Unlocking the Potential: Atomically Thin 2D Fluoritene from Exfoliated Fluorite Ore and Its Electrochemical Activity.

Fluorite mineral holds significant importance because of its optoelectronic properties and wide range of applications. Here, we report the successful exfoliation of bulk fluorite ore (calcium fluoride, CaF2) crystals into atomically thin two-dimensional fluoritene (2D CaF2) using a highly scalable liquid-phase exfoliation method. The microscopic and spectroscopy characterizations show the formation of (111) plane-oriented 2D CaF2 sheets with exfoliation-induced material strain due to bond breaking, leading to the changes in lattice parameter. Its potential role in electrocatalysis is further explored for deeper insight, and a probable mechanism is also discussed. The 2D CaF2 with long-term stability shows overpotential values of 670 and 770 mV vs RHE for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, at 10 mA cm-2. Computational simulations demonstrate the unique "direct-indirect" band gap switching with odd and even numbers of layers. Current work offers new avenues for exploring the structural and electrochemical properties of 2D CaF2 and its potential applicability.

Flexible Nanogenerators Based on Enhanced Flexoelectricity in Mn3O4 Membranes.

Atomically thin, few-layered membranes of oxides show unique physical and chemical properties compared to their bulk forms. Manganese oxide (Mn3O4) membranes are exfoliated from the naturally occurring mineral Hausmannite and used to make flexible, high-performance nanogenerators (NGs). An enhanced power density in the membrane NG is observed with the best-performing device showing a power density of 7.99 mW m-2 compared to 1.04 µW m-2 in bulk Mn3O4. A sensitivity of 108 mV kPa-1 for applied forces <10 N in the membrane NG is observed. The improved performance of these NGs is attributed to enhanced flexoelectric response in a few layers of Mn3O4. Using first-principles calculations, the flexoelectric coefficients of monolayer and bilayer Mn3O4 are found to be 50-100 times larger than other 2D transition metal dichalcogenides (TMDCs). Using a model based on classical beam theory, an increasing activation of the bending mode with decreasing thickness of the oxide membranes is observed, which in turn leads to a large flexoelectric response. As a proof-of-concept, flexible NGs using exfoliated Mn3O4 membranes are made and used in self-powered paper-based devices. This research paves the way for the exploration of few-layered membranes of other centrosymmetric oxides for application as energy harvesters.

Enhanced Thermoelectric Performance of Nanostructured 2D Tin Telluride.

A lot of experimental studies are conducted on theoretically predicted thermoelectric 2D materials. Such materials can pave the way for charging ultra-thin electronic devices, self-charging wearable devices, and medical implants. This study systematically explores the thermoelectric attributes of bulk and 2D nanostructured Tin Telluride (SnTe), employing experimental investigations and theoretical analyses based on semiclassical Boltzmann transport theory. The bulk SnTe is synthesized through flame melting, while the 2D SnTe is produced via liquid phase exfoliation. The comprehensive assessment of thermoelectric properties integrated experimental measurements utilizing a Physical Property Measurement System and theoretical calculations from the BoltzTraP code. Experimental thermoelectric studies show a high ZT of 0.17 for 2D SnTe when compared to bulk (0.005) at room temperature. This rise in ZT is due to the high Seebeck coefficient and low thermal conductivity of nanostructured 2D SnTe. Density functional theory (DFT) studies reveal the contribution of the density of states (DOS) and energy bandgap in enhancing the Seebeck coefficient and lowering thermal conductivity by interface scattering.

Gd3+ Encapsulation on 2D-g-C3N4 Nanostructure for Spintronics and Ultrasound Assisted Photocatalytic Applications: First-Principles and Experimental Studies.

