Showing papers by "Yury Gogotsi published in 2016"
TL;DR: The mechanical flexibility and easy coating capability offered by MXenes and their composites enable them to shield surfaces of any shape while providing high EMI shielding efficiency.
Abstract: Materials with good flexibility and high conductivity that can provide electromagnetic interference (EMI) shielding with minimal thickness are highly desirable, especially if they can be easily processed into films. Two-dimensional metal carbides and nitrides, known as MXenes, combine metallic conductivity and hydrophilic surfaces. Here, we demonstrate the potential of several MXenes and their polymer composites for EMI shielding. A 45-micrometer-thick Ti3C2Tx film exhibited EMI shielding effectiveness of 92 decibels (>50 decibels for a 2.5-micrometer film), which is the highest among synthetic materials of comparable thickness produced to date. This performance originates from the excellent electrical conductivity of Ti3C2Tx films (4600 Siemens per centimeter) and multiple internal reflections from Ti3C2Tx flakes in free-standing films. The mechanical flexibility and easy coating capability offered by MXenes and their composites enable them to shield surfaces of any shape while providing high EMI shielding efficiency.
3,251 citations
TL;DR: This review addresses the cutting edge of electrical energy storage technology, outlining approaches to overcome current limitations and providing future research directions towards the next generation of electricalEnergy storage devices whose characteristics represent a true hybridization of batteries and electrochemical capacitors.
Abstract: Electrical energy storage plays a vital role in daily life due to our dependence on numerous portable electronic devices. Moreover, with the continued miniaturization of electronics, integration of wireless devices into our homes and clothes and the widely anticipated ‘Internet of Things', there are intensive efforts to develop miniature yet powerful electrical energy storage devices. This review addresses the cutting edge of electrical energy storage technology, outlining approaches to overcome current limitations and providing future research directions towards the next generation of electrical energy storage devices whose characteristics represent a true hybridization of batteries and electrochemical capacitors.
1,200 citations
1,178 citations
TL;DR: In this article, a computational screening study of 2D layered transition metal carbides, MXenes, was performed for the hydrogen evolution reaction (HER) and the results showed that the basal planes of Mo2CTx are catalytically active toward the HER, unlike in the case of widely studied MoS2.
Abstract: The hydrogen evolution reaction (HER) is an important energy conversion process that underpins many clean energy technologies including water splitting. Herein, we report for the first time the application of two-dimensional (2D) layered transition metal carbides, MXenes, as electrocatalysts for the HER. Our computational screening study of 2D layered M2XTx (M = metal; X = (C, N); and Tx = surface functional groups) predicts Mo2CTx to be an active catalyst candidate for the HER. We synthesized both Mo2CTx and Ti2CTx MXenes, and in agreement with our theoretical predictions, Mo2CTx was found to exhibit far higher HER activity than Ti2CTx. Theory suggests that the basal planes of Mo2CTx are catalytically active toward the HER, unlike in the case of widely studied MoS2, in which only the edge sites of the 2H phase are active. This work paves the way for the development of novel 2D layered materials that can be applied in a multitude of other clean energy reactions for a sustainable energy future.
985 citations
TL;DR: In this article, a modified synthetic method is reported for producing high-quality monolayer 2D transition metal carbide Ti3C2Tx flakes, and their electronic properties are measured.
