Stabilizing Ti3C2Tx MXene flakes in air by removing confined water.

MXenes have demonstrated potential for various applications owing to their tunable surface chemistry and metallic conductivity. However, high temperatures can accelerate MXene film oxidation in air. Understanding the mechanisms of MXene oxidation at elevated temperatures, which is still limited, is critical in improving their thermal stability for high-temperature applications. Here, we demonstrate that Ti[Formula: see text]C[Formula: see text]T[Formula: see text] MXene monoflakes have exceptional thermal stability at temperatures up to 600[Formula: see text]C in air, while multiflakes readily oxidize in air at 300[Formula: see text]C. Density functional theory calculations indicate that confined water between Ti[Formula: see text]C[Formula: see text]T[Formula: see text] flakes has higher removal energy than surface water and can thus persist to higher temperatures, leading to oxidation. We demonstrate that the amount of confined water correlates with the degree of oxidation in stacked flakes. Confined water can be fully removed by vacuum annealing Ti[Formula: see text]C[Formula: see text]T[Formula: see text] films at 600[Formula: see text]C, resulting in substantial stability improvement in multiflake films (can withstand 600[Formula: see text]C in air). These findings provide fundamental insights into the kinetics of confined water and its role in Ti[Formula: see text]C[Formula: see text]T[Formula: see text] oxidation. This work enables the use of stable monoflake MXenes in high-temperature applications and provides guidelines for proper vacuum annealing of multiflake films to enhance their stability.

Design of Atomic Ordering in Mo2Nb2C3Tx MXenes for Hydrogen Evolution Electrocatalysis.

The need for novel materials for energy storage and generation calls for chemical control at the atomic scale in nanomaterials. Ordered double-transition-metal MXenes expanded the chemical diversity of the family of atomically layered 2D materials since their discovery in 2015. However, atomistic tunability of ordered MXenes to achieve ideal composition-property relationships has not been yet possible. In this study, we demonstrate the synthesis of Mo2+αNb2-αAlC3 MAX phases (0 ≤ α ≤ 0.3) and confirm the preferential ordering behavior of Mo and Nb in the outer and inner M layers, respectively, using density functional theory, Rietveld refinement, and electron microscopy methods. We also synthesize their 2D derivative Mo2+αNb2-αC3Tx MXenes and exemplify the effect of preferential ordering on their hydrogen evolution reaction electrocatalytic behavior. This study seeks to inspire further exploration of the ordered double-transition-metal MXene family and contribute composition-behavior tools toward application-driven design of 2D materials.

Spherical Templating of CoSe2 Nanoparticle-Decorated MXenes for Lithium-Sulfur Batteries.

Two-dimensional MXenes produce competitive performances when incorporated into lithium-sulfur batteries (LSBs), solving key problems such as the poor electronic conductivity of sulfur and dissolution of its polysulfide intermediates. However, MXene nanosheets are known to easily aggregate and restack during electrode fabrication, filtration, or water removal, limiting their practical applicability. Furthermore, in complex electrocatalytic reactions like the multistep sulfur reduction process in LSBs, MXene alone is insufficient to ensure an optimal reaction pathway. In this work, we demonstrate for the first time a loose templating of sulfur spheres using Ti3C2Tx MXene nanosheets decorated with polymorphic CoSe2 nanoparticles. This work shows that the templating of sulfur spheres using nanoparticle-decorated MXene nanosheets can prevent nanosheet aggregation and exert a strong electrocatalytic effect, thereby enabling improved reaction kinetics and battery performance. The S@MXene-CoSe2 cathode demonstrated a long cycle life of 1000 cycles and a low capacity decay rate of 0.06% per cycle in LSBs.

Accelerating 2D materials discovery.

A large-scale theory-driven approach predicts many new 2D materials.

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.

Treatment of carbon electrodes with Ti3C2Tx MXene coating and thermal method for vanadium redox flow batteries: a comparative study.

One of the significant challenges of vanadium redox flow batteries is connected to the negative electrode where the main reaction of V(ii)/V(iii) and the side reaction of hydrogen evolution compete. To address this issue, we used titanium carbide (Ti3C2Tx) MXene coating via drop-casting to introduce oxygen functional groups and metals on the carbon electrode surface. Characterization through scanning electron microscopy and X-ray photoelectron spectroscopy confirmed the even distribution of Ti3C2Tx MXene on the electrodes and the presence of titanium and termination groups (-O, -Cl, and -F). The cyclic voltammetry analysis of MXene-coated electrodes showed more sharp electrochemical peaks for the V(ii)/V(iii) reaction than thermal-treated electrodes, even at relatively high scan rates. Notably, a relatively high reaction rate of 5.61 × 10-4 cm s-1 was achieved for the V(ii)/V(iii) reaction on MXene-coated electrodes, which shows the competitiveness of the method compared to thermal treatment (4.17 × 10-4 cm s-1). The flow battery tests, at a current density of 130 mA cm-2, using MXene-coated electrodes showed pretty stable discharge capacity for over 100 cycles. In addition, the voltage and energy efficiency were significantly higher than those of the system using untreated electrodes. Overall, this work highlights the potential application of MXene coating in carbon electrode treatment for vanadium redox flow batteries due to remarkable electrocatalytic activity and battery performance, providing a competitive method for thermal treatment.

