Chang E. Ren

Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide

Toward Titanium Carbide Batteries Many batteries and capacitors make use of lithium intercalation as a means of storing and transporting charge. Lithium is commonly used because it offers the best energy density, but also because there are difficulties in storing larger cations without disrupting the crystal structure of the host. Lukatskaya et al. (p. 1500) developed a series of MX compounds, where M represents a transition metal and X is carbon or nitrogen.The compound Ti3C2 forms a two dimensional layered structure, which is capable of accommodating a wide range of cations, including multivalent ones, either spontaneously or electrochemically The layered material Ti3C2 can intercalate much larger cations than Li+, allowing for energy storage applications. The intercalation of ions into layered compounds has long been exploited in energy storage devices such as batteries and electrochemical capacitors. However, few host materials are known for ions much larger than lithium. We demonstrate the spontaneous intercalation of cations from aqueous salt solutions between two-dimensional (2D) Ti3C2 MXene layers. MXenes combine 2D conductive carbide layers with a hydrophilic, primarily hydroxyl-terminated surface. A variety of cations, including Na+, K+, NH4+, Mg2+, and Al3+, can also be intercalated electrochemically, offering capacitance in excess of 300 farads per cubic centimeter (much higher than that of porous carbons). This study provides a basis for exploring a large family of 2D carbides and carbonitrides in electrochemical energy storage applications using single- and multivalent ions.

Flexible MXene/Carbon nanotube Composite Paper with High Volumetric Capacitance

Free-standing and flexible sandwich-like MXene/carbon nanotube (CNT) paper, composed of alternating MXene and CNT layers, is fabricated using a simple filtration method. These sandwich-like papers exhibit high volumetric capacitances, good rate performances, and excellent cycling stability when employed as electrodes in supercapacitors.

Flexible and conductive MXene films and nanocomposites with high capacitance

Significance Two-dimensional transition metal carbides (MXenes) offer a quite unique combination of excellent mechanical properties, hydrophilic surfaces, and metallic conductivity. In this first report (to our knowledge) on MXene composites of any kind, we show that adding polymer binders/spacers between atomically thin MXenes layers or reinforcing polymers with MXenes results in composite films that have excellent flexibility, good tensile and compressive strengths, and electrical conductivity that can be adjusted over a wide range. The volumetric capacitances of freestanding Ti3C2Tx MXene and its composite films exceed all previously published results. Owing to their mechanical strength and impressive capacitive performance, these films have the potential to be used for structural energy storage devices, electrochemical actuators, radiofrequency shielding, among other applications. MXenes, a new family of 2D materials, combine hydrophilic surfaces with metallic conductivity. Delamination of MXene produces single-layer nanosheets with thickness of about a nanometer and lateral size of the order of micrometers. The high aspect ratio of delaminated MXene renders it promising nanofiller in multifunctional polymer nanocomposites. Herein, Ti3C2Tx MXene was mixed with either a charged polydiallyldimethylammonium chloride (PDDA) or an electrically neutral polyvinyl alcohol (PVA) to produce Ti3C2Tx/polymer composites. The as-fabricated composites are flexible and have electrical conductivities as high as 2.2 × 104 S/m in the case of the Ti3C2Tx/PVA composite film and 2.4 × 105 S/m for pure Ti3C2Tx films. The tensile strength of the Ti3C2Tx/PVA composites was significantly enhanced compared with pure Ti3C2Tx or PVA films. The intercalation and confinement of the polymer between the MXene flakes not only increased flexibility but also enhanced cationic intercalation, offering an impressive volumetric capacitance of ∼530 F/cm3 for MXene/PVA-KOH composite film at 2 mV/s. To our knowledge, this study is a first, but crucial, step in exploring the potential of using MXenes in polymer-based multifunctional nanocomposites for a host of applications, such as structural components, energy storage devices, wearable electronics, electrochemical actuators, and radiofrequency shielding, to name a few.

Charge- and Size-Selective Ion Sieving Through Ti3C2Tx MXene Membranes.

Nanometer-thin sheets of 2D Ti3C2Tx (MXene) have been assembled into freestanding or supported membranes for the charge- and size-selective rejection of ions and molecules. MXene membranes with controllable thicknesses ranging from hundreds of nanometers to several micrometers exhibited flexibility, high mechanical strength, hydrophilic surfaces, and electrical conductivity that render them promising for separation applications. Micrometer-thick MXene membranes demonstrated ultrafast water flux of 37.4 L/(Bar·h·m(2)) and differential sieving of salts depending on both the hydration radius and charge of the ions. Cations with a larger charge and hydration radii smaller than the interlayer spacing of MXene (∼6 Å) demonstrate an order of magnitude slower permeation compared to single-charged cations. Our findings may open a door for developing efficient and highly selective separation membranes from 2D carbides.

Antibacterial Activity of Ti3C2Tx MXene

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. Concentration dependent antibacterial activity was observed and more than 98% bacterial cell viability loss was found at 200 μg/mL Ti3C2Tx for both bacterial cells within 4 h of exposure, as confirmed by colony forming unit (CFU) and regrowth curve. Antibacterial mechanism investigation by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) coupled with lactate dehydrogenase (LDH) release assay indicated the damage to the cell membrane, which resulted in release of cytoplasmic materials from the bacterial cells. Reactive oxygen species (ROS) dependent and independent stress induction by Ti3C2Tx was investigated in two separate abiotic assays. MXenes are expected to be resistant to biofouling and offer bactericidal properties.

Charge transfer induced polymerization of EDOT confined between 2D titanium carbide layers

In situ polymerization of 3,4-ethylenedioxythiophene (EDOT) is achieved on the surface of 2D Ti3C2Tx MXene without using any oxidant, resulting in improved lithium ion storage capability of Ti3C2Tx/poly-EDOT hybrids. A combined experimental and theoretical study revealed the mechanism of charge-transfer-induced polymerization of EDOT, which can be extended to other similar polymers.

Metallic Ti3C2Tx MXene Gas Sensors with Ultrahigh Signal-to-Noise Ratio

Achieving high sensitivity in solid-state gas sensors can allow the precise detection of chemical agents. In particular, detection of volatile organic compounds (VOCs) at the parts per billion (ppb) level is critical for the early diagnosis of diseases. To obtain high sensitivity, two requirements need to be simultaneously satisfied: (i) low electrical noise and (ii) strong signal, which existing sensor materials cannot meet. Here, we demonstrate that 2D metal carbide MXenes, which possess high metallic conductivity for low noise and a fully functionalized surface for a strong signal, greatly outperform the sensitivity of conventional semiconductor channel materials. Ti3C2Tx MXene gas sensors exhibited a very low limit of detection of 50-100 ppb for VOC gases at room temperature. Also, the extremely low noise led to a signal-to-noise ratio 2 orders of magnitude higher than that of other 2D materials, surpassing the best sensors known. Our results provide insight in utilizing highly functionalized metallic sensing channels for developing highly sensitive sensors.

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

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 Å, as being swelled with water, resulting in an effective interlayer spacing of around 5 Å, which corresponds to two layers of water molecules. The composite membranes effectively rejected dye molecules with hydrated radii above 5 Å, 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 Å, respectively). Additionally, the rejections of composite membrane were compared with GO membrane and Ti3C2Tx membrane.