Effect of Substitutional Oxygen on Properties of Ti3 C2 Tx MXene Produced Using Recycled TiO2 Source.

MXenes are an emerging class of 2D materials with unique properties including metallic conductivity, mechanical flexibility, and surface tunability, which ensure their utility for diverse applications. However, the synthesis of MXenes with high crystallinity and atomic stoichiometry in a low-cost process is still challenging because of the difficulty in controlling the oxygen substitute in the precursors and final products of MXenes, which limits their academic understanding and practical applications. Here, a novel cost-effective method is reported to synthesize a highly crystalline and stoichiometric Ti3 C2 Tx MXene with minimum substitutional oxygen impurities by controlling the amount of excess carbon and time of high-energy milling in carbothermal reduction of recycled TiO2 source. The highest used content (2 wt%) of excess-carbon yields TiC with the highest carbon content and minimal oxygen substitutes, which leads to the Ti3 AlC2 MAX phase with improved crystallinity and atomic stoichiometry, and finally Ti3 C2 Tx MXene with the highest electrical conductivity (11738 S cm-1 ) and superior electromagnetic shielding effectiveness. Additionally, the effects of carbon content and substitutional oxygen on the physical properties of TiC and Ti3 AlC2 are elucidated by density-functional-theory calculations. This inexpensive TiO2 -based method of synthesizing high-quality Ti3 C2 Tx MXene can facilitate large-scale production and thus accelerate global research on MXenes.

Universal Ligands for Dispersion of Two-Dimensional MXene in Organic Solvents.

Ligands can control the surface chemistry, physicochemical properties, processing, and applications of nanomaterials. MXenes are the fastest growing family of two-dimensional (2D) nanomaterials, showing promise for energy, electronic, and environmental applications. However, complex oxidation states, surface terminal groups, and interaction with the environment have hindered the development of organic ligands suitable for MXenes. Here, we demonstrate a simple, fast, scalable, and universally applicable ligand chemistry for MXenes using alkylated 3,4-dihydroxy-l-phenylalanine (ADOPA). Due to the strong hydrogen-bonding and π-electron interactions between the catechol head and surface terminal groups of MXenes and the presence of a hydrophobic fluorinated alkyl tail compatible with organic solvents, the ADOPA ligands functionalize MXene surfaces under mild reaction conditions without sacrificing their properties. Stable colloidal solutions and highly concentrated liquid crystals of various MXenes, including Ti2CTx, Nb2CTx, V2CTx, Mo2CTx, Ti3C2Tx, Ti3CNTx, Mo2TiC2Tx, Mo2Ti2C3Tx, and Ti4N3Tx, have been produced in various organic solvents. Such products offer excellent electrical conductivity, improved oxidation stability, and excellent processability, enabling applications in flexible electrodes and electromagnetic interference shielding.

Tunable Ti3C2Tx MXene-Derived TiO2 Nanocrystals at Controlled pH and Temperature.

While two-dimensional (2D) Ti3C2Tx MXene in aqueous dispersions spontaneously oxidizes into titanium dioxide (TiO2) nanocrystals, the crystallization mechanism has not been comprehensively understood and the resultant crystal structures are not controlled among three representative polymorphs: anatase, rutile, and brookite. In this study, such control on the lattice structures and domain sizes of the MXene-derived TiO2 crystallites is demonstrated by means of the oxidation conditions, pH, and temperature (3.0-11.0 and 20-100 °C, respectively). It is observed that the formation of anatase phase is preferred against rutile phase in more basic and hotter oxidizing solutions, and even 100% anatase can be obtained at pH 11.0 and 100 °C. At lower pH and temperature, the portion of rutile phase increases such that it reaches ∼70% at pH 3 and 20 °C. Under certain circumstances, small portion of brookite phase is also observed. Smaller domain sizes of both anatase and rutile phases are observed in more basic oxidizing solutions and at lower temperatures. Based on these experimental results, we propose the crystallization mechanism in which the oxidative dissociation of Ti3C2Tx first produces Ti ions as the intermediate state, and they bind to abundant oxygen in the aqueous dispersions, and nucleate and crystallize into TiO2.

Mechanism and Kinetics of Oxidation Reaction of Aqueous Ti3C2Tx Suspensions at Different pHs and Temperatures.