Plasmonic Copper-activated ZnO Microarrays for Efficient Photoelectrocatalytic Applications.

In the present work, green synthesized plasmonic copper nanostructures derived from carbon quantum dots (PCQDs) activated ZnO microarrays (MAs) based catalyst system is developed and studied for photocatalytic activity and photoelectrocatalytic water splitting. CQDs are synthesized from pharmaceutical waste and used as a reducing agent to synthesize PCQDs of an average size of 10±2 nm. PCQDs decorated ZnO (PCQDs/ZnO) MAs exhibited enhanced photocurrent density of ∼7.1 mA/cm2 at 1.23 V (vs. RHE), which is ∼11 fold to ZnO MAs alone (0.65 mA/cm2 ). The catalyst exhibits an ABPE of 1.07% at 0.7 V (vs. RHE), IPEC of 8.8% for 450 nm, and hydrogen production rate of 435 µmol/h. The enhanced PEC characteristics are assigned to the improved photons collection and better charge transfer for their participation in oxidation/reduction reaction. The same is well supported with DFT studies for the PCQDs/ZnO MAs catalyst for the first time.

Excitonic effects on the optical spectra of TiB2nanosheets.

Two-dimensional (2D) transition metal borides, have recently attracted tremendous interest and become an emerging class of 2D materials due to their intriguing properties. We report systematic investigation of stability, electronic properties and optical activity of 2D-TiB2nanosheets using first-principles calculations. By combining elastic and phonon-dispersion calculations, we substantiated the mechanical and dynamic stability of 2D-TiB2nanosheets. Our results of elastic calculations reveal that addition of an extra layer destroys the auxetic behaviour of monolayer (ML) 2D-TiB2with significant reduction in the brittleness. Further, based on the spin-polarised electronic structure calculations, we find that a low-dimensional metallic state of ML can be achieved by tuning the distance between the titanium and boron layers. The calculations clearly reveal that metallic nature does not destroys the auxetic behaviour of ML. Subsequently, we investigated the optical response of 2D-TiB2nanosheets (ML and bilayer (BL)) at the level of density functional theory and many-body perturbation theory. The results obtained by solving Bethe-Salpeter equation (GW+BSE formalism) shows that excitonic effects causes a slight blue-shift in the absorption spectra of the nanosheets with ML being optically active with sharp peaks in infrared (IR) and ultraviolet (UV) regions while BL shows the reduced optical activity across wide range of photon energies spanning the near-IR to UV region. In addition, electronic polarisability of the nanosheet decreases with addition of another layer in ML 2D-TiB2. Further investigation of transition probabilities clearly indicates that the response of ML at Dirac point is tunable by spin-orbital coupling effects which makes these nanosheets promising for spintronic applications. The BL exhibits distinct electronic, and optical properties compared to ML. Our study unravels the structural, elastic, electronic, and optical properties of 2D-TiB2nanosheets and suggests them as promising candidate for variety of optoelectronic and spintronic applications.

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.

The Evolution of MXenes Conductivity and Optical Properties Upon Heating in Air.

MXenes, a family of 2D transition-metal carbides and nitrides, have excellent electrical conductivity and unique optical properties. However, MXenes oxidize in ambient conditions, which is accelerated upon heating. Intercalation of water also causes hydrolysis accelerating oxidation. Developing new tools to readily characterize MXenes' thermal stability can enable deeper insights into their structure-property relationships. Here, in situ spectroscopic ellipsometry (SE) is employed to characterize the optical properties of three types of MXenes (Ti3 C2 Tx , Mo2 TiC2 Tx , and Ti2 CTx ) with varied composition and atomistic structures to investigate their thermal degradation upon heating under ambient environment. It is demonstrated that changes in MXene extinction and optical conductivity in the visible and near-IR regions correlate well with the amount of intercalated water and hydroxyl termination groups and the degree of oxidation, measured using thermogravimetric analysis. Among the three MXenes, Ti3 C2 Tx and Ti2 CTx , respectively, have the highest and lowest thermal stability, indicating the role of transition-metal type, synthesis route, and the number of atomic layers in MXene flakes. These findings demonstrate the utility of SE as a powerful in situ technique for rapid structure-property relationship studies paving the way for the further design, fabrication, and property optimization of novel MXene materials.

