Recovery of oxidized two-dimensional MXenes through high frequency nanoscale electromechanical vibration.

MXenes hold immense potential given their superior electrical properties. The practical adoption of these promising materials is, however, severely constrained by their oxidative susceptibility, leading to significant performance deterioration and lifespan limitations. Attempts to preserve MXenes have been limited, and it has not been possible thus far to reverse the material's performance. In this work, we show that subjecting oxidized micron or nanometer thickness dry MXene films-even those constructed from nanometer-order solution-dispersed oxidized flakes-to just one minute of 10 MHz nanoscale electromechanical vibration leads to considerable removal of its surface oxide layer, whilst preserving its structure and characteristics. Importantly, electrochemical performance is recovered close to that of their original state: the pseudocapacitance, which decreased by almost 50% due to its oxidation, reverses to approximately 98% of its original value, with good capacitance retention ( ≈ 93%) following 10,000 charge-discharge cycles at 10 A g-1. These promising results allude to the exciting possibility for rejuvenating the material for reuse, therefore offering a more economical and sustainable route that improves its potential for practical translation.

Acoustomicrofluidic Synthesis of Pristine Ultrathin Ti3C2Tz MXene Nanosheets and Quantum Dots.

The conversion of layered transition metal carbides and/or nitrides (MXenes) into zero-dimensional structures with thicknesses and lateral dimensions of a few nanometers allows these recently discovered materials with exceptional electronic properties to exploit the additional benefits of quantum confinement, edge effects, and large surface area. Conventional methods for the conversion of MXene nanosheets and quantum dots, however, involve extreme conditions such as high temperatures and/or harsh chemicals that, among other disadvantages, lead to significant degradation of the material as a consequence of their oxidation. Herein, we show that the large surface acceleration-on the order of 10 million g's-produced by high-frequency (10 MHz) nanometer-order electromechanical vibrations on a chip-scale piezoelectric substrate is capable of efficiently nebulizing, and consequently dimensionally reducing, a suspension of multilayer Ti3C2Tz (MXene) into predominantly monolayer nanosheets and quantum dots while, importantly, preserving the material from any appreciable oxidation. As an example application, we show that the high-purity MXene quantum dots produced using this room-temperature chemical-free synthesis method exhibit superior performance as electrode materials for electrochemical sensing of hydrogen peroxide compared to the highly oxidized samples obtained through conventional hydrothermal synthesis. The ability to detect concentrations as low as 5 nM is a 10-fold improvement to the best reported performance of Ti3C2Tz MXene electrochemical sensors to date.

Flexible Free-Standing MoO3/Ti3C2T z MXene Composite Films with High Gravimetric and Volumetric Capacities.

Enhancing both the energy storage and power capabilities of electrochemical capacitors remains a challenge. Herein, Ti3C2T z MXene is mixed with MoO3 nanobelts in various mass ratios and the mixture is used to vacuum filter binder free, open, flexible, and free-standing films. The conductive Ti3C2T z flakes bridge the nanobelts, facilitating electron transfer; the randomly oriented, and interconnected, MoO3 nanobelts, in turn, prevent the restacking of the Ti3C2T z nanosheets. Benefitting from these advantages, a MoO3/Ti3C2T z film with a 8:2 mass ratio exhibits high gravimetric/volumetric capacities with good cyclability, namely, 837 C g-1 and 1836 C cm-3 at 1 A g-1 for an ≈ 10 µm thick film; and 767 C g-1 and 1664 C cm-3 at 1 A g-1 for ≈ 50 µm thick film. To further increase the energy density, hybrid capacitors are fabricated with MoO3/Ti3C2T z films as the negative electrodes and nitrogen-doped activated carbon as the positive electrodes. This device delivers maximum gravimetric/volumetric energy densities of 31.2 Wh kg-1 and 39.2 Wh L-1, respectively. The cycling stability of 94.2% retention ratio after 10 000 continuous charge/discharge cycles is also noteworthy. The high energy density achieved in this work can pave the way for practical applications of MXene-containing materials in energy storage devices.

Improved charge storage performance of a layered Mo1.33C MXene/MoS2/graphene nanocomposite.

The construction of nanocomposite electrodes based on 2D materials is an efficient route for property enrichment and for exploitation of constituent 2D materials. Herein, a flexible Mo1.33C i-MXene/MoS2/graphene (MOMG) composite electrode is constructed, utilizing an environment-friendly method for high-quality graphene and MoS2 synthesis. The presence of graphene and MoS2 between MXene sheets limits the commonly observed restacking, increases the interlayer spacing, and facilitates the ionic and electronic conduction. The as-prepared MOMG electrode delivers a volumetric capacitance of 1600 F cm-3 (450 F g-1) at the scan rate of 2 mV s-1 and retains 96% of the initial capacitance after 15 000 charge/discharge cycles (10 A g-1). The current work demonstrates that the construction of nanocomposite electrodes is a promising route towards property enhancement for energy storage applications.

