Building 3D Crosslinked Graphene-MXene Nanoarchitectures Decorated with MoS2 Quantum Dots Enables Efficient Electrocatalytic Hydrogen Evolution.

Although MoS2 quantum dots with abundant edge sites have been regarded as promising eletrode materials for the hydrogen evolution reaction (HER), their electrocatalytic capacity still requires improvements in actual applications. Herein. we demonstrate a controllable and robust bottom-up approach to build 3D crosslinked graphene-Ti3C2Tx MXene frameworks decorated with MoS2 quantum dots (MQD/RGO-MX) via a convenient co-assembly process. The novel structural design gives the MQD/RGO-MX nanoarchitectures a series of superior textural attributes, including 3D interconnected networks, continuous meso- and macropores, well-dispersed quantum dots, ameliorative electronic configuration, and excellent electrical conductivity. Accordingly, the resulting hybrid nanoarchitectures express superior electrocatalytic properties in terms of a low onset potential of only 45 mV, a small Tafel slope of 61 mV dec-1 as well as a long service life towards the HER, which make it quite competitive against bare MoS2 quantum dots, MXene as well as binary MQD/RGO and MQD/MXene electrocatalysts.

Top-down design of high-performance V-based MBene anode for Li/Na-ion batteries.

Two-dimensional (2D) MBenes have enormous potential in energy applications. Vanadium metal, with its versatile and tunable electronic states, can further enhance the electrochemical performance of MBenes. However, most MBenes are composed of a few atomic layers as the metal boron (MB) block, e.g., M2B2, which might lead to instability and poor mechanical response. Herein, we designed and predicted 2D V4B6 associated with different terminations (T = Cl, O, S) using a top-down method and global search for parental V4AB6. Among the A element candidates, the P-glued MAB phase exhibited high stability and easy synthesizability. Moreover, 2D V4B6 was feasibly formed and easily exfoliated owing to its weak V-P bonding. Most of the surface functionalization could improve both the mechanical and electrochemical properties of the V4B6 monolayer. In particular, 2D V4B6S2 exhibited a high potential as an anode material for lithium-ion batteries (LIBs) with high theoretical capacity (297 mA h g-1), low diffusion barrier (0.166 eV), and low open circuit voltage (0.136 V), outperforming a majority of MXenes and transition metal sulfide layers. This work offers a new strategy for designing desirable 2D layers from parental materials, and tuning their properties via composition and surface functionalization, which could shed light on the development of other 2D metal-ion anodes.

Self-Healable and Reprocessable Silicon Elastomers Based on Imine-Boroxine Bonds for Flexible Strain Sensor.

Silicon elastomers with excellent self-healing and reprocessing abilities are highly desirable for the advancement of next-generation energy, electronic, and robotic applications. In this study, a dual cross-linked self-healing polysiloxane elastomer was facilely fabricated by introducing an exchangeable imine bond and boroxine into polydimethylsiloxane (PDMS) networks. The PDMS elastomers exhibited excellent self-healing properties due to the synergistic effect of dynamic reversible imine bonds and boroxine. After healing for 2 h, the mechanical strength of the damaged elastomers completely and rapidly recovered at room temperature. Furthermore, the prepared PDMS elastomers could be repeatedly reprocessed multiple times under milder conditions without significant degradation in mechanical performance. In addition, a stretchable and self-healable electrical sensor was developed by integrating carbon nanotubes (CNTs) with the PDMS elastomer, which can be employed to monitor multifarious human motions in real time. Therefore, this work provides a new inspiration for preparing self-healable and reprocessable silicone elastomers for future flexible electronics.

MXene (Ti3C2) Vacancy-Confined Single-Atom Catalyst for Efficient Functionalization of CO2.

