Showing papers by "Yury Gogotsi published in 2017"

2D metal carbides and nitrides (MXenes) for energy storage

Abstract: The family of 2D transition metal carbides, carbonitrides and nitrides (collectively referred to as MXenes) has expanded rapidly since the discovery of Ti3C2 in 2011. The materials reported so far always have surface terminations, such as hydroxyl, oxygen or fluorine, which impart hydrophilicity to their surfaces. About 20 different MXenes have been synthesized, and the structures and properties of dozens more have been theoretically predicted. The availability of solid solutions, the control of surface terminations and a recent discovery of multi-transition-metal layered MXenes offer the potential for synthesis of many new structures. The versatile chemistry of MXenes allows the tuning of properties for applications including energy storage, electromagnetic interference shielding, reinforcement for composites, water purification, gas- and biosensors, lubrication, and photo-, electro- and chemical catalysis. Attractive electronic, optical, plasmonic and thermoelectric properties have also been shown. In this Review, we present the synthesis, structure and properties of MXenes, as well as their energy storage and related applications, and an outlook for future research. More than twenty 2D carbides, nitrides and carbonitrides of transition metals (MXenes) have been synthesized and studied, and dozens more predicted to exist. Highly electrically conductive MXenes show promise in electrical energy storage, electromagnetic interference shielding, electrocatalysis, plasmonics and other applications.

Guidelines for Synthesis and Processing of Two-Dimensional Titanium Carbide (Ti3C2Tx MXene)

Abstract: Two-dimensional (2D) transition metal carbides, carbonitrides, and nitrides (MXenes) were discovered in 2011. Since the original discovery, more than 20 different compositions have been synthesized by the selective etching of MAX phase and other precursors and many more theoretically predicted. They offer a variety of different properties, making the family promising candidates in a wide range of applications, such as energy storage, electromagnetic interference shielding, water purification, electrocatalysis, and medicine. These solution-processable materials have the potential to be highly scalable, deposited by spin, spray, or dip coating, painted or printed, or fabricated in a variety of ways. Due to this promise, the amount of research on MXenes has been increasing, and methods of synthesis and processing are expanding quickly. The fast evolution of the material can also be noticed in the wide range of synthesis and processing protocols that determine the yield of delamination, as well as the quality...

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

Abstract: Pseudocapacitors based on redox-active materials have relatively high energy density but suffer from low power capability. Here the authors report that two-dimensional transition metal carbides exhibit high gravimetric, volumetric and areal capacitance values at high char…

Flexible MXene/Graphene Films for Ultrafast Supercapacitors with Outstanding Volumetric Capacitance

Abstract: A strategy to prepare flexible and conductive MXene/graphene (reduced graphene oxide, rGO) supercapacitor electrodes by using electrostatic self-assembly between positively charged rGO modified with poly(diallyldimethylammonium chloride) and negatively charged titanium carbide MXene nanosheets is presented. After electrostatic assembly, rGO nanosheets are inserted in-between MXene layers. As a result, the self-restacking of MXene nanosheets is effectively prevented, leading to a considerably increased interlayer spacing. Accelerated diffusion of electrolyte ions enables more electroactive sites to become accessible. The freestanding MXene/rGO-5 wt% electrode displays a volumetric capacitance of 1040 F cm−3 at a scan rate of 2 mV s−1 , an impressive rate capability with 61% capacitance retention at 1 V s−1 and long cycle life. Moreover, the fabricated binder-free symmetric supercapacitor shows an ultrahigh volumetric energy density of 32.6 Wh L−1, which is among the highest values reported for carbon and MXene based materials in aqueous electrolytes. This work provides fundamental insight into the effect of interlayer spacing on the electrochemical performance of 2D hybrid materials and sheds light on the design of next-generation flexible, portable and highly integrated supercapacitors with high volumetric and rate performances.