Understanding the oxidation reaction of aqueous Ti3C2Tx MXene suspensions is very important for fostering fundamental academic studies as well as widespread industrial applications. Herein, we investigated the mechanism and kinetics of the oxidation reaction of aqueous Ti3C2Tx suspensions at various pH and temperature conditions. Through comprehensive analysis, the mechanism of the chemical oxidative degradation of aqueous Ti3C2Tx colloids was established. Chemical oxidation produces solid products such as TiO2 and amorphous carbon as well as various gaseous species including CH4, CO, CO2, and HF. Additionally, our comprehensive kinetic study proposes that aqueous Ti3C2Tx dispersions are degraded via an acid-catalyzed oxidation reaction, where, under acidic conditions, the protonation of the hydroxyl terminal groups on the Ti3C2Tx flakes induces electron localization on titanium atoms and accelerates their oxidation reaction. In contrast, under basic conditions, the electrostatically alkali-metalized hydroxyl intermediates forming a bulky solvent cage results in less electron localization on titanium atoms, and thus retards their oxidative degradation.

Reduction of Electrochemically Exfoliated Graphene Films for High-Performance Electromagnetic Interference Shielding.

Two-dimensional graphene is of great interest for electromagnetic interference (EMI) shielding owing to its inherent electrical conductivity, lightweight, and excellent mechanical flexibility even at minor thicknesses. However, the complex synthesis and quality-control difficulties limit its application. In this study, we demonstrate that electrochemically exfoliated graphene (EEG) with post-reduction treatment is a promising candidate for lightweight EMI shielding materials. A facile electrochemical exfoliation approach produces a high-quality multilayer graphene with a high electrical conductivity of ∼600 S cm-1, owing to its low degree of oxidation. The reduction of EEG by three different methods, including chemical, thermal, and microwave treatments, causes the removal of surface functional groups as well as significant changes in the microstructure of the final films. The reduced graphene films by microwaves, which are driven by the improved electrical conductivity and large volume expansion, exhibit an EMI shielding effectiveness of 108 dB at a thickness of 125 µm, one of the largest EMI shielding values ever reported for graphene at comparable thicknesses.

Anomalous absorption of electromagnetic waves by 2D transition metal carbonitride Ti3CNT x (MXene).

Lightweight, ultrathin, and flexible electromagnetic interference (EMI) shielding materials are needed to protect electronic circuits and portable telecommunication devices and to eliminate cross-talk between devices and device components. Here, we show that a two-dimensional (2D) transition metal carbonitride, Ti3CNT x MXene, with a moderate electrical conductivity, provides a higher shielding effectiveness compared with more conductive Ti3C2T x or metal foils of the same thickness. This exceptional shielding performance of Ti3CNT x was achieved by thermal annealing and is attributed to an anomalously high absorption of electromagnetic waves in its layered, metamaterial-like structure. These results provide guidance for designing advanced EMI shielding materials but also highlight the need for exploring fundamental mechanisms behind interaction of electromagnetic waves with 2D materials.

Electromagnetic Shielding of Monolayer MXene Assemblies.

Miniaturization of electronics demands electromagnetic interference (EMI) shielding of nanoscale dimension. The authors report a systematic exploration of EMI shielding behavior of 2D Ti3 C2 Tx MXene assembled films over a broad range of film thicknesses, monolayer by monolayer. Theoretical models are used to explain the shielding mechanism below skin depth, where multiple reflection becomes significant, along with the surface reflection and bulk absorption of electromagnetic radiation. While a monolayer assembled film offers ≈20% shielding of electromagnetic waves, a 24-layer film of ≈55 nm thickness demonstrates 99% shielding (20 dB), revealing an extraordinarily large absolute shielding effectiveness (3.89 × 106 dB cm2 g-1 ). This remarkable performance of nanometer-thin solution processable MXene proposes a paradigm shift in shielding of lightweight, portable, and compact next-generation electronic devices.

Nonpolar Organic Dispersion of 2D Ti3C2Tx MXene Flakes via Simultaneous Interfacial Chemical Grafting and Phase Transfer Method.

Herein, we demonstrate a simple and versatile way for preparing stable Ti3C2Tx MXene dispersions in nonpolar organic solvents through a simultaneous interfacial chemical grafting reaction and phase transfer method. Alkylphosphonic acid ligands were chemically grafted on the hydroxyl terminal groups of Ti3C2Tx flakes at the liquid-liquid interface between water and water-immiscible organic medium to form a covalent Ti-O-P bond via interfacial nucleophilic addition and sequential condensation reaction at room temperature; the surface-functionalized Ti3C2Tx flakes concurrently migrated from the aqueous phase to the organic phase. Unlike conventional surface chemical modification methods that require many complex and tedious steps, this is a simple and easy process for fabricating a Ti3C2Tx organic dispersion in various organic solvents, from highly polar to nonpolar. The nonpolar Ti3C2Tx dispersion in chloroform also exhibits strong oxidation resistance and stable long-term storage. This approach provides an opportunity for preparing MXene nanocomposites with nonpolar polymeric matrices that are soluble in organic media for future applications such as stretchable electrode.