A central topic in single-atom catalysis is building strong interactions between single atoms and the support for stabilization. Herein we report the preparation of stabilized single-atom catalysts via a simultaneous self-reduction stabilization process at room temperature using ultrathin two-dimensional Ti3- xC2T yMXene nanosheets characterized by abundant Ti-deficit vacancy defects and a high reducing capability. The single atoms therein form strong metal-carbon bonds with the Ti3- xC2T y support and are therefore stabilized onto the sites previously occupied by Ti. Pt-based single-atom catalyst (SAC) Pt1/Ti3- xC2T y offers a green route to utilizing greenhouse gas CO2, via the formylation of amines, as a C1 source in organic synthesis. DFT calculations reveal that, compared to Pt nanoparticles, the single Pt atoms on Ti3- xC2T y support feature partial positive charges and atomic dispersion, which helps to significantly decrease the adsorption energy and activation energy of silane, CO2, and aniline, thereby boosting catalytic performance. We believe that these results would open up new opportunities for the fabrication of SACs and the applications of MXenes in organic synthesis.

3D Lightweight Interconnected Melamine Foam Modified with Hollow CoFe2O4/MXene toward Efficient Microwave Absorption.

Considering the increasing severity of electromagnetic wave pollution, the development of high-performance low-filler-content microwave absorbers possessing wide frequency bands and strong absorption for practical applications is a demanding research hotspot. In this study, from the perspectives of the electromagnetic component coordination and structural design, a three-dimensional (3D) interconnected CoFe2O4/MXene-melamine foam (MF) was constructed via simple impregnation and a single freeze-drying step. By changing the absorber (CoFe2O4/MXene) concentration, the pore opening and electromagnetic properties of the 3D foams can be effectively adjusted. When the absorber concentration is sufficiently high to clog the internal pores, the microwave absorption is hindered. When the filler (CoFe2O4/MXene-MF) content is just ∼5.8 wt % (at a density of ∼33.3 mg cm-3), a minimum reflection loss (RLmin) of -72.1 dB is achieved at a matching thickness of 3.32 mm, and an effective absorption bandwidth (4.54 GHz) covering the whole X band is achieved at a thickness of 3 mm. CoFe2O4/MXene-MF, which possesses a 3D porous electromagnetic network structure, optimizes impedance matching and enhances multiple polarization relaxations and reflections/scattering, resulting in superior absorption capabilities. In particular, the continuous network structure ensures the uniform distribution of electromagnetic fields in the microstructure, achieving high absorption at low filler contents. This work provides a reference for subsequent 3D absorber concentration studies and a novel engineering strategy for preparing a low-filler-content, lightweight, and efficient electromagnetic wave absorber, which could be applied in the fields of radar security and information communications.

Thermal Shock Behavior of Si3N4/BN Fibrous Monolithic Ceramics.

To develop materials suitable for aerospace applications, silicon nitride/boron nitride (Si3N4/BN) fibrous monolithic ceramics with varying BN contents were prepared. Employing analytical techniques such as XRD and SEM, coupled with mechanical testing equipment, the influence of BN concentration on the thermal shock resistance of Si3N4/BN fibrous monolithic ceramics was assessed. When the thermal shock differential is less than 800 °C, its residual flexural strength gradually decreases as the thermal shock differential increases. Conversely, when the differential exceeds 1000 °C, the residual flexural strength of the material increases. The residual strength of all samples reached its peak after undergoing a thermal shock assessment at a 1500 °C differential. When the BN mass fraction is 5 wt.%, the residual strength after a thermal shock at a temperature difference of 1500 °C is 387 ± 19 MPa, which is 124% higher than the original strength of the sample that did not undergo thermal shock (25 °C, 311 ± 18 MPa). The oxide layer formed on the thermal shock surface played a role in bridging defects introduced during material surface processing.

Advanced Fabrication Method and Mechanical Properties of Silicon Nitride/Boron Nitride Fibrous Monolithic Ceramics.

Silicon nitride ceramics are regarded as a promising material for high-temperature structural applications due to their remarkable characteristics, including high strength, hardness, thermal conductivity, low dielectric properties, and resistance to creep at elevated temperatures. However, their susceptibility to catastrophic fracture at high temperatures remains a concern. Herein, Si3N4/BN fibrous monolithic ceramics have been successfully prepared by employing wet-spinning and hot-pressing techniques. We delved into the design and optimization of the spinning slurry and examined how the Si3N4/BN fiber diameter affects the ceramics' microstructure and mechanical properties. The spinning slurry exhibited exceptional stability and spinnability. Decreasing the fiber diameter contributed to material densification and improved mechanical properties. Notably, when the fiber diameter is 0.9 mm, the fabricated Si3N4/BN fibrous monolithic ceramics demonstrate a carbon content of 0.82%, a three-point bending strength of 357 ± 24 MPa, and a fracture toughness of 8.8 ± 0.36 MPa·m1/2. This investigation offers valuable insights into producing high-performance Si3N4/BN composite ceramics utilizing hot-pressing technology.