Oxidation Stability of Colloidal Two-Dimensional Titanium Carbides (MXenes)

Abstract: Two-dimensional (2D) transition metal carbides and nitrides (MXenes) have shown outstanding performances in electrochemical energy storage and many other applications. Delamination of MXene flakes in water produces colloidal solutions that are used to manufacture all kinds of products (thin films, coatings, and electrodes, etc.). However, the stability of MXene colloidal solutions, which is of critical importance to their application, remains largely unexplored. Here we report on the degradation of delaminated-Ti3C2Tx colloidal solutions (T represents the surface functionalities) and outline protocols to improve their stability. Ti3C2Tx MXene solutions in open vials degraded by 42%, 85%, and 100% after 5, 10, and 15 days, respectively, leading to the formation of cloudy-white colloidal solutionss containing primarily anatase (TiO2). On the other hand, the solution could be well-preserved when Ti3C2Tx MXene colloidal solutionss were stored in hermetic Ar-filled bottles at 5 °C, because dissolved oxygen, th...

Diverse Applications of Nanomedicine

Abstract: The design and use of materials in the nanoscale size range for addressing medical and health-related issues continues to receive increasing interest. Research in nanomedicine spans a multitude of areas, including drug delivery, vaccine development, antibacterial, diagnosis and imaging tools, wearable devices, implants, high-throughput screening platforms, etc. using biological, nonbiological, biomimetic, or hybrid materials. Many of these developments are starting to be translated into viable clinical products. Here, we provide an overview of recent developments in nanomedicine and highlight the current challenges and upcoming opportunities for the field and translation to the clinic.

Transparent, Flexible, and Conductive 2D Titanium Carbide (MXene) Films with High Volumetric Capacitance.

Abstract: 2D transition-metal carbides and nitrides, known as MXenes, have displayed promising properties in numerous applications, such as energy storage, electromagnetic interference shielding, and catalysis. Titanium carbide MXene (Ti3 C2 Tx ), in particular, has shown significant energy-storage capability. However, previously, only micrometer-thick, nontransparent films were studied. Here, highly transparent and conductive Ti3 C2 Tx films and their application as transparent, solid-state supercapacitors are reported. Transparent films are fabricated via spin-casting of Ti3 C2 Tx nanosheet colloidal solutions, followed by vacuum annealing at 200 °C. Films with transmittance of 93% (≈4 nm) and 29% (≈88 nm) demonstrate DC conductivity of ≈5736 and ≈9880 S cm-1 , respectively. Such highly transparent, conductive Ti3 C2 Tx films display impressive volumetric capacitance (676 F cm-3 ) combined with fast response. Transparent solid-state, asymmetric supercapacitors (72% transmittance) based on Ti3 C2 Tx and single-walled carbon nanotube (SWCNT) films are also fabricated. These electrodes exhibit high capacitance (1.6 mF cm-2 ) and energy density (0.05 µW h cm-2 ), and long lifetime (no capacitance decay over 20 000 cycles), exceeding that of graphene or SWCNT-based transparent supercapacitor devices. Collectively, the Ti3 C2 Tx films are among the state-of-the-art for future transparent, conductive, capacitive electrodes, and translate into technologically viable devices for next-generation wearable, portable electronics.

Hollow MXene Spheres and 3D Macroporous MXene Frameworks for Na-Ion Storage.

Abstract: 2D transition metal carbides and nitrides, named MXenes, are attracting increasing attentions and showing competitive performance in energy storage devices including electrochemical capacitors, lithium- and sodium-ion batteries, and lithium-sulfur batteries. However, similar to other 2D materials, MXene nanosheets are inclined to stack together, limiting the device performance. In order to fully utilize MXenes' electrochemical energy storage capability, here, processing of 2D MXene flakes into hollow spheres and 3D architectures via a template method is reported. The MXene hollow spheres are stable and can be easily dispersed in solvents such as water and ethanol, demonstrating their potential applications in environmental and biomedical fields as well. The 3D macroporous MXene films are free-standing, flexible, and highly conductive due to good contacts between spheres and metallic conductivity of MXenes. When used as anodes for sodium-ion storage, these 3D MXene films exhibit much improved performances compared to multilayer MXenes and MXene/carbon nanotube hybrid architectures in terms of capacity, rate capability, and cycling stability. This work demonstrates the importance of MXene electrode architecture on the electrochemical performance and can guide future work on designing high-performance MXene-based materials for energy storage, catalysis, environmental, and biomedical applications.