Abstract: 2D transition metal carbide Ti3C2Tx (T stands for surface termination), the most widely studied MXene, has shown outstanding electrochemical properties and promise for a number of bulk applications. However, electronic properties of individual MXene flakes, which are important for understanding the potential of these materials, remain largely unexplored. Herein, a modified synthetic method is reported for producing high-quality monolayer Ti3C2Tx flakes. Field-effect transistors (FETs) based on monolayer Ti3C2Tx flakes are fabricated and their electronic properties are measured. Individual Ti3C2Tx flakes exhibit a high conductivity of 4600 ± 1100 S cm−1 and field-effect electron mobility of 2.6 ± 0.7 cm2 V−1 s−1. The resistivity of multilayer Ti3C2Tx films is only one order of magnitude higher than the resistivity of individual flakes, which indicates a surprisingly good electron transport through the surface terminations of different flakes, unlike in many other 2D materials. Finally, the fabricated FETs are used to investigate the environmental stability and kinetics of oxidation of Ti3C2Tx flakes in humid air. The high-quality Ti3C2Tx flakes are reasonably stable and remain highly conductive even after their exposure to air for more than 24 h. It is demonstrated that after the initial exponential decay the conductivity of Ti3C2Tx flakes linearly decreases with time, which is consistent with their edge oxidation.
981 citations
TL;DR: In this article, large scale synthesis and delamination of 2D Mo2CTx (where T is a surface termination group) has been achieved by selectively etching gallium from the recently discovered nanolaminated, ternary tra...
Abstract: Large scale synthesis and delamination of 2D Mo2CTx (where T is a surface termination group) has been achieved by selectively etching gallium from the recently discovered nanolaminated, ternary tra ...
829 citations
TL;DR: The antibacterial properties of single- and few-layer Ti3C2Tx MXene flakes in colloidal solution were investigated and showed a higher antibacterial efficiency toward both Gram-negative E. coli and Gram-positive B. subtilis compared with graphene oxide (GO), which has been widely reported as an antibacterial agent.
Abstract: MXenes are a family of atomically thin, two-dimensional (2D) transition metal carbides and carbonitrides with many attractive properties. Two-dimensional Ti3C2Tx (MXene) has been recently explored for applications in water desalination/purification membranes. A major success indicator for any water treatment membrane is the resistance to biofouling. To validate this and to understand better the health and environmental impacts of the new 2D carbides, we investigated the antibacterial properties of single- and few-layer Ti3C2Tx MXene flakes in colloidal solution. The antibacterial properties of Ti3C2Tx were tested against Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis) by using bacterial growth curves based on optical densities (OD) and colonies growth on agar nutritive plates. Ti3C2Tx shows a higher antibacterial efficiency toward both Gram-negative E. coli and Gram-positive B. subtilis compared with graphene oxide (GO), which has been widely reported as an antibacterial agent. Concentratio...
785 citations
01 Apr 2016
TL;DR: Heterocyclic pyrrole molecules are in situ aligned and polymerized in the absence of an oxidant between layers of the 2D Ti3C2Tx (MXene), resulting in high volumetric and gravimetric capacitances with capacitance retention of 92% after 25,000 cycles at a 100 mV s(-1) scan rate as discussed by the authors.
Abstract: Heterocyclic pyrrole molecules are in situ aligned and polymerized in the -absence of an oxidant between layers of the 2D Ti3C2Tx (MXene), resulting in high volumetric and gravimetric capacitances with capacitance retention of 92% after 25,000 cycles at a 100 mV s(-1) scan rate.
692 citations
TL;DR: The first two-dimensional transition metal nitride, Ti4N3-based MXene is synthesised using a molten fluoride salt to etch Al from a Ti4AlN3 powder precursor at 550 °C under an argon atmosphere and delaminated the resulting MXene to produce few-layered nanosheets and monolayers of Ti4n3Tx.
Abstract: We report on the synthesis of the first two-dimensional transition metal nitride, Ti4N3-based MXene. In contrast to the previously reported MXene synthesis methods – in which selective etching of a MAX phase precursor occurred in aqueous acidic solutions – here a molten fluoride salt is used to etch Al from a Ti4AlN3 powder precursor at 550 °C under an argon atmosphere. We further delaminated the resulting MXene to produce few-layered nanosheets and monolayers of Ti4N3Tx, where T is a surface termination (F, O, or OH). Density functional theory calculations of bare, non-terminated Ti4N3 and terminated Ti4N3Tx were performed to determine the most energetically stable form of this MXene. Bare and functionalized Ti4N3 are predicted to be metallic. Bare Ti4N3 is expected to show magnetism, which is significantly reduced in the presence of functional groups.