Immobilizing ultrasmall Pt nanocrystals on 3D interweaving BCN nanosheet-graphene networks enables efficient methanol oxidation reaction.

Currently, the state-of-the-art anode catalysts employed in direct methanol fuel cells (DMFCs) consist of nanosize Pt dispersed on a carbonaceous support; however, the relatively weak Pt-carbon interfacial interactions severely affect their overall electrocatalytic activity and service life. Herein, we demonstrate a convenient and robust stereo-assembly strategy for the efficient immobilization of ultrasmall Pt nanocrystals on 3D interweaving porous B-doped g-C3N4 nanosheet-graphene networks (Pt/BCN-G) by combining thermal annealing and solvothermal processes. This delicate configuration endowed the resulting hybrid nanoarchitecture with unusual textural merits, including 3D crosslinked porous skeletons, well-separated ultrathin nanosheets, rich B and N species, homogeneous Pt dispersion, stable heterointerface, and high electrical conductivity. Consequently, the 3D Pt/BCN-G nanoarchitecture with an optimized composition exhibited a large electrochemically active surface area of up to 121.2 m2 g-1, high mass activity of 1782.2 mA mg-1, superior poison tolerance, and excellent cycling stability towards the electrooxidation of methanol, all of which exceeded that of the reference Pt/graphene, Pt/BCN, Pt/carbon nanotube, Pt/carbon black, and Pt/g-C3N4 catalysts.

The Ablation Performance of Silicon Nitride/Boron Nitride Fibrous Monolithic Ceramics under an Oxyacetylene Combustion Torch.

In this study, Si3N4/BN fibrous monolithic ceramics were successfully prepared by wet spinning extrusion and hot pressing, and the effects on its ablation performance and microstructure were studied. The samples were burned in an oxyacetylene flame for 60 s × 30 to evaluate the ablation resistance. With the increase in ablation time, the fibrous monolithic ceramics exhibited specific mass and linear ablation rates, which show a trend of first increasing, then decreasing, and then increasing again. When the ablation time is 60 s × 10, 60 s × 20, and 60 s × 30, the mass ablation rates of the fibrous monolithic ceramics are 1 × 10-5 mg/s, -8.3 × 10-6 mg/s, -6.7 × 10-7 mg/s, respectively; the linear ablation rates are 4.7 × 10-5 µg/s, -1.2 × 10-5 µg/s and 1.7 × 10-6 µg/s. After 60 s × 30 of ablation, the surface oxides of the species are washed away by the oxyacetylene flame, revealing a porous coral-like structure with many cracks. A glass phase layer, predominantly constituted by sintering aids, envelops the Si3N4 ceramic surface on the ablated sample, serving as an effective barrier against additional ablation.

Urchin-like Fe3O4@C hollow spheres with core-shell structure: Controllable synthesis and microwave absorption.

The steadily increasing use of microwave stealth materials in aerospace flying vehicles needs the development of lightweight absorbers with low density and high thermal stability for printing or spraying. In that regard, the structural designability of typical microwave absorbers made of Fe3O4 seems to be a significant roadmap. In this work, a hollow spherical structure with a uniform carbon shell around the urchin-like Fe3O4 core (Fe3O4@C) was produced via a two-step hydrothermal method and annealing. The Fe3O4@C absorber exhibited a strong minimum reflection loss (RLmin) of -73.5 dB at the matching thickness of 3.23 mm. The maximum effective absorption bandwidth (EABmax) was 4.78 GHz at 4.55 mm. The proposed urchin-like core-shell structure was shown to provide good impedance matching and electromagnetic loss ability due to the synergistic effect of Fe3O4 and C. In particular, the urchin-like structure increases the heterogeneous interfaces and effectively improves their polarization and relaxation. On the other hand, it reduces the density of the absorber and enhances multiple scattering attenuations of electromagnetic waves (EMWs). Therefore, the findings of the present study open up prospects for the design of high-efficiency lightweight microwave absorbers with specialized structures.