Two-dimensional heterostructures for energy storage

Abstract: Two-dimensional (2D) materials provide slit-shaped ion diffusion channels that enable fast movement of lithium and other ions. However, electronic conductivity, the number of intercalation sites, and stability during extended cycling are also crucial for building high-performance energy storage devices. While individual 2D materials, such as graphene, show some of the required properties, none of them can offer all properties needed to maximize energy density, power density, and cycle life. Here we argue that stacking different 2D materials into heterostructured architectures opens an opportunity to construct electrodes that would combine the advantages of the individual building blocks while eliminating the associated shortcomings. We discuss characteristics of common 2D materials and provide examples of 2D heterostructured electrodes that showed new phenomena leading to superior electrochemical performance. We also consider electrode fabrication approaches and finally outline future steps to create 2D heterostructured electrodes that could greatly expand current energy storage technologies. Heterostructures with alternating layers of different 2D materials are finding increasing attention in energy applications. Pomerantseva and Gogotsi survey the opportunities and challenges of both developing the heterostructures and their implementation in energy storage devices.

Dispersions of Two-Dimensional Titanium Carbide MXene in Organic Solvents

Abstract: Two-dimensional titanium carbide (Ti3C2Tx) MXene has attracted a great deal of attention in the research community and has already showed promise in numerous applications, but only its dispersions in aqueous solutions have previously been available. Here we show that Ti3C2Tx can be dispersed in many polar organic solvents, but the best dispersions were achieved in N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene carbonate, and ethanol. The dispersions were examined by measuring the concentration and absorbance spectra of MXene in organic solvents as well as correlating the concentration to solvent physical properties, such as surface tension, boiling point, and polarity index. Hildebrand and Hansen solubility parameters were additionally used to provide an initial understanding of how Ti3C2Tx MXene behaves in organic media and potentially develop quantitative correlations to select solvents and their combinations that can disperse Ti3C2Tx and other MXenes. Using this analysis, ...

Metallic MXene Saturable Absorber for Femtosecond Mode-Locked Lasers.

Abstract: 2D transition metal carbides, nitrides, and carbonitides called MXenes have attracted much attention due to their outstanding properties. However, MXene's potential in laser technology is not explored. It is demonstrated here that Ti3 CN, one of MXene compounds, can serve as an excellent mode-locker that can produce femtosecond laser pulses from fiber cavities. Stable laser pulses with a duration as short as 660 fs are readily obtained at a repetition rate of 15.4 MHz and a wavelength of 1557 nm. Density functional theory calculations show that Ti3 CN is metallic, in contrast to other 2D saturable absorber materials reported so far to be operative for mode-locking. 2D structural and electronic characteristics are well conserved in their stacked form, possibly due to the unique interlayer coupling formed by MXene surface termination groups. Noticeably, the calculations suggest a promise of MXenes in broadband saturable absorber applications due to metallic characteristics, which agrees well with the experiments of passively Q-switched lasers using Ti3 CN at wavelengths of 1558 and 1875 nm. This study provides a valuable strategy and intuition for the development of nanomaterial-based saturable absorbers opening new avenues toward advanced photonic devices based on MXenes.

Salt-Templated Synthesis of 2D Metallic MoN and Other Nitrides

Abstract: Two-dimensional (2D) transition-metal nitrides just recently entered the research arena, but already offer a potential for high-rate energy storage, which is needed for portable/wearable electronics and many other applications. However, a lack of efficient and high-yield synthesis methods for 2D metal nitrides has been a major bottleneck for the manufacturing of those potentially very important materials, and only MoN, Ti4N3, and GaN have been reported so far. Here we report a scalable method that uses reduction of 2D hexagonal oxides in ammonia to produce 2D nitrides, such as MoN. MoN nanosheets with subnanometer thickness have been studied in depth. Both theoretical calculation and experiments demonstrate the metallic nature of 2D MoN. The hydrophilic restacked 2D MoN film exhibits a very high volumetric capacitance of 928 F cm–3 in sulfuric acid electrolyte with an excellent rate performance. We expect that the synthesis of metallic 2D MoN and two other nitrides (W2N and V2N) demonstrated here will pro...

Nanodiamonds suppress the growth of lithium dendrites.