690 citations
TL;DR: The atomic structure of freestanding monolayer Ti3C2Tx flakes prepared via the minimally intensive layer delamination method is determined and it is determined that the Ti vacancy concentration can be controlled by the etchant concentration during preparation.
Abstract: The 2D transition metal carbides or nitrides, or MXenes, are emerging as a group of materials showing great promise in lithium ion batteries and supercapacitors. Until now, characterization and properties of single-layer MXenes have been scarcely reported. Here, using scanning transmission electron microscopy, we determined the atomic structure of freestanding monolayer Ti3C2Tx flakes prepared via the minimally intensive layer delamination method and characterized different point defects that are prevalent in the monolayer flakes. We determine that the Ti vacancy concentration can be controlled by the etchant concentration during preparation. Density function theory-based calculations confirm the defect structures and predict that the defects can influence the surface morphology and termination groups, but do not strongly influence the metallic conductivity. Using devices fabricated from single- and few-layer Ti3C2Tx MXene flakes, the effect of the number of layers in the flake on conductivity has been de...
670 citations
TL;DR: In this paper, the authors reported on the fabrication of porous Ti3C2 MXene/CNT composite paper electrodes for sodium-based energy storage devices, which can accommodate larger Na ions and still provide high charging rate and high volumetric capacity.
TL;DR: The internal surface terminations of Ti3C2Tx MXene are identified and quantified and there are found to be significantly fewer -OH terminations than -F and -O, with the proportions highly dependent on the synthesis method.
Abstract: 1H and 19F NMR experiments have identified and quantified the internal surface terminations of Ti3C2Tx MXene. –F and –OH terminations are shown to be intimately mixed and there are found to be significantly fewer –OH terminations than –F and –O, with the proportions highly dependent on the synthesis method.
TL;DR: In this paper, it is shown that 2D Ti3C2 can be assembled from aqueous solutions into optical quality, nanometer thin films that, at 6500 S cm−1, surpass the conductivity of other solution-processed 2D materials, while simultaneously transmitting >97% of visible light per-nanometer thickness.
Abstract: MXenes comprise a new class of solution-dispersable, 2D nanomaterials formed from transition metal carbides and nitrides such as Ti3C2. Here, it is shown that 2D Ti3C2 can be assembled from aqueous solutions into optical quality, nanometer thin films that, at 6500 S cm−1, surpass the conductivity of other solution-processed 2D materials, while simultaneously transmitting >97% of visible light per-nanometer thickness. It is shown that this high conductivity is due to a metal-like free-electron density as well as a high degree of coplanar alignment of individual nanosheets achieved through spincasting. Consequently, the spincast films exhibit conductivity over a macroscopic scale that is comparable to the intrinsic conductivity of the constituent 2D sheets. Additionally, optical characterization over the ultraviolet-to-near-infrared range reveals the onset of free-electron plasma oscillations above 1130 nm. Ti3C2 is therefore a potential building block for plasmonic applications at near-infrared wavelengths and constitutes the first example of a new class of solution-processed, carbide-based 2D optoelectronic materials.
TL;DR: A wafer-scale process for manufacturing strongly adhering carbide-derived carbon films and interdigitated micro-supercapacitors with embedded titanium carbide current collectors is described, fully compatible with current microfabrication and silicon-based device technology.
Abstract: Integration of electrochemical capacitors with silicon-based electronics is a major challenge, limiting energy storage on a chip. We describe a wafer-scale process for manufacturing strongly adhering carbide-derived carbon films and interdigitated micro-supercapacitors with embedded titanium carbide current collectors, fully compatible with current microfabrication and silicon-based device technology. Capacitance of those films reaches 410 farads per cubic centimeter/200 millifarads per square centimeter in aqueous electrolyte and 170 farads per cubic centimeter/85 millifarads per square centimeter in organic electrolyte. We also demonstrate preparation of self-supported, mechanically stable, micrometer-thick porous carbon films with a Young’s modulus of 14.5 gigapascals, with the possibility of further transfer onto flexible substrates. These materials are interesting for applications in structural energy storage, tribology, and gas separation.