Absolute film separation of dyes/salts and emulsions with a superhigh water permeance through graded nanofluidic channels.

The development of multifunctional films with a high permeability has been of great concern for effective separation of complex aqueous contaminants, especially in the face of zero or near-zero release regulations. Inspired by the natural structure of sandy soils, polydopamine-wrapped/connected polypyrrole sub-micron spheres (PPSM) were closely packed onto a polypyrrole-coated bacterial cellulose (PBC) support, by which a new two-layered PBC/PPSM composite film formed with graded nanofluidic channels. Interestingly, after being soaked in complex water environments of ethanol, acids, bases, heat, cold and high salinity, or else bended/folded for more than 10 times, the structure and performance of this film still stayed the same, validating its high structural stability and flexibility. Even in a high salinity environment over seawater, this PBC/PPSM film exhibits a dye-separation capacity of almost 100% with a surprisingly superhigh water permeance over one thousand L h-1 m-2 bar-1, one or two magnitudes higher than that of the related films reported in the literature. Meanwhile, the ability for effective oil-water-separation was also validated. Besides the superhydrophilicity and underwater superoleophobicity, the synapse-like-structure-induced graded nanofluidic channels are also proposed to play a key role for rendering such an outstandingly comprehensive performance of the film by greatly overcoming fluid resistance and reducing permeation viscosity.

Inkjet Printing Transparent and Conductive MXene (Ti3C2Tx) Films: A Strategy for Flexible Energy Storage Devices.

MXene is a generic name for a large family of two-dimensional transition metal carbides or nitrides, which show great promise in the field of transparent supercapacitors. However, the manufacturing of supercapacitor electrodes with a high charge storage capacity and desirable transmittance is a challenging task. Herein, a low-cost, large-scale, and rapid preparation of flexible and transparent MXene films via inkjet printing is reported. The MXene films realized the sheet resistance (Rs) of 1.66 ± 0.16 MΩ sq-1 to 1.47 ± 0.1 kΩ sq-1 at the transmissivity of 87-24% (λ = 550 nm), respectively, corresponding to the figure of merit (the ratio of electronic to optical conductivity, σDC/σOP) of ∼0.0012 to 0.13. Furthermore, the potential of inkjet-printed transparent MXene films in transparent supercapacitors was assessed by electrochemical characterization. The MXene film, with a transmittance of 24%, exhibited a superior areal capacitance of 887.5 µF cm-2 and retained 85% of the initial capacitance after 10,000 charge/discharge cycles at the scan rate of 10 mV s-1. Interestingly, the areal capacitance (192 µF cm-2) of an assembled symmetric MXene transparent supercapacitor, with a high transmittance of 73%, still surpasses the performance of previously reported graphene and single-walled carbon nanotube (SWCNT)-based transparent electrodes. The convenient manufacturing and superior electrochemical performance of inkjet-printed flexible and transparent MXene films widen the application horizon of this strategy for flexible energy storage devices.

Attapulgite-MXene Hybrids with Ti3C2Tx Lamellae Surface Modified by Attapulgite as a Mechanical Reinforcement for Epoxy Composites.

As a member of two-dimensional (2D) materials, MXene is an ideal reinforcement phase for modified polymers due to its large number of polar functional groups on the surface. However, it is still relatively difficult to modify any functional groups on the surface of MXene at present, which limits its application in enhancing some polymers. Herein, one-dimensional (1D) attapulgite (ATP) nanomaterials were introduced onto the surface of MXene to form ATP-MXene hybrids, which successfully improved the mechanical properties of the epoxy composites. ATP with appropriate content can increase the surface roughness of the MXene lamellae to obtain better interface interaction. Therefore, remarkable enhancement on the mechanical property was achieved by adding M02A025 (0.2 wt % MXene and 0.25 wt % ATP), which is the optimum composition in the hybrids for composite mechanical properties. Compared to neat epoxy, the tensile strength, flexural strength and critical stress intensity factor (KIC) of M02A025/epoxy are increased by 88%, 57%, and 195%, respectively, showing a high application prospect.