Abstract: Lithium metal has been regarded as the future anode material for high-energy-density rechargeable batteries due to its favorable combination of negative electrochemical potential and high theoretical capacity. However, uncontrolled lithium deposition during lithium plating/stripping results in low Coulombic efficiency and severe safety hazards. Herein, we report that nanodiamonds work as an electrolyte additive to co-deposit with lithium ions and produce dendrite-free lithium deposits. First-principles calculations indicate that lithium prefers to adsorb onto nanodiamond surfaces with a low diffusion energy barrier, leading to uniformly deposited lithium arrays. The uniform lithium deposition morphology renders enhanced electrochemical cycling performance. The nanodiamond-modified electrolyte can lead to a stable cycling of lithium | lithium symmetrical cells up to 150 and 200 h at 2.0 and 1.0 mA cm–2, respectively. The nanodiamond co-deposition can significantly alter the lithium plating behavior, affording a promising route to suppress lithium dendrite growth in lithium metal-based batteries.

Efficient Antibacterial Membrane based on Two-Dimensional Ti3C2Tx (MXene) Nanosheets.

Abstract: Advanced membranes that enable ultrafast water flux while demonstrating anti-biofouling characteristics can facilitate sustainable water/wastewater treatment processes. MXenes, two-dimensional (2D) metal carbides and nitrides, have attracted attention for applications in water/wastewater treatment. In this work, we reported the antibacterial properties of micrometer-thick titanium carbide (Ti3C2Tx) MXene membranes prepared by filtration on a polyvinylidene fluoride (PVDF) support. The bactericidal properties of Ti3C2Tx modified membranes were tested against Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis) by bacterial growth on the membrane surface and its exposure to bacterial suspensions. The antibacterial rate of fresh Ti3C2Tx MXene membranes reaches more than 73% against B. subtilis and 67% against E. coli as compared with that of control PVDF, while aged Ti3C2Tx membrane showed over 99% growth inhibition of both bacteria under same conditions. Flow cytometry showed about 70% population of dead and compromised cells after 24 h of exposure of both bacterial strains. The damage of the cell surfaces was also revealed by scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis, respectively. The demonstrated antibacterial activity of MXene coated membranes against common waterborne bacteria, promotes their potential application as anti-biofouling membrane in water and wastewater treatment processes.

Laminated and Two-Dimensional Carbon-Supported Microwave Absorbers Derived from MXenes

Abstract: Microwave absorbers with layered structures that can provide abundant interfaces are highly desirable for enhancing electromagnetic absorbing capability and decreasing the thickness. The atomically thin layers of two-dimensional (2D) transition-metal carbides (MXenes) make them a convenient precursor for synthesis of other 2D and layered structures. Here, laminated carbon/TiO2 hybrid materials composed of well-aligned 2D carbon sheets with embedded TiO2 nanoparticles were synthesized and showed excellent microwave absorption. Disordered 2D carbon layers with an unusual structure were obtained by annealing multilayer Ti3C2 MXene in a CO2 atmosphere. The minimum reflection coefficient of laminated carbon/TiO2 composites reaches −36 dB, and the effective absorption bandwidth ranges from 3.6 to 18 GHz with the tunable thickness from 1.7 to 5 mm. The effective absorption bandwidth covers the whole Ku band (12.4–18 GHz) when the thickness of carbon/TiO2/paraffin composite is 1.7 mm. This study is expected to pa...

Tunable Magnetism and Transport Properties in Nitride MXenes.

Abstract: Two-dimensional materials with intrinsic and robust ferromagnetism and half-metallicity are of great interest to explore the exciting physics and applications of nanoscale spintronic devices, but no such materials have been experimentally realized In this study, we predict several M2NTx nitride MXene structures that display these characteristics based on a comprehensive study using a crystal field theory model and first-principles simulations We demonstrate intrinsic ferromagnetism in Mn2NTx with different surface terminations (T = O, OH, and F), as well as in Ti2NO2 and Cr2NO2 High magnetic moments (up to 9 μB per unit cell), high Curie temperatures (1877 to 566 K), robust ferromagnetism, and intrinsic half-metallic transport behavior of these MXenes suggest that they are promising candidates for spintronic applications, which should stimulate interest in their synthesis

2D molybdenum and vanadium nitrides synthesized by ammoniation of 2D transition metal carbides (MXenes).