TL;DR: Heterocyclic pyrrole molecules are in situ aligned and polymerized in the -absence of an oxidant between layers of the 2D Ti3C2Tx (MXene), resulting in high volumetric and gravimetric capacitances with capacitance retention of 92% after 25,000 cycles at a 100 mV s(-1) scan rate.
Abstract: Heterocyclic pyrrole molecules are in situ aligned and polymerized in the -absence of an oxidant between layers of the 2D Ti3C2Tx (MXene), resulting in high volumetric and gravimetric capacitances with capacitance retention of 92% after 25,000 cycles at a 100 mV s(-1) scan rate.
TL;DR: In this article, a simple, scalable method is proposed to fabricate transparent conductive thin films using delaminated Ti3C2 MXene flakes by spray coating, which can be used as transparent conductors in electronic, electrochromic, and sensor applications.
Abstract: MXenes, a new class of 2D transition metal carbides and carbonitrides, show great promise in supercapacitors, Li-ion batteries, fuel cells, and sensor applications. A unique combination of their metallic conductivity, hydrophilic surface, and excellent mechanical properties renders them attractive for transparent conductive electrode application. Here, a simple, scalable method is proposed to fabricate transparent conductive thin films using delaminated Ti3C2 MXene flakes by spray coating. Homogenous films, 5–70 nm thick, are produced at ambient conditions over a large area as shown by scanning electron microscopy and atomic force microscopy. The sheet resistances (Rs) range from 0.5 to 8 kΩ sq−1 at 40% to 90% transmittance, respectively, which corresponds to figures of merit (the ratio of electronic to optical conductivities, σDC/σopt) around 0.5–0.7. Flexible, transparent, and conductive films are also produced and exhibit stable Rs values at up to 5 mm bend radii. Furthermore, the films' optoelectronic properties are tuned by chemical or electrochemical intercalation of cations. The films show reversible changes of transmittance in the UV–visible region during electrochemical intercalation/deintercalation of tetramethylammonium hydroxide. This work shows the potential of MXenes to be used as transparent conductors in electronic, electrochromic, and sensor applications.
TL;DR: An insight into the progress made towards the application of 2D nanomaterials for capacitive energy storage is provided and the design of hybrid and hierarchical 2D and 3D structures based on 2D nano-structures is presented.
Abstract: The unique properties and great variety of two-dimensional (2D) nanomaterials make them highly attractive for energy storage applications. Here, an insight into the progress made towards the application of 2D nanomaterials for capacitive energy storage is provided. Synthesis methods, and electrochemical performance of various classes of 2D nanomaterials, particularly based on graphene, transition metal oxides, dichalcogenides, and carbides, are presented. The factors that directly influence capacitive performance are discussed throughout the text and include nanosheet composition, morphology and texture, electrode architecture, and device configuration. Recent progress in the fabrication of 2D-nanomaterials-based microsupercapacitors and flexible and free-standing supercapacitors is presented. The main electrode manufacturing techniques with emphasis on scalability and cost-effectiveness are discussed, and include laser scribing, printing, and roll-to-roll manufacture. Various issues that prevent the use of the full energy-storage potential of 2D nanomaterials and how they have been tackled are discussed, and include nanosheet aggregation and the low electrical conductivity of some 2D nanomaterials. Particularly, the design of hybrid and hierarchical 2D and 3D structures based on 2D nanomaterials is presented. Other challenges and opportunities are discussed and include: control of nanosheets size and thickness, chemical and electrochemical instability, and scale-up of electrode films.
TL;DR: In this paper, the fabrication of all-MXene (Ti3C2Tx) solid-state interdigital microsupercapacitors by employing a solution spray-coating method, followed by a photoresist-free direct laser cutting method was reported.