Double-Transition-Metal MXene Films Promoting Deeply Rechargeable Magnesium Metal Batteries.

Magnesium metal batteries are promising candidates for next-generation high-energy-density and low-cost energy storage systems. Their application, however, is precluded by infinite relative volume changes and inevitable side reactions of Mg metal anodes. These issues become more pronounced at large areal capacities that are required for practical batteries. Herein, for the first time, double-transition-metal MXene films are developed to promote deeply rechargeable magnesium metal batteries using Mo2 Ti2 C3 as a representative example. The freestanding Mo2 Ti2 C3 films, which are prepared using a simple vacuum filtration method, possess good electronic conductivity, unique surface chemistry, and high mechanical modulus. These superior electro-chemo-mechanical merits of Mo2 Ti2 C3 films help to accelerate electrons/ions transfer, suppress electrolyte decomposition and dead Mg formation, as well as maintain electrode structural integrity during long-term and large-capacity operation. As a result, the as-developed Mo2 Ti2 C3 films exhibit reversible Mg plating/stripping with high Coulombic efficiency of 99.3% at a record-high capacity of 15 mAh cm-2 . This work not only sheds innovative insights into current collector design for deeply cyclable Mg metal anodes, but also paves the way for the application of double-transition-metal MXene materials in other alkali and alkaline earth metal batteries.

Step-by-Step Guide for Synthesis and Delamination of Ti3 C2 Tx MXene.

To advance the MXene field, it is crucial to optimize each step of the synthesis process and create a detailed, systematic guide for synthesizing high-quality MXene that can be consistently reproduced. In this study, a detailed guide is provided for an optimized synthesis of titanium carbide (Ti3 C2 Tx ) MXene using a mixture of hydrofluoric and hydrochloric acids for the selective etching of the stoichimetric-Ti3 AlC2 MAX phase and delamination of the etched multilayered Ti3 C2 Tx MXene using lithium chloride at 65 °C for 1 h with argon bubbling. The effect of different synthesis variables is investigated, including the stoichiometry of the mixed powders to synthesize Ti3 AlC2 , pre-etch impurity removal conditions, selective etching, storage, and drying of MXene multilayer powder, and the subsequent delamination conditions. The synthesis yield and the MXene film electrical conductivity are used as the two parameters to evaluate the MXene quality. Also the MXenes are characterized with scanning electron microscopy, x-ray diffraction, atomic force microscopy, and ellipsometry. The Ti3 C2 Tx film made via the optimized method shows electrical conductivity as high as ≈21,000 S/cm with a synthesis yield of up to 38 %. A detailed protocol is also provided for the Ti3 C2 Tx MXene synthesis as the supporting information for this study.

A Comprehensive Review on Water Quality Monitoring Devices: Materials Advances, Current Status, and Future Perspective.

Water quality monitoring has become more critical in recent years to ensure the availability of clean and safe water from natural aquifers and to understand the evolution of water contaminants across time and space. The conventional water monitoring techniques comprise of sample collection, preservation, preparation, tailed by laboratory testing and analysis with cumbersome wet chemical routes and expensive instrumentation. Despite the high accuracy of these methods, the high testing costs, laborious procedures, and maintenance associated with them don't make them lucrative for end end-users and field testing. As the participation of ultimate stakeholders, that is, common man for water quality and quantity can play a pivotal role in ensuring the sustainability of our aquifers, thus it is essential to develop and deploy portable and user-friendly technical systems for monitoring water sources in real-time or on-site. The present review emphasizes here on possible approaches including optical (absorbance, fluorescence, colorimetric, X-ray fluorescence, chemiluminescence), electrochemical (ASV, CSV, CV, EIS, and chronoamperometry), electrical, biological, and surface-sensing (SPR and SERS), as candidates for developing such platforms. The existing developments, their success, and bottlenecks are discussed in terms of various attributes of water to escalate the essentiality of water quality devices development meeting ASSURED criterion for societal usage. These platforms are also analyzed in terms of their market potential, advancements required from material science aspects, and possible integration with IoT solutions in alignment with Industry 4.0 for environmental application.

A machine learning-based approach to determine infection status in recipients of BBV152 (Covaxin) whole-virion inactivated SARS-CoV-2 vaccine for serological surveys.