Atomically thin two-dimensional (2D) semiconductors have high potential in optoelectronics and magneto-optics appliances due to their tunable band structures and physicochemical stability. The work demonstrates that Gd3+ incorporated 2D-g-C3N4 nanosheet (Gd3+/2D-g-C3N4 NS) is synthesized through chemisorption methodology for defect enrichment. The material characterizations reveal that the ion decoration enhances the surface area and defect concentration of the 2D sheet. The experimental observations have been further corroborated with the help of density functional theory (DFT) simulation. Spin asymmetry polarizations near the Fermi level, obtained through the partial density of states (PDOS) analyses, reveal the magnetic nature of the synthesized material, validating the room temperature ferromagnetism obtained through a vibrating-sample magnetometer (VSM). Gd3+/2D-g-C3N4 NS shows significant enhancement in saturation magnetization (Ms) experimentally and computationally compared to the pristine one. The magnetic catalyst shows 98% remediation efficiency for ultrasound-assisted visible-light-driven photodegradation of methyl orange (MO). The synergistic approach of liquid chromatography-mass spectrometry (LC-MS) analyses and DFT studies elucidates reaction intermediates and unveils the degradation mechanism. Post-characterization studies assure the stability of the magnetic catalyst through optical, chemical, magnetic, and microscopic analyses. So, the synthesized material can be proficiently used as a magnetic nanocatalyst in wastewater treatments and spin-electronics applications.

Utilization of DNA and 2D metal oxide interaction for an optical biosensor.

The efficient monitoring and early detection of viruses may provide essential information about diseases. In this work, we have highlighted the interaction between DNA and a two-dimensional (2D) metal oxide for developing biosensors for further detection of viral infections. Spectroscopic measurements have been used to probe the efficient interactions between single-stranded DNA (ssDNA) and the 2D metal oxide and make them ideal candidates for detecting viral infections. We have also used fully atomistic molecular dynamics (MD) simulation to give a microscopic understanding of the experimentally observed ssDNA-metal oxide interaction. The adsorption of ssDNA on the inorganic surface was found to be driven by favourable enthalpy change, and 5'-guanine was identified as the interacting nucleotide base. Additionally, the in silico assessment of the conformational changes of the ssDNA chain during the adsorption process was also performed in a quantitative manner. Finally, we comment on the practical implications of these developments for sensing that could help design advanced systems for preventing virus-related pandemics.

Low bandgap high entropy alloy for visible light-assisted photocatalytic degradation of pharmaceutically active compounds: Performance assessment and mechanistic insights.

The incessant accumulation of pharmaceutically active compounds (PhACs) in various environmental compartments represents a global menace. Herein, an equimolar high entropy alloy (HEA), i.e., FeCoNiCuZn, is synthesized via a facile and scalable method, and its effectiveness in eliminating four different PhACs from aqueous matrices is rigorously examined. Attributing to its relatively low bandgap and multielement active sites, the as-synthesized quinary HEA demonstrates more pronounced photocatalytic decomposition efficiency, towards tetracycline (86%), sulfamethoxazole (94%), ibuprofen (80%), and diclofenac (99%), than conventional semiconductor-based photocatalysts, under visible light irradiation. Additionally, radical trapping assays are conducted, and the dissociation intermediates are identified, to probe the plausible photocatalytic degradation pathways. Further, the end-products of FeCoNiCuZn-mediated photocatalysis are apparently non-toxic, and the HEA can be successfully recycled repeatedly, with no obvious leaching of heavy metal ions. Overall, the findings of this study testify the applicability of FeCoNiCuZn as a visible light-active photocatalyst, for treating wastewaters contaminated with PhACs.

Synthesis and Characterization of Biotene: A New 2D Natural Oxide From Biotite.

In this work, the synthesis and characterization of ultrathin metal oxide, called biotene, using liquid-phase exfoliation from naturally abundant biotite are demonstrated. The atomically thin biotene is used for energy harvesting using its flexoelectric response under multiple bending. The effective flexoelectric response increases due to the presence of surface charges, and the voltage increases up to ≈8 V, with a high mechano-sensitivity of 0.79 V N-1 for normal force. This flexoelectric response is further validated by density functional theory (DFT) simulations. The atomically thin biotene shows an increased response in the magnetic field and thermal heating. The synthesis of two-dimensional (2D) metal-oxide biotene suggests a wealth of future 2D-oxide material for energy generation and energy harvesting applications.

Identification of aggregated 2D cobalt tellurides using a spatial self-phase modulation technique.