Abstract: On-chip energy storage is a rapidly evolving research topic, opening doors for the integration of batteries and supercapacitors at the microscale on rigid and flexible platforms. Recently, a new class of two-dimensional (2D) transition metal carbides and nitrides (so-called MXenes) has shown great promise in electrochemical energy storage applications. Here, we report the fabrication of all-MXene (Ti3C2Tx) solid-state interdigital microsupercapacitors by employing a solution spray-coating method, followed by a photoresist-free direct laser cutting method. Our prototype devices consisted of two layers of Ti3C2Tx with two different flake sizes. The bottom layer was stacked large-size MXene flakes (lateral dimensions of 3–6 μm) serving mainly as current collectors. The top layer was made of small-size MXene flakes (∼1 μm) with a large number of defects and edges as the electroactive layer responsible for energy storage. Compared to Ti3C2Tx micro-supercapacitors with platinum current collectors, the all-MXene devices exhibited a much lower contact resistance, higher capacitances and better rate-capabilities. Areal and volumetric capacitances of ∼27 mF cm−2 and ∼357 F cm−3, respectively, at a scan rate of 20 mV s−1 were achieved. The devices also demonstrated excellent cyclic stability, with 100% capacitance retention after 10 000 cycles at a scan rate of 50 mV s−1. This study opens up a plethora of possible designs for high-performance on-chip devices employing different chemistries, flake sizes and morphologies of MXenes and their heterostructures.
TL;DR: In this article, the authors investigated the effects of the presence of LiCl during the chemical etching of the MAX phase Ti3AlC2 into MXene Ti3C2Tx (T stands for surface termination) and found that the resulting MXene has Li+ cations in the interlayer space.
Abstract: Ti3C2 and other two-dimensional transition metal carbides known as MXenes are currently being explored for many applications involving intercalated ions, from electrochemical energy storage, to contaminant sorption from water, to selected ion sieving. We report here a systematic investigation of ion exchange in Ti3C2 MXene and its hydration/dehydration behavior. We have investigated the effects of the presence of LiCl during the chemical etching of the MAX phase Ti3AlC2 into MXene Ti3C2Tx (T stands for surface termination) and found that the resulting MXene has Li+ cations in the interlayer space. We successfully exchanged the Li+ cations with K+, Na+, Rb+, Mg2+, and Ca2+ (supported by X-ray photoelectron and energy-dispersive spectroscopy) and found that the exchanged material expands on the unit-cell level in response to changes in humidity, with the nature of expansion dependent on the intercalated cation, similar to behavior of clay minerals; stepwise expansions of the basal spacing were observed, wit...
TL;DR: In this paper, a rational design of freestanding anode materials is reported for sodium-ion batteries, consisting of molybdenum disulfide (MoS2) nanosheets aligned vertically on carbon paper derived from paper towel.
Abstract: The development of sodium-ion batteries for large-scale applications requires the synthesis of electrode materials with high capacity, high initial Coulombic efficiency (ICE), high rate performance, long cycle life, and low cost. A rational design of freestanding anode materials is reported for sodium-ion batteries, consisting of molybdenum disulfide (MoS2) nanosheets aligned vertically on carbon paper derived from paper towel. The hierarchical structure enables sufficient electrode/electrolyte interaction and fast electron transportation. Meanwhile, the unique architecture can minimize the excessive interface between carbon and electrolyte, enabling high ICE. The as-prepared MoS2@carbon paper composites as freestanding electrodes for sodium-ion batteries can liberate the traditional electrode manufacturing procedure, thereby reducing the cost of sodium-ion batteries. The freestanding MoS2@carbon paper electrode exhibits a high reversible capacity, high ICE, good cycling performance, and excellent rate capability. By exploiting in situ Raman spectroscopy, the reversibility of the phase transition from 2H-MoS2 to 1T-MoS2 is observed during the sodium-ion intercalation/deintercalation process. This work is expected to inspire the development of advanced electrode materials for high-performance sodium-ion batteries.