Abstract: MXenes are a rapidly growing class of 2D transition metal carbides and nitrides, finding applications in fields ranging from energy storage to electromagnetic interference shielding and transparent conductive coatings. However, while more than 20 carbide MXenes have already been synthesized, Ti4N3 and Ti2N are the only nitride MXenes reported so far. Here by ammoniation of Mo2CTx and V2CTx MXenes at 600 °C, we report on their transformation to 2D metal nitrides. Carbon atoms in the precursor MXenes are replaced with N atoms, resulting from the decomposition of ammonia molecules. The crystal structures of the resulting Mo2N and V2N were determined with transmission electron microscopy and X-ray pair distribution function analysis. Our results indicate that Mo2N retains the MXene structure and V2C transforms to a mixed layered structure of trigonal V2N and cubic VN. Temperature-dependent resistivity measurements of the nitrides reveal that they exhibit metallic conductivity, as opposed to semiconductor-like behavior of their parent carbides. As important, room-temperature electrical conductivity values of Mo2N and V2N are three and one order of magnitude larger than those of the Mo2CTx and V2CTx precursors, respectively. This study shows how gas treatment synthesis such as ammoniation can transform carbide MXenes into 2D nitrides with higher electrical conductivities and metallic behavior, opening a new avenue in 2D materials synthesis.

Two-Dimensional Titanium Carbide (MXene) as Surface-Enhanced Raman Scattering Substrate

Abstract: Noble metal (gold or silver) nanoparticles or patterned films are typically used as substrates for surface-enhanced Raman spectroscopy (SERS). Two-dimensional (2D) carbides and nitrides (MXenes) exhibit unique electronic and optical properties, including metallic conductivity and plasmon resonance in the visible or near-infrared range, making them promising candidates for a wide variety of applications. Herein, we show that 2D titanium carbide, Ti3C2Tx, enhances Raman signal from organic dyes on a substrate and in solution. As a proof of concept, MXene SERS substrates were manufactured by spray-coating and used to detect several common dyes, with calculated enhancement factors reaching ∼106. Titanium carbide MXene demonstrates SERS effect in aqueous colloidal solutions, suggesting the potential for biomedical or environmental applications, where MXene can selectively enhance positively charged molecules.

Thermoelectric Properties of Two-Dimensional Molybdenum-Based MXenes

Abstract: MXenes are an interesting class of 2D materials consisting of transition metal carbides and nitrides, which are currently a subject of extensive studies. Although there have been theoretical calculations estimating the thermoelectric properties of MXenes, no experimental measurements have been reported so far. In this report, three compositions of Mo-based MXenes (Mo2CTx, Mo2TiC2Tx, and Mo2Ti2C3Tx) have been synthesized and processed into free-standing binder-free papers by vacuum-assisted filtration, and their electrical and thermoelectric properties are measured. Upon heating to 800 K, these MXene papers exhibit high conductivity and n-type Seebeck coefficient. The thermoelectric power reaches 3.09 × 10–4 W m–1 K–2 at 803 K for the Mo2TiC2Tx MXene. While the thermoelectric properties of MXenes do not reach that of the best materials, they exceed their parent ternary and quaternary layered carbides. Mo2TiC2Tx shows the highest electrical conductivity in combination with the largest Seebeck coefficient of...

Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores

Abstract: Ionic liquids are composed of equal quantities of positive and negative ions. In the bulk, electrical neutrality occurs in these liquids due to Coulombic ordering, in which ion shells of alternating charge form around a central ion. Their structure under confinement is far less well understood. This hinders the widespread application of ionic liquids in technological applications. Here we use scattering experiments to resolve the structure of a widely used ionic liquid (EMI–TFSI) when it is confined inside nanoporous carbons. We show that Coulombic ordering reduces when the pores can accommodate only a single layer of ions. Instead, equally charged ion pairs are formed due to the induction of an electric potential of opposite sign in the carbon pore walls. This non-Coulombic ordering is further enhanced in the presence of an applied external electric potential. This finding opens the door for the design of better materials for electrochemical applications.