We report a previously unreported application of the spatial self-phase modulation (SSPM) technique for recognizing solute-solvent interaction in a suspension of 2D material. Broadband optical absorption of the 2D Co2Te3 leads to a nonlinear optical (NLO) susceptibility for the monolayer, i.e., χ M o n o(3) of 1.5 ×10-9 (3.3 ×10-9) esu at 532 (632) nm, which is 1-2 orders higher than for the 2D CoTe and CoTe2. The fine structure of the SSPM patterns is analyzed to explore the foundations of the observed NLO effects. With increasing polarity of the liquid media, a change of 2D Co2Te3 from homophonous dispersion to aggregation occurs, as confirmed from in situ optical microscopy and UV-vis absorption spectroscopy. As a result, type-I (thickest outer ring) SSPM ring patterns are converted to type-II (thinnest outer ring) SSPM ring patterns. Therefore, using SSPM with a CW laser as an optical tool to identify solvent-polarity-induced aggregation in 2D materials is possible.

Spontaneous Time-Reversal Symmetry Breaking at Individual Grain Boundaries in Graphene.

Graphene grain boundaries (GBs) have attracted interest for their ability to host nearly dispersionless electronic bands and magnetic instabilities. Here, we employ quantum transport and universal conductance fluctuation measurements to experimentally demonstrate a spontaneous breaking of time-reversal symmetry across individual GBs of chemical vapor deposited graphene. While quantum transport across the GBs indicate spin-scattering-induced dephasing and hence formation of local magnetic moments, below T≲4 K we observe complete lifting of time-reversal symmetry at high carrier densities (n≳5×10^{12} cm^{-2}) and low temperature (T≲2 K). An unprecedented thirtyfold reduction in the universal conductance fluctuation magnitude with increasing doping density further supports the possibility of an emergent frozen magnetic state at the GBs. Our experimental results suggest that realistic GBs of graphene can be a promising resource for new electronic phases and spin-based applications.

A multivariate modeling and experimental realization of photocatalytic system of engineered S-C3N4/ZnO hybrid for ciprofloxacin removal: Influencing factors and degradation pathways.

Ciprofloxacin, a pharmaceutically active compound, is present as a micropollutant in wastewater, which cannot be removed by conventional techniques due to its recalcitrant nature. Therefore, in the present study, the photocatalytic degradation of this bio-toxic compound was demonstrated using a three-dimensional sulfur-doped graphitic-carbon nitride/zinc oxide hybrid, with enriched oxygen vacancies. The influence of various water matrices and experimental conditions on the ciprofloxacin degradation was optimized. The hybrid material showed 98.8% and 75.8% degradation efficiency under optimum experimental conditions (i.e., catalyst dose: 1 g/L; pH: 5; initial ciprofloxacin concentration: 20 mg/L; temperature: 27 °C) under ultraviolet (UV) and visible light, respectively. A neural-network-based multivariate approach was used to predict a significant model considering the experimental conditions that showed adequate statistical significance (R2: 0.992 and F-value: 8707.1). The relative significance of the experimental conditions was assessed, suggesting that the initial ciprofloxacin concentration has a more significant effect on the degradation efficiency than the other factors. The rate kinetics and reaction mechanisms for ciprofloxacin degradation were demonstrated, and the driving radicals involved were identified. A higher rate of reaction was found under UV irradiation (0.01702 min-1) than under visible light (0.00802 min-1). Superoxide radicals were identified as the main driving radicals, which caused substantial photocatalytic reactions among the hybrid and ciprofloxacin molecules. Microscopic and macroscopic analyses of the used hybrid were conducted, which confirmed the presence of higher defect concentrations, crystallinity, and interlinked stacked structure in the hybrid. Hence, the 3D hybrid can be efficiently used and reused for ciprofloxacin degradation. This advanced photocatalytic system can be widely used to remediate emerging contaminants in wastewater treatment.

Scale-Enhanced Magnetism in Exfoliated Atomically Thin Magnetite Sheets.

The discovery of ferromagnetism in atomically thin layers at room temperature widens the prospects of 2D materials for device applications. Recently, two independent experiments demonstrated magnetic ordering in two dissimilar 2D systems, CrI3 and Cr2 Ge2 Te6 , at low temperatures and in VSe2 at room temperature, but observation of intrinsic room-temperature magnetism in 2D materials is still a challenge. Here a transition at room temperature that increases the magnetization in magnetite while thinning down the bulk material to a few atom-thick sheets is reported. DC magnetization measurements prove ferrimagnetic ordering with increased magnetization and density functional theory calculations ascribe their origin to the low dimensionality of the magnetite layers. In addition, surface energy calculations for different cleavage planes in passivated magnetite crystal agree with the experimental observations of obtaining 2D sheets from non-van der Waals crystals.