01 May 2016
TL;DR: In this paper, a chemical etching method was developed to produce porous two-dimensional (2D) Ti3C2Tx MXenes at room temperature in aqueous solutions.
Abstract: Herein we develop a chemical etching method to produce porous two-dimensional (2D) Ti3C2Tx MXenes at room temperature in aqueous solutions. The as-produced porous Ti3C2Tx (p-Ti3C2Tx) have larger sp ...
10 Jun 2016
TL;DR: In this article, a rational design of freestanding anode materials is reported for sodium-ion batteries, consisting of molybdenum disulfide (MoS2) nanosheets aligned vertically on carbon paper derived from paper towel.
Abstract: The development of sodium-ion batteries for large-scale applications requires the synthesis of electrode materials with high capacity, high initial Coulombic efficiency (ICE), high rate performance, long cycle life, and low cost. A rational design of freestanding anode materials is reported for sodium-ion batteries, consisting of molybdenum disulfide (MoS2) nanosheets aligned vertically on carbon paper derived from paper towel. The hierarchical structure enables sufficient electrode/electrolyte interaction and fast electron transportation. Meanwhile, the unique architecture can minimize the excessive interface between carbon and electrolyte, enabling high ICE. The as-prepared MoS2@carbon paper composites as freestanding electrodes for sodium-ion batteries can liberate the traditional electrode manufacturing procedure, thereby reducing the cost of sodium-ion batteries. The freestanding MoS2@carbon paper electrode exhibits a high reversible capacity, high ICE, good cycling performance, and excellent rate capability. By exploiting in situ Raman spectroscopy, the reversibility of the phase transition from 2H-MoS2 to 1T-MoS2 is observed during the sodium-ion intercalation/deintercalation process. This work is expected to inspire the development of advanced electrode materials for high-performance sodium-ion batteries.
TL;DR: The synthesis of various two-dimensional transition metal oxides and the demonstration of high capacitance are expected to enable fundamental studies of dimensionality effects on their properties and facilitate their use in energy storage and other applications.
Abstract: Two-dimensional atomic crystals, such as two-dimensional oxides, have attracted much attention in energy storage because nearly all of the atoms can be exposed to the electrolyte and involved in redox reactions. However, current strategies are largely limited to intrinsically layered compounds. Here we report a general strategy that uses the surfaces of water-soluble salt crystals as growth templates and is applicable to not only layered compounds but also various transition metal oxides, such as hexagonal-MoO3, MoO2, MnO and hexagonal-WO3. The planar growth is hypothesized to occur via a match between the crystal lattices of the salt and the growing oxide. Restacked two-dimensional hexagonal-MoO3 exhibits high pseudocapacitive performances (for example, 300 F cm(-3) in an Al2(SO4)3 electrolyte). The synthesis of various two-dimensional transition metal oxides and the demonstration of high capacitance are expected to enable fundamental studies of dimensionality effects on their properties and facilitate their use in energy storage and other applications.
TL;DR: In this article, a novel way of modeling layered materials with real interfaces (diverse surface functional groups and stacking order between the adjacent monolayers) against experimental data is described and benchmarked.
Abstract: MXenes are a recently discovered family of two-dimensional (2D) early transition metal carbides and carbonitrides, which have already shown many attractive properties and great promise in energy storage and many other applications. However, a complex surface chemistry and small coherence length have been obstacles in some applications of MXenes, also limiting the accuracy of predictions of their properties. In this study, we describe and benchmark a novel way of modeling layered materials with real interfaces (diverse surface functional groups and stacking order between the adjacent monolayers) against experimental data. The structures of three kinds of Ti3C2Tx MXenes (T stands for surface terminating species, including O, OH, and F) produced under different synthesis conditions were resolved for the first time using atomic pair distribution function obtained by high-quality neutron total scattering. The true nature of the material can be easily captured with the sensitivity of neutron scattering to the s...