MXene (Ti3C2Tx) Functionalized Short Carbon Fibers as a Cross-Scale Mechanical Reinforcement for Epoxy Composites.

The surface modification technology of carbon fibers (CFs) have achieved considerable development, and it has achieved great success in improving the interfacial shear strength (IFSS) of the polymer matrix. Among them, MXene (Ti3C2Tx) functionalized CFs have been proven to improve the interface performance significantly. Unfortunately, the results on the microscopic scale are rarely applied to the preparation of macroscopic composite materials. Herein, the process of MXene functionalized CFs were attempted to be extended to short carbon fibers (SCFs) and used to strengthen epoxy materials. The results show that the cross-scale reinforcement of MXene functionalized SCFs can be firmly bonded to the epoxy matrix, which significantly improves the mechanical properties. Compared to neat epoxy, the tensile strength (141.2 ± 2.3 MPa), flexural strength (199.3 ± 8.9 MPa) and critical stress intensity factor (KIC, 2.34 ± 0.04 MPa·m1/2) are increased by 100%, 67%, and 216%, respectively.

Three-Dimensional Porous Ti3C2Tx-NiO Composite Electrodes with Enhanced Electrochemical Performance for Supercapacitors.

Ti3C2Tx and Ti3C2Tx-NiO composites with three-dimensional (3D) porous networks were successfully fabricated via vacuum freeze-drying. The microstructure, absorption, and electrochemical properties of the developed composites were investigated. Nickel oxide (NiO) nanoparticles could be evenly distributed on the three-dimensional network of three-dimensional Ti3C2Tx using solution processing. When employed as electrochemical capacitor electrodes in 1 M environmentally friendly sodium sulfate, Na2SO4, solution, the three-dimensional porous Ti3C2Tx-NiO composite electrodes exhibited considerable volume specific capacitance as compared to three-dimensional porous Ti3C2Tx. The three-dimensional porous Ti3C2Tx-NiO composite delivered a remarkable cycling performance with a capacitance retention of up to 114% over 2500 cycles. The growth trend of the capacitance with NiO content shows that nickel oxide plays a crucial role in the composite electrodes. These results present a roadmap for the development of convenient and economical supercapacitors in consideration with the possibilities of morphological control and the extensibility of the process.

Alkali-induced crumpling of Ti3C2Tx (MXene) to form 3D porous networks for sodium ion storage.

We present a novel strategy for constructing three-dimensional (3D) porous Ti3C2Tx (MXene) networks by alkali-induced crumpling of Ti3C2Tx nanosheets. The 3D porous Ti3C2Tx networks display high capacity and outstanding rate performance as anode materials for sodium-ion batteries.

Inkjet-printed flexible V2CTx film electrodes with excellent photoelectric properties and high capacities for energy storage device.

Energy storage devices are progressively advancing in the light-weight, flexible, and wearable direction. Ti3C2Tx flexible film electrodes fabricated via a non-contact, cost-effective, high-efficiency, and large-scale inkjet printing technology were capable of satisfying these demands in our previous report. However, other MXenes that can be employed in flexible energy storage devices remain undiscovered. Herein, flexible V2CTx film electrodes (with the low formula weight vs Ti3C2Tx film electrodes) with both high capacities and excellent photoelectric properties were first fabricated. The area capacitances of V2CTx film electrodes reached 531.3-5787.0 µF⋅cm-2 at 5 mV⋅s-1, corresponding to the figure of merits (FoMs) of 0.07-0.15. Noteworthy, V2CTx film electrode exhibited excellent cyclic stability with the capacitance retention of 83 % after 7,000 consecutive charge-discharge cycles. Furthermore, flexible all solid-state symmetric V2CTx supercapacitor was assembled with the area capacitance of 23.4 µF⋅cm-2 at 5 mV⋅s-1. Inkjet printing technology reaches the combination of excellent photoelectric properties and high capacities of flexible V2CTx film electrodes, which provides a new strategy for manufacturing MXene film electrodes, broadening the application prospect of flexible energy storage devices.