Data science has been an invaluable part of the COVID-19 pandemic response with multiple applications, ranging from tracking viral evolution to understanding the vaccine effectiveness. Asymptomatic breakthrough infections have been a major problem in assessing vaccine effectiveness in populations globally. Serological discrimination of vaccine response from infection has so far been limited to Spike protein vaccines since whole virion vaccines generate antibodies against all the viral proteins. Here, we show how a statistical and machine learning (ML) based approach can be used to discriminate between SARS-CoV-2 infection and immune response to an inactivated whole virion vaccine (BBV152, Covaxin). For this, we assessed serial data on antibodies against Spike and Nucleocapsid antigens, along with age, sex, number of doses taken, and days since last dose, for 1823 Covaxin recipients. An ensemble ML model, incorporating a consensus clustering approach alongside the support vector machine model, was built on 1063 samples where reliable qualifying data existed, and then applied to the entire dataset. Of 1448 self-reported negative subjects, our ensemble ML model classified 724 to be infected. For method validation, we determined the relative ability of a random subset of samples to neutralize Delta versus wild-type strain using a surrogate neutralization assay. We worked on the premise that antibodies generated by a whole virion vaccine would neutralize wild type more efficiently than delta strain. In 100 of 156 samples, where ML prediction differed from self-reported uninfected status, neutralization against Delta strain was more effective, indicating infection. We found 71.8% subjects predicted to be infected during the surge, which is concordant with the percentage of sequences classified as Delta (75.6%-80.2%) over the same period. Our approach will help in real-world vaccine effectiveness assessments where whole virion vaccines are commonly used.

Nanostructures derived from expired drugs and their applications toward sensing, security ink, and bactericidal material.

In this research, a facile and economical route is introduced for the transformation of pharmaceutical waste (i.e., expired medicines) into value-added fluorescent carbon quantum dots (pharmaceutically derived CQDs abbreviated as 'P-CQDs'). The synthesized P-CQDs were identified to have surface functionalities of -OH, C=O, and C=C with an average size of ~2-3 nm and a high quantum yield of 35.3%. The photoluminescence of P-CQDs recorded a maximum optical emission intensity at 2.8 eV (425 nm). The binding of Cu (II) ions by -COOH functionalities on the surface of P-CQDs led to its fluorescence quenching (turn-off) over a wide Cu (II) concentration range of 0.25-50 ppm. The P-CQDs exhibited the detection limit of 0.66 ppm (well below the WHO permissible limit of 2 ppm). The fluorescence intensity of the P-CQDs-Cu (II) complex was recovered from NaHCO3.Hence, their "off-on" behavior was also explored for security ink applications for information encryption and decryption. Moreover, the rich oxygenated groups on the surface of the P-CQDs were utilized for green synthesis of plasmonic Ag@P-CQDs nanostructures, which were also demonstrated to have enhanced potential as bactericidal materials (e.g., against both E. coli and S. aureus). The overall results of this study are demonstrated to help create new and diverse routes for converting expired drugs into value-added nanostructures.

TiO2 nanofibres decorated with green-synthesized PAu/Ag@CQDs for the efficient photocatalytic degradation of organic dyes and pharmaceutical drugs.

Organic pollutants such as dyes and pharmaceutical drugs have become an environmental menace, particularly in water bodies owing to their unregulated discharge. It is thus required to develop an economically viable and environment-friendly approach for their degradation in water bodies. In this study, for the first time, we report green route-synthesized plasmonic nanostructures (PM-CQDs (where M: Au and Ag)) decorated onto TiO2 nanofibers for the treatment of toxic dye- and pharmaceutical drug-based wastewater. PM-CQDs are efficaciously synthesized using carbon quantum dots (CQDs) as the sole reducing and capping agent, wherein CQDs are derived via a green synthesis approach from Citrus limetta waste. The characteristic electron-donating property of CQDs played a key role in the reduction of Au3+ to Au0 and Ag+ to Ag0 under visible light irradiation to obtain PAu-CQDs and PAg-CQDs, respectively. Thus, the obtained CQDs, PAu-CQDs, and PAg-CQDs are loaded onto TiO2 nanofibers to obtain a PM-CQD/TiO2 nanocomposite (NC), and are further probed via transmission electron microscopy, scanning electron microscopy and UV-visible spectrophotometry. The degradation of organic pollutants and pharmaceutical drugs using methylene blue and erythromycin as model pollutants is mapped with UV-vis and NMR spectroscopy. The results demonstrate the complete MB dye degradation in 20 minutes with 1 mg mL-1 of PAu-CQD/TiO2 NC, which otherwise is 30 minutes for PAg@CQD/TiO2 dose under visible light irradiation. Similarly, the pharmaceutical drug was found to degrade in 150 minutes with PAu-CQD/TiO2 photocatalysts. These findings reveal the enhanced photocatalytic performance of the green-synthesized Au decorated with TiO2 nanofibers and are attributed to the boosted SPR effect and aqueous-phase stability of Au nanostructures. This study opens a new domain of utilizing waste-derived and green-synthesized plasmonic nanostructures for the degradation of toxic/hazardous dyes and pharmaceutical pollutants in water.