TL;DR: In this paper, a simple and scalable direct laser machining process to fabricate MXene-on-paper coplanar microsupercapacitors is reported, where commercially available printing paper is employed as a platform to coat either hydrofluoric acid-etched or clay-like 2D Ti3C2 MXene sheets.
Abstract: A simple and scalable direct laser machining process to fabricate MXene-on-paper coplanar microsupercapacitors is reported. Commercially available printing paper is employed as a platform in order to coat either hydrofluoric acid-etched or clay-like 2D Ti3C2 MXene sheets, followed by laser machining to fabricate thick-film MXene coplanar electrodes over a large area. The size, morphology, and conductivity of the 2D MXene sheets are found to strongly affect the electrochemical performance due to the efficiency of the ion-electron kinetics within the layered MXene sheets. The areal performance metrics of Ti3C2 MXene-on-paper microsupercapacitors show very competitive power-energy densities, comparable to the reported state-of-the-art paper-based microsupercapacitors. Various device architectures are fabricated using the MXene-on-paper electrodes and successfully demonstrated as a micropower source for light emitting diodes. The MXene-on-paper electrodes show promise for flexible on-paper energy storage devices.
25 Apr 2016
TL;DR: The electronic properties of these Mo-containing MXenes are compared with their Ti3C2 counterparts, and are found to be no longer metallic-like conductors; instead the resistance increases mildly with decreasing temperatures, and density functional theory calculations suggest that OH terminated Mo-Ti MXene are semiconductors with narrow band gaps.
Abstract: In this study, a transition from metallic to semiconducting-like behavior has been demonstrated in two-dimensional (2D) transition metal carbides by replacing titanium with molybdenum in the outer transition metal (M) layers of M3C2 and M4C3 MXenes. The MXene structure consists of n + 1 layers of near-close packed M layers with C or N occupying the octahedral site between them in an [MX]nM arrangement. Recently, two new families of ordered 2D double transition metal carbides MXenes were discovered, M′2M′′C2 and M′2M′′2C3 – where M′ and M′′ are two different early transition metals, such as Mo, Cr, Ta, Nb, V, and Ti. The M′ atoms only occupy the outer layers and the M′′ atoms fill the middle layers. In other words, M′ atomic layers sandwich the middle M′′–C layers. Using X-ray atomic pair distribution function (PDF) analysis on Mo2TiC2 and Mo2Ti2C3 MXenes, we present the first quantitative analysis of structures of these novel materials and experimentally confirm that Mo atoms are in the outer layers of the [MC]nM structures. The electronic properties of these Mo-containing MXenes are compared with their Ti3C2 counterparts, and are found to be no longer metallic-like conductors; instead the resistance increases mildly with decreasing temperatures. Density functional theory (DFT) calculations suggest that OH terminated Mo–Ti MXenes are semiconductors with narrow band gaps. Measurements of the temperature dependencies of conductivities and magnetoresistances have confirmed that Mo2TiC2Tx exhibits semiconductor-like transport behavior, while Ti3C2Tx is a metal. This finding opens new avenues for the control of the electronic and optical applications of MXenes and for exploring new applications, in which semiconducting properties are required.
TL;DR: It is shown that the performance of H2O2 treated MXene as an anode material in Li ion batteries (LIBs) was significantly improved as compared to as-prepared MXenes.
