A Self-Thickening and Self-Strengthening Strategy for 3D Printing High-Strength and Antiswelling Supramolecular Polymer Hydrogels as Meniscus Substitutes

3D printing of high-strength and antiswelling hydrogel-based load-bearing soft tissue scaffolds with similar geometric shape to natural tissues remains a great challenge owing to insurmountable trade-off between strength and printability. Herein, capitalizing on the concentration-dependent H-bonding-strengthened mechanism of supramolecular poly(N-acryloyl glycinamide) (PNAGA) hydrogel, a self-thickening and self-strengthening strategy, that is, loading the concentrated NAGA monomer into the thermoreversible low-strength PNAGA hydrogel is proposed to directly 3D printing latently H-bonding-reinforced hydrogels. The low-strength PNAGA serves to thicken the concentrated NAGA monomer, affording an appropriate viscosity for thermal-assisted extrusion 3D printing of soft PNAGA hydrogels bearing NAGA monomer and initiator, which are further polymerized to eventually generate high-strength and antiswelling hydrogels, due to the reconstruction of strong H-bonding interactions from postcompensatory PNAGA. Diverse polymer hydrogels can be printed with self-thickened corresponding monomer inks. Further, the self-thickened high-strength PNAGA hydrogel is printed into a meniscus, which is implanted in rabbit's knee as a substitute with in vivo outcome showing an appealing ability to efficiently alleviate the cartilage surface wear. The self-thickening strategy is applicable to directly printing a variety of polymer-hydrogel-based tissue engineering scaffolds without sacrificing mechanical strength, thus circumventing problems of printing high-strength hydrogels and facilitating their application scope.     

3D Porous Oxidation-Resistant MXene/Graphene Architectures Induced by In Situ Zinc Template toward High-Performance Supercapacitors

2D MXene materials have attracted intensive attention in energy storage application. However, MXene usually undergoes serious face-to-face restacking and inferior stability, significantly preventing its further commercial application. Herein, to suppress the oxidation and self-restacking of MXene, an efficient and fast self-assembly route to prepare a 3D porous oxidation-resistant MXene/graphene (PMG) composite with the assistance of an in situ sacrificial metallic zinc template is demonstrated. The self-assembled 3D porous architecture can effectively prevent the oxidation of MXene layers with no evident variation in electrical conductivity in air at room temperature after two months, guaranteeing outstanding electrical conductivity and abundant electrochemical active sites accessible to electrolyte ions. Consequently, the PMG-5 electrode possesses a striking specific capacitance of 393 F g⁻¹, superb rate performance (32.7% at 10 V s⁻¹), and outstanding cycling stability. Furthermore, the as-assembled asymmetric supercapacitor possesses a pronounced energy density of 50.8 Wh kg⁻¹ and remarkable cycling stability with a 4.3% deterioration of specific capacitance after 10 000 cycles. This work paves a new avenue to solve the two long-standing significant challenges of MXene in the future.     

Polymerization of vegetable oils and their uses in printing inks

Ink vehicles were prepared by the polymerization of vegetable oils. By controlling the polymerization conditions, the desired viscosity, color and molecular weight could be achieved for a variety of vegetable oils with a broad range of iodine values and fatty acid compositions. The effect of temperature and catalyst on polymerization rates were evaluated, and polymerization rate constants were calculated. Of the oils tested, the polymerization rate constant of safflower oil was the highest, followed by soybean, sunflower, cottonseed and canola oils in decreasing order. Use of a catalyst shortened the heating time by about 25–50% or lowered the polymerization temperature requirement by 25–30°C.     

Inkjet Printing of Self‐Assembled 2D Titanium Carbide and Protein Electrodes for Stimuli‐Responsive Electromagnetic Shielding

2D titanium carbides (MXene) possess significant characteristics including high conductivity and electromagnetic interference shielding efficiency (EMI SE) that are important for applications in printed and flexible electronics. However, MXene‐based ink formulations are yet to be demonstrated for proper inkjet printing of MXene patterns. Here, tandem repeat synthetic proteins based on squid ring teeth (SRT) are employed as templates of molecular self‐assembly to engineer MXene inks that can be printed as stimuli‐responsive electrodes on various substrates including cellulose paper, glass, and flexible polyethylene terephthalate (PET). MXene electrodes printed on PET substrates are able to display electrical conductivity values as high as 1080 ± 175 S cm^?1, which significantly exceeds electrical conductivity values of state‐of‐the‐art inkjet‐printed electrodes composed of other 2D materials including graphene (250 S cm^?1) and reduced graphene oxide (340 S cm^?1). Furthermore, this high electrical conductivity is sustained under excessive bending deformation. These flexible electrodes also exhibit effective EMI SE values reaching 50 dB at films with thicknesses of 1.35 µm, which mainly originate from their high electrical conductivity and layered structure.     