Photo-induced degradation of bio-toxic Ciprofloxacin using the porous 3D hybrid architecture of an atomically thin sulfur-doped g-C3N4/ZnO nanosheet.

Ciprofloxacin is a pharmaceutically active compound which belongs to a class of micropollutants that cannot be removed using conventional water treatment systems. In this study, photocatalytic degradation using materials with high surface area and active sites was proposed to remove such contaminants. We demonstrated an easily scalable and simple synthesis route to prepare a 3D porous sulfur-doped g-C3N4/ZnO hybrid material, and the preparation process parameters were optimized using response surface methodology targeting Ciprofloxacin degradation. The hybrid material removed up to 98% of the bio-toxic Ciprofloxacin from synthetic water. The porous, defect engineered, thermally stable, and chemically interconnected hybrid material presented an 18 and 38% improved degradation efficiency compared to ZnO and sulfur-doped g-C3N4 (or S-C3N4), respectively. Based on our experimental results, an empirical relation correlating synthesis process parameters and degradation efficiency was developed using face-centered central composite design (FCCD) and response surface methodology (RSM). The current model can be used to design catalytic materials for removing bio-toxic and other micropollutants from water.

Two-Dimensional Lateral Epitaxy of 2H (MoSe2)-1T' (ReSe2) Phases.

Two-dimensional (2D) transition metal dichalcogenide (TMDC) heterostructures have been proposed as potential candidates for a variety of applications like quantum computing, neuromorphic computing, solar cells, and flexible field effective transistors. The 2D TMDC heterostructures at the present stage face difficulties being implemented in these applications because of lack of large and sharp heterostructure interfaces. Herein, we address this problem via a CVD technique to grow thermodynamically stable heterostructure of 2H/1T' MoSe2-ReSe2 using conventional transition metal phase diagrams as a reference. We demonstrate how the thermodynamics of mixing in the MoReSe2 system during CVD growth dictates the formation of atomically sharp interfaces between MoSe2 and ReSe2, which can be confirmed by high-resolution scanning transmission electron microscopy imaging, revealing zigzag selenium-terminated interface between the epitaxial 2H and 1T' lattices. Our work provides useful insights for understanding the stability of 2D heterostructures and interfaces between chemically, structurally, and electronically different phases.

Optical Control of Non-Equilibrium Phonon Dynamics.

The light-induced selective population of short-lived far-from-equilibrium vibration modes is a promising approach for controlling ultrafast and irreversible structural changes in functional nanomaterials. However, this requires a detailed understanding of the dynamics and evolution of these phonon modes and their coupling to the excited-state electronic structure. Here, we combine femtosecond mega-electronvolt electron diffraction experiments on a prototypical layered material, MoTe2, with non-adiabatic quantum molecular dynamics simulations and ab initio electronic structure calculations to show how non-radiative energy relaxation pathways for excited electrons can be tuned by controlling the optical excitation energy. We show how the dominant intravalley and intervalley scattering mechanisms for hot and band-edge electrons leads to markedly different transient phonon populations evident in electron diffraction patterns. This understanding of how tuning optical excitations affect phonon populations and atomic motion is critical for efficiently controlling light-induced structural transitions of optoelectronic devices.

3D Printed Tubulanes as Lightweight Hypervelocity Impact Resistant Structures.

Lightweight materials with high ballistic impact resistance and load-bearing capabilities are regarded as a holy grail in materials design. Nature builds these complementary properties into materials using soft organic materials with optimized, complex geometries. Here, the compressive deformation and ballistic impact properties of three different 3D printed polymer structures, named tubulanes, are reported, which are the architectural analogues of cross-linked carbon nanotubes. The results show that macroscopic tubulanes are remarkable high load-bearing, hypervelocity impact-resistant lightweight structures. They exhibit a lamellar deformation mechanism, arising from the tubulane ordered pore structure, manifested across multiple length scales from nano to macro dimensions. This approach of using complex geometries inspired by atomic and nanoscale models to generate macroscale printed structures allows innovative morphological engineering of materials with tunable mechanical responses.