Abstract: Herein we demonstrate that a prominent member of the MXene family, Ti2C, undergoes surface oxidation at room temperature when treated with hydrogen peroxide (H2O2). The H2O2 treatment results in opening up of MXene sheets and formation of TiO2 nanocrystals on their surface, which is evidenced by the high surface area of H2O2 treated MXene and X-ray diffraction (XRD) analysis. We show that the reaction time and the amount of hydrogen peroxide used are the limiting factors, which determine the morphology and composition of the final product. Furthermore, it is shown that the performance of H2O2 treated MXene as an anode material in Li ion batteries (LIBs) was significantly improved as compared to as-prepared MXenes. For instance, after 50 charge/discharge cycles, specific discharge capacities of 389 mA h g−1, 337 mA h g−1 and 297 mA h g−1 were obtained for H2O2 treated MXene at current densities of 100 mA g−1, 500 mA g−1 and 1000 mA g−1, respectively. In addition, when tested at a very high current density, such as 5000 mA g−1, the H2O2 treated MXene showed a specific capacity of 150 mA h g−1 and excellent rate capability. These results clearly demonstrate that H2O2 treatment of Ti2C MXene improves MXene properties in energy storage applications, such as Li ion batteries or capacitors.
TL;DR: In this paper, the authors demonstrate the synthesis of orthorhombic Nb2O5@Nb4C3Tx (or @Nb2CTx) hierarchical composites via a one-step oxidation in flowing CO2 at 850 °C.
Abstract: Engineering electrode nanostructures is critical in developing high-capacity, fast rate-response, and safe Li-ion batteries. This study demonstrates the synthesis of orthorhombic Nb2O5@Nb4C3Tx (or @Nb2CTx) hierarchical composites via a one-step oxidation —in flowing CO2 at 850 °C —of 2D Nb4C3Tx (or Nb2CTx) MXene. The composites possess a layered architecture with orthorhombic Nb2O5 nanoparticles decorated uniformly on the surface of the MXene flakes and interconnected by disordered carbon. The composites have a capacity of 208 mAh g−1 at a rate of 50 mA g−1 (0.25 C) in 1–3 V versus Li+/Li, and retain 94% of the specific capacity with 100% Coulombic efficiency after 400 cycles. The good electrochemical performances could be attributed to three synergistic effects: (1) the high conductivity of the interior, unoxidized Nb4C3Tx layers, (2) the fast rate response and high capacity of the external Nb2O5 nanoparticles, and (3) the electron “bridge” effects of the disordered carbon. This oxidation method was successfully extended to Ti3C2Tx and Nb2CTx MXenes to prepare corresponding composites with similar hierarchical structures. Since this is an early report on producing this structure, there is much room to push the boundaries further and achieve better electrochemical performance.
TL;DR: The as-prepared noble metal nanoparticles on MXene show a highly sensitive SERS detection of methylene blue (MB) with calculated enhancement factors on the order of 105, opening a pathway for extending visible-range SERS applications of novel 2D hybrid materials in sensors, catalysis, and biomedical applications.
Abstract: We report on one-step hybridization of silver, gold and palladium nanoparticles from solution onto exfoliated two-dimensional (2D) Ti3C2 titanium carbide (MXene) nanosheets. The produced hybrid materials can be used as substrates for surface-enhanced Raman spectroscopy (SERS). An approximate analytical approach is also developed for the calculation of the surface plasmon resonance (SPR) frequency of nanoparticles immersed in a medium, near the interface of two dielectric media with different dielectric constants. We obtained a good match with the experimental data for SPR wavelengths, 440 nm and 558 nm, respectively for silver and gold nanoparticles. In the case of palladium, our calculated SPR wavelength for the planar geometry was 160 nm, demonstrating that non-spherical palladium nanoparticles coupled with 2D MXene yield a broad, significanlty red-shifted SPR band with a peak at 230 nm. We propose a possible mechanism of the plasmonic hybridization of nanoparticles with MXene. The as-prepared noble metal nanoparticles on MXene show a highly sensitive SERS detection of methylene blue (MB) with calculated enhancement factors on the order of 105. These findings open a pathway for extending visible-range SERS applications of novel 2D hybrid materials in sensors, catalysis, and biomedical applications.
TL;DR: In this paper, the authors proposed three different methods: alternating filtration, spray coating, and in-situ wet chemistry synthesis, to achieve the hybridization of two-dimensional (2D) Ti 3 C 2 T x MXene and transition metal oxides (TMOs), such as Co 3 O 4 and NiCo 2 O 4.