Ultrafast assembly of swordlike Cu3(1,3,5-benzenetricarboxylate)n metal-organic framework crystals with exposed active metal sites.

Owing to their large surface area and high uptake capacity, metal-organic frameworks (MOFs) have attracted considerable attention as potential materials for gas storage, energy conversion, and electrocatalysis. Various strategies have recently been proposed to manipulate the MOF surface chemistry to facilitate exposure of the embedded metal centers at the crystal surface to allow more effective binding of target molecules to these active sites. Nevertheless, such strategies remain complex, often requiring strict control over the synthesis conditions to avoid blocking pore access, reduction in crystal quality, or even collapse of the entire crystal structure. In this work, we exploit the hydrodynamics and capillary resonance associated with acoustically-driven dynamically spreading and nebulizing thin films as a new method for ultrafast synthesis of swordlike Cu3(1,3,5-benzenetricarboxylate)n (Cu-BTC) MOFs with unique monoclinic crystal structures (P21/n) distinct to that obtained via conventional bulk solvothermal synthesis, with 'swordlike' morphologies whose lengths far exceed their thicknesses. Through pulse modulation and taking advantage of the rapid solvent evaporation associated with the high nebulisation rates, we are also able to control the thicknesses of these large aspect ratio (width and length with respect to the thickness) crystals by arresting their vertical growth, which, in turn, allows exposure of the metal active sites at the crystal surface. An upshot of such active site exposure on the crystal surface is the concomitant enhancement in the conductivity of the MOF, evident from the improvement in its current density by two orders of magnitude.

Flexible Freestanding MoO3-x -Carbon Nanotubes-Nanocellulose Paper Electrodes for Charge-Storage Applications.

Herein, a one-step synthesis protocol was developed for synthesizing freestanding/flexible paper electrodes composed of nanostructured molybdenum oxide (MoO3-x ) embedded in a carbon nanotube (CNT) and Cladophora cellulose (CC) matrix. The preparation method involved sonication of the precursors, nanostructured MoO3-x , CNTs, and CC with weight ratios of 7:2:1, in a water/ethanol mixture, followed by vacuum filtration. The electrodes were straightforward to handle and possessed a thickness of approximately 12 µm and a mass loading of MoO3-x -CNTs of approximately 0.9 mg cm-2 . The elemental mapping showed that the nanostructured MoO3-x was uniformly embedded inside the CNTs-CC matrix. The MoO3-x -CNTs-CC paper electrodes featured a capacity of 30 C g-1 , normalized to the mass of MoO3-x -CNTs, at a current density of 78 A g-1 (corresponding to a rate of approximately 210 C based on the MoO3 content, assuming a theoretical capacity of 1339 C g-1 ), and exhibited a capacity retention of 91 % over 30 000 cycles. This study paves the way for the manufacturing of flexible/freestanding nanostructured MoO3-x -based electrodes for use in charge-storage devices at high charge/discharge rates.

Tailoring Structure, Composition, and Energy Storage Properties of MXenes from Selective Etching of In-Plane, Chemically Ordered MAX Phases.

The exploration of 2D solids is one of our time's generators of materials discoveries. A recent addition to the 2D world is MXenes that possses a rich chemistry due to the large parent family of MAX phases. Recently, a new type of atomic laminated phases (coined i-MAX) is reported, in which two different transition metal atoms are ordered in the basal planes. Herein, these i-MAX phases are used in a new route for tailoriong the MXene structure and composition. By employing different etching protocols to the parent i-MAX phase (Mo2/3 Y1/3 )2 AlC, the resulting MXene can be either: i) (Mo2/3 Y1/3 )2 C with in-plane elemental order through selective removal of Al atoms or ii) Mo1.33 C with ordered vacancies through selective removal of both Al and Y atoms. When (Mo2/3 Y1/3 )2 C (ideal stoichiometry) is used as an electrode in a supercapacitor-with KOH electrolyte-a volumetric capacitance exceeding 1500 F cm-3 is obtained, which is 40% higher than that of its Mo1.33 C counterpart. With H2 SO4 , the trend is reversed, with the latter exhibiting the higher capacitance (≈1200 F cm-3 ). This additional ability for structural tailoring will indubitably prove to be a powerful tool in property-tailoring of 2D materials, as exemplified here for supercapacitors.