Stabilization of a Highly Concentrated Colloidal Suspension of Pristine Metallic Nanoparticles.

A colloidal suspension containing a high concentration of metallic nanoparticles (NPs) finds potential applications in flexible electronic printing, nanofluids, healthcare, antifouling coating, and so on. Here, we demonstrate a generic, easily scalable, simple, and contamination-free cryogenic temperature grinding method, which can effectively be used to prepare pristine NPs that can be stabilized in polar liquids in high concentrations. These surfactant-free pristine NPs have been found to remain dispersed in different polar liquids (CH3OH, C2H5OH, glycol, etc.) for weeks. The long-term stability of the NPs in these liquids has been investigated using zeta potential, in situ Fourier transform infrared spectroscopy, indicating electrostatic stabilization for ultrapure, surfactant-free NPs. Furthermore, stabilization of the NPs has been probed with detailed calculations using the Derjaguin Landau Verwey Overbeek theory as well as atomistic molecular dynamics simulation (MD). Experimental measurements along with theoretical calculations categorically indicate that the electrostatic energy is helping these NPs to be stabilized in a polar liquid.

Effect of Carrier Localization on Electrical Transport and Noise at Individual Grain Boundaries in Monolayer MoS2.

Despite its importance in the large-scale synthesis of transition metal dichalcogenides (TMDC) molecular layers, the generic quantum effects on electrical transport across individual grain boundaries (GBs) in TMDC monolayers remain unclear. Here we demonstrate that strong carrier localization due to the increased density of defects determines both temperature dependence of electrical transport and low-frequency noise at the GBs of chemical vapor deposition (CVD)-grown MoS2 layers. Using field effect devices designed to explore transport across individual GBs, we show that the localization length of electrons in the GB region is ∼30-70% lower than that within the grain, even though the room temperature conductance across the GB, oriented perpendicular to the overall flow of current, may be lower or higher than the intragrain region. Remarkably, we find that the stronger localization is accompanied by nearly 5 orders of magnitude enhancement in the low-frequency noise at the GB region, which increases exponentially when the temperature is reduced. The microscopic framework of electrical transport and noise developed in this paper may be readily extended to other strongly localized two-dimensional systems, including other members of the TMDC family.

Thermoelectricity Enhanced Electrocatalysis.

We show that thermoelectric materials can function as electrocatalysts and use thermoelectric voltage generated to initiate and boost electrocatalytic reactions. The electrocatalytic activity is promoted by the use of nanostructured thermoelectric materials in a hydrogen evolution reaction (HER) by the thermoelectricity generated from induced temperature gradients. This phenomenon is demonstrated using two-dimensional layered thermoelectric materials Sb2Te3 and Bi0.5Sb1.5Te3 where a current density approaching ∼50 mA/cm2 is produced at zero potential for Bi0.5Sb1.5Te3 in the presence of a temperature gradient of 90 °C. In addition, the turnover frequency reaches to 2.7 s-1 at 100 mV under this condition which was zero in the absence of temperature gradient. This result adds a new dimension to the properties of thermoelectric materials which has not been explored before and can be applied in the field of electrocatalysis and energy generation.

Worm-Shape Pt Nanocrystals Grown on Nitrogen-Doped Low-Defect Graphene Sheets: Highly Efficient Electrocatalysts for Methanol Oxidation Reaction.

Although direct methanol fuel cell offers high energy use efficiency and low pollution emission, the lack of suitable electrode materials poses a great challenge to its commercial application. Herein, a facile and scalable approach is developed to fabricate a hybrid electrocatalyst consisting of strongly coupled worm-shape Pt nanocrystals and nitrogen-doped low-defect graphene (N-LDG) sheets. Interestingly, it is found that the formation of Pt nanoworms (NWs) is induced by the N atoms in the high-quality carbon matrix, which also allows the integration of their respective structural advantages and leads to a strong synergetic coupling effect. As a result, the obtained Pt NW/N-LDG catalyst exhibits an extremely high mass activity of 1283.1 mA mg-1 toward methanol oxidation reaction, accompanied by reliable long-term stability and good antipoisoning ability, which are dramatically enhanced as compared with conventional Pt nanoparticle catalysts dispersed on undoped LDG, reduced graphene oxide, and commercial carbon black supports.