Waste derivitized blue luminescent carbon quantum dots for selenite sensing in water.

Herein, we report an environmental friendly, facile, and completely green synthetic method for producing carbon quantum dots (CQDs) from whey, a major dairy waste. The as-prepared monodispersed diameter CQDs exhibit blue luminescence with noteworthy quantum yield (~11.4%) and excitation dependent emission behaviour. Nuclear magnetic resonance (NMR) analysis reveals the presence of aromatized carbon peaks, leading to polymerized CQDs diameter architecture during whey pyrolysis. The X-ray and selected area electron diffraction patterns confirm their amorphous nature. Further, we demonstrate, these CQDs as an effective sensor probe for selective selenite monitoring in water upon functionalization with appropriate ligand. The functionalized GCQDs probe is shown to detect selenite with high sensitivity in 10-1000ppb detection range. Further it is selective for selenite over other relevant ions (such as Cu2+, As3+, As5+, Pb2+, Ni2+, Se6+, Cl-, Br-, NO3-, NO2- and F-) and displays a sub-ppb detection limit at 1.1% relative standard deviation.

A "Turn-On" thiol functionalized fluorescent carbon quantum dot based chemosensory system for arsenite detection.

Carbon quantum dots (CQDs) have emerged out as promising fluorescent probes for hazardous heavy metals detection in recent past. In this study, water soluble CQDs were synthesized by facile microwave pyrolysis of citric acid & cysteamine, and functionalized with ditheritheritol to impart thiol functionalities at surface for selective detection of toxic arsenite in water. Microscopic analysis reveals that the synthesized CQDs are of uniform size (diameter ∼5nm) and confirmed to have surface SH groups by FT-IR. The functionalized probe is then demonstrated for arsenite detection in water by "Turn-On" read out mechanism, which reduces the possibility of false positive signals associated with "turn off' probes reported earlier. The blue luminescent functionalized CQDs exhibit increase in fluorescence intensity on arsenite addition in 5-100ppb wide detection range. The probe can be used for sensitive detection of arsenite in environmental water to a theoretical detection limit (3s) of 0.086ppb (R2=0.9547) with good reproducibility at 2.6% relative standard deviation. The presented reliable, sensitive, rapid fCQDs probe demonstrated to exhibit high selectivity towards arsenite and exemplified for real water samples as well. The analytical performance of the presented probe is comparable to existing organic & semiconductor based optical probes.

Ultrasensitive and Selective Sensing of Selenium Using Nitrogen-Rich Ligand Interfaced Carbon Quantum Dots.

This work reports a label-free, ultrasensitive, and selective optical chemosensory system for trace level detection of selenite (SeO32-), the most toxic form of selenium, in water. The probe, i.e., carbon quantum dots (CQDs), is designed from citric acid by means of pyrolysis and is interfaced with a newly synthesized nitrogen-rich ligand to create a selective sensor platform (functionalized CQDs, fCQDs) for selenite in a water matrix. Spectral (NMR, UV-vis, photoluminescence, Raman, and Fourier transform infrared analyses) and structural (high-resolution transmission electron microscopy) characteristics of the designed new probe were investigated. The developed sensor exhibits high sensitivity (limit of detection = 0.1 ppb), a wide detection range (0.1-1000 ppb range, relative standard deviation: 3.2%), and high selectivity even in the presence of commonly interfering ions reported to date, including Cl-, NO3-, NO2-, Br-, F-, As(V), As(III), Cu2+, Pb2+, Cd2+, Zn2+, Sr2+, Rb2+, Na+, Ca2+, Cs+, K+, Mg2+, Li+, NH4+, Co2+, etc. The observed selectivity is due to designed ligand characteristics in terms of strong Se-N chemistry. Ultrafast spectroscopic analysis of the fCQDs in the absence and presence of selenite was studied to understand the sensing mechanism. The sensor was successfully exemplified for real water samples and exhibits comparative performance to conventional ion channel chromatography as well as flame atomic absorption spectroscopy for selenite analysis. The promising results pave ways for realization of a field deployable device based upon a developed probe for selenite quantification in water.