Flexible MXene–graphene electrodes with high volumetric capacitance for integrated co-cathode energy conversion/storage devices

Abstract: Developing self-powered integrated energy conversion and storage devices (ECSDs) is regarded as a promising approach to meet the quickly increasing demand for portable and wearable electronics. In this work, we describe a concept of using reduced graphene oxide (rGO) as a binder bridging electrochemically active conducting particles and enabling the manufacturing of flexible all-solid-state rGO/Ti3C2Tx (MXene) film-based supercapacitors. These supercapacitors were integrated with flexible thin-film solar cells by the co-cathode method to fabricate ECSDs. The porous rGO/Ti3C2Tx films were produced by vacuum-assisted filtration of the GO/Ti3C2Tx dispersion, followed by reduction at 300 °C under vacuum. This approach eliminated the need for the delamination of MXenes and allowed for the manufacturing of thick electrodes with good electrolyte accessibility. The volumetric and gravimetric capacitance of the rGO/Ti3C2Tx film in 6 M KOH reached 370 F cm−3 and 405 F g−1, respectively, which can be related to the synergistic effect of rGO and Ti3C2Tx. The assembled all-solid-state supercapacitors (SCs) using the polyvinyl alcohol (PVA)/KOH gel electrolyte exhibited a high energy density of 63 mW h cm−3 at a power density of 0.06 W cm−3. Their capacitance did not change after 10 000 charge/discharge cycles at the current density of 5 A g−1, ensuring stable performance of the ECSDs.

BN Nanosheet/Polymer Films with Highly Anisotropic Thermal Conductivity for Thermal Management Applications

Abstract: The development of advanced thermal transport materials is a global challenge. Two-dimensional nanomaterials have been demonstrated as promising candidates for thermal management applications. Here, we report a boron nitride (BN) nanosheet/polymer composite film with excellent flexibility and toughness prepared by vacuum-assisted filtration. The mechanical performance of the composite film is highly flexible and robust. It is noteworthy that the film exhibits highly anisotropic properties, with superior in-plane thermal conductivity of around 200 W m-1 K-1 and extremely low through-plane thermal conductivity of 1.0 W m-1 K-1, making this material an excellent candidate for thermal management in electronics. Importantly, the composite film shows fire-resistant properties. The newly developed unconventional flexible, tough, and refractory BN films are also promising for heat dissipation in a variety of applications.

Two-Dimensional Titanium Carbide MXene As a Cathode Material for Hybrid Magnesium/Lithium-Ion Batteries

Abstract: As an alternative to pure lithium-ion, Li+, systems, a hybrid magnesium, Mg2+, and Li+ battery can potentially combine the high capacity, high voltage, and fast Li+ intercalation of Li-ion battery cathodes and the high capacity, low cost, and dendrite-free Mg metal anodes. Herein, we report on the use of two-dimensional titanium carbide, Ti3C2Tx (MXene), as a cathode in hybrid Mg2+/Li+ batteries, coupled with a Mg metal anode. Free-standing and flexible Ti3C2Tx/carbon nanotube composite “paper” delivered ∼100 mAh g–1 at 0.1 C and ∼50 mAh g–1 at 10 C. At 1 C the capacity was maintained for >500 cycles at 80 mAh g–1. The Mo2CTx MXene also demonstrated good performance as a cathode material in this hybrid battery. Considering the variety of available MXenes, this work opens the door for exploring a new large family of 2D materials with high electrical conductivity and large intercalation capacity as cathodes for hybrid Mg2+/Li+ batteries.

High and Stable Ionic Conductivity in 2D Nanofluidic Ion Channels between Boron Nitride Layers.

Abstract: Achieving a high rate of ionic transport through porous membranes and ionic channels is important in numerous applications ranging from energy storage to water desalination, but it still remains a challenge. Herein we show that ions can quickly pass through interlayer spaces in hydrated boron nitride (BN) membranes. Measurements of surface-charge governed ionic currents between BN nanosheets in a variety of salt solutions (KCl, NaCl and CaCl2) at low salt concentrations (<10–4 M) showed several orders of magnitude higher ionic conductivity compared to that of the bulk solution. Moreover, due to the outstanding chemical and thermal stability of BN, the ionic conduits remain fully functional at temperatures up to 90 °C. The BN conduits can operate in acidic and basic environments and do not degrade after immersing in solutions with extreme pH (pH ∼ 0 or 14) for 1 week. Those excellent properties make the BN ionic conduits attractive for applications in nanofluidic devices and membrane separation.

