phenomena like molecular interactions, molecular configuration, and charge transfer, which are important in several electronic, electrochemical, and optoelectronic systems. Here, the effect of the change in the dipole moment of a tethered molecule on the carrier properties of (functionalized) trilayer graphene--a stack of three layers of sp(2)-hybridized carbon atoms--is demonstrated. It is shown that, due to the high carrier confinement and large quantum capacitance, the trans-to-cis isomerisation of 'covalently attached' azobenzene molecules, with a change in dipole moment of 3D, leads to the generation of a high effective gating voltage. Consequently, 6 units of holes are produced per azobenzene molecule (hole density increases by 440 000 holes µm(-2)). Based on Raman and X-ray photoelectron spectroscopy data, a model is outlined for outer-layer, azobenzene-functionalized trilayer graphene with current modulation in the inner sp(2) matrix. Here, 0.097 V are applied by the isomerisation of the functionalized azobenzene. Further, the large measured quantum capacitance of 72.5 µF cm(-2) justifies the large Dirac point in the heavily doped system. The mechanism defining the effect of dipole modulation of covalently tethered molecules on graphene will enable future sensors and molecular-machine interfaces with graphene.

Implantation and growth of dendritic gold nanostructures on graphene derivatives: electrical property tailoring and Raman enhancement.

Interfacing electron-rich metal nanoparticles with graphene derivatives can sensitively regulate the properties of the resultant hybrid with potential applications in metal-doped graphene field-effect transistors (FETs), surface-enhanced Raman spectroscopy, and catalysis. Here, we show that by controlling the rate of diffusion and catalytic reduction of gold ions on graphene oxide (GO), dendritic "snowflake-shaped" gold nanostructures (SFGNs) can be templated on graphene. The structural features of the SFGNs and their interfacing mechanism with GO were characterized by microscopic analysis and Raman-scattering. We demonstrate that (a) SFGNs grow on GO-surface via diffusion limited aggregation; (b) SFGN's morphology (dendritic to globular), size (diameter of 150-500 nm and a height of 45-55 nm), coverage density, and dispersion stability can be controlled by regulating the chemiophysical forces; (c) SFGNs enhance the Raman signal by 2.5 folds; and (d) SFGNs act as antireduction resist during GO-SFGN's chemical reduction. Further, the SFGNs interfacing with graphene reduces the apparent band gap (from 320 to 173 meV) and the Schottky barrier height (from 126 to 56 meV) of the corresponding FET.