SnS@Ti_3C_2复合材料的制备及其储锂性能研究

MXene是一类新型二维过渡金属碳化物晶体,该类材料具有一些优异的性质,如高的电导率、低的锂离子扩散能垒、独特的金属离子吸附特性等等,但是,作为锂离子电极材料时,MXene材料容量较低,限制了它在锂离子电池领域的进一步应用。本文以Ti_3C_2(最具代表性的一种MXene材料)为基体材料,通过液相插层、水热合成以及高温热处理,成功制备出二维SnS@Ti_3C_2复合材料。研究发现,当Ti_3C_2:L-半胱氨酸的质量比为1:3时(L-半胱氨酸:Na2Sn O3·4H2O=1:4),合成出来的Sn S@Ti_3C_2在0.1 A×g~(-1)的电流密度下循环50次之后,容量达到735.8 m Ah×g~(-1),且保持稳定;在3 A×g~(-1)的电流密度下,其容量能达到525.4 m Ah g~(-1);而当电流恢复到0.1 A×g~(-1)时,其容量能恢复到689.2 m Ah×g~(-1),展现出了优异的倍率性能。     

Highly Conductive Transition Metal Carbide/Carbonitride(MXene)@polystyrene Nanocomposites Fabricated by Electrostatic Assembly for Highly Efficient Electromagnetic Interference Shielding

Highly conductive polymer nanocomposites are greatly desired for electromagnetic interference (EMI) shielding applications. Although transition metal carbide/carbonitride (MXene) has shown its huge potential for producing highly conductive films and bulk materials, it still remains a great challenge to fabricate extremely conductive polymer nanocomposites with outstanding EMI shielding performance at minimal amounts of MXenes. Herein, an electrostatic assembly approach for fabricating highly conductive MXene@polystyrene nanocomposites by electrostatic assembling of negative MXene nanosheets on positive polystyrene microspheres is demonstrated, followed by compression molding. Thanks to the high conductivity of MXenes and their highly efficient conducting network within polystyrene matrix, the resultant nanocomposites exhibit not only a low percolation threshold of 0.26 vol% but also a superb conductivity of 1081 S m^?1 and an outstanding EMI shielding performance of >54 dB over the whole X‐band with a maximum of 62 dB at the low MXene loading of 1.90 vol%, which are among the best performances for electrically conductive polymer nanocomposites by far. Moreover, the same nanocomposite has a highly enhanced storage modulus, 54% and 56% higher than those of neat polystyrene and conventional MXene@polystyrene nanocomposite, respectively. This work provides a novel methodology to produce highly conductive polymer nanocomposites for highly efficient EMI shielding applications.     

Two-dimensional MXene hollow fiber membrane for divalent ions exclusion from water

Two-dimensional material membranes with fast transport channels and versatile chemical functionality are promising for molecular separation.Herein,for the first time,we reported design and engineering of two-dimensional Ti3C2Tx MXene (called transition metal carbides and nitrides) membranes supported on asymmetric polymeric hollow fiber substrate for water desalination.The membrane morphology,physic-ochemical properties and ions exclusion performance were systematically investigated.The results demonstrated that surface hydrophilicity and electrostatic repulsion and size sieving effect of interlayer channels synergistically endowed the MXene hollow fiber membrane with fast water permeation and efficient rejection of divalent ions during nanofiltration process.     

剥离的碳化钛（d-Ti3C2Tx）纳米片吸波性能

目的研究剥离的碳化钛(d-Ti3C2Tx)纳米片的吸波性能。方法利用HCl/LiF刻蚀,通过高速离心的方法得到d-Ti3C2Tx纳米片。利用X射线衍射仪(XRD)分析d-Ti3C2Tx的物相组成。用扫描电子显微镜(SEM)和透射电子显微镜(TEM)对d-Ti3C2Tx进行形貌分析。利用原子力显微镜(AFM)测量了d-Ti3C2Tx纳米片的厚度。利用矢量网络分析仪(VNA)测试了d-Ti3C2Tx纳米片与石蜡复合材料X波段的电磁参数。利用Cole-Cole图分析了复合材料的损耗来源,并通过电磁参数计算分析了d-Ti3C2Tx的吸波性能。结果d-Ti3C2Tx纳米片与石蜡复合材料的介电实部/虚部随着d-Ti3C2Tx浓度的增加而增大,极化的增强和电导网络的扩大是导致复合材料介电实部/虚部增加的主要原因。Cole-Cole图分析表明,复合材料中存在多种类型的极化,这分别是由缺陷、官能团和界面等引起的多重弛豫极化。吸波性能分析表明,通过改变d-Ti3C2Tx浓度,可以调控复合材料的吸波性能。当填充量达到15%时,吸波性能最佳。其在厚度为4 mm下最小反射损耗为−20.1 dB,相应的微波吸收带宽(<‒10 dB)为1.9 GHz。结论d-Ti3C2Tx/石蜡复合材料表现了优异的微波吸收性能,且通过改变d-Ti3C2Tx浓度,可以调控d-Ti3C2Tx复合材料的微波吸收性能。     

Layered NiFe-LDH/MXene nanocomposite electrode for high-performance supercapacitor

Layered double hydroxide (LDH) is potentially excellent supercapacitor (SC) materials, but the low conductivity and easy agglomeration limit the further improvement of their electrochemical properties. Therefore, LDHs are requisite to grow