Selective Molecular Separation on Ti3C2Tx–Graphene Oxide Membranes during Pressure-Driven Filtration: Comparison with Graphene Oxide and MXenes

Abstract: In this work, we prepared 90 nm thick Ti3C2Tx–graphene oxide (GO) membranes laminated on a porous support by mixing GO with Ti3C2Tx. This process was chosen to prevent the penetration of target molecules through inter-edge defects or voids with poor packing. The lattice period of the prepared membrane was 14.28 A, as being swelled with water, resulting in an effective interlayer spacing of around 5 A, which corresponds to two layers of water molecules. The composite membranes effectively rejected dye molecules with hydrated radii above 5 A, as well as positively charged dye molecules, during pressure-driven filtration at 5 bar. Rejection rates were 68% for methyl red, 99.5% for methylene blue, 93.5% for rose Bengal, and 100% for brilliant blue (hydrated radii of 4.87, 5.04, 5.88, and 7.98 A, respectively). Additionally, the rejections of composite membrane were compared with GO membrane and Ti3C2Tx membrane.

Na-Ion Intercalation and Charge Storage Mechanism in 2D Vanadium Carbide

Abstract: 2D vanadium carbide MXene containing surface functional groups (denoted as V2CTx, where Tx are surface functional groups) is synthesized and studied as anode material for Na-ion batteries. V2CTx anode exhibits reversible charge storage with good cycling stability and high rate capability through electrochemical test. The charge storage mechanism of V2CTx material during Na+ intercalation/deintercalation and the redox reaction of vanadium are studied using a combination of synchrotron based X-ray diffraction, hard X-ray absorption near edge spectroscopy (XANES), and soft X-ray absorption spectroscopy (sXAS). Experimental evidence of a major contribution of redox reaction of vanadium to the charge storage and the reversible capacity of V2CTx during sodiation/desodiation process are provided through V K-edge XANES and V L2,3-edge sXAS results. A correlation between the CO32− content and the Na+ intercalation/deintercalation states in the V2CTx electrode observed from C and O K-edge in sXAS results implies that some additional charge storage reactions may take place between the Na+-intercalated V2CTx and the carbonate-based nonaqueous electrolyte. The results of this study provide valuable information for the further studies on V2CTx as anode material for Na-ion batteries and capacitors.

Interaction of Polar and Nonpolar Polyfluorenes with Layers of Two-Dimensional Titanium Carbide (MXene): Intercalation and Pseudocapacitance

Abstract: This article provides insight into the interaction of synthetic conjugated polymers [polyfluorene derivatives (PFDs)] with layers of two-dimensional titanium carbide (Ti3C2Tx). Three derivatives with nonpolar, polar, and charged nitrogen-containing functionalities were synthesized via the Suzuki polycondensation reaction. The organic–inorganic PFD/Ti3C2Tx hybrids were prepared and characterized using X-ray diffraction and a range of microscopic and spectroscopic techniques to elucidate the host–guest interaction mechanism. We show that polar polymers with charged nitrogen-containing ends have the strongest interaction with the Ti3C2Tx layers, yielding an increase in interlayer spacing and large shifts in spectroscopic peaks. Furthermore, the effect of polymer backbone juxtaposition between Ti3C2Tx layers on pseudocapacitance is discussed in detail. Our results suggest that new organic materials capable of intercalation between the layers of Ti3C2Tx and other MXenes may be used in the design of hybrid stru...

Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes

Abstract: Two-dimensional (2D) materials that display robust ferromagnetism have been pursued intensively for nanoscale spintronic applications, but suitable candidates have not been identified. Here we present theoretical predictions on the design of ordered double-transition-metal MXene structures to achieve such a goal. On the basis of the analysis of electron filling in transition-metal cations and first-principles simulations, we demonstrate robust ferromagnetism in Ti2MnC2Tx monolayers regardless of the surface terminations (T = O, OH, and F), as well as in Hf2MnC2O2 and Hf2VC2O2 monolayers. The high magnetic moments (3–4 μB/unit cell) and high Curie temperatures (495–1133 K) of these MXenes are superior to those of existing 2D ferromagnetic materials. Furthermore, semimetal-to-semiconductor and ferromagnetic-to-antiferromagnetic phase transitions are predicted to occur in these materials in the presence of small or moderate tensile in-plane strains (0–3%), which can be externally applied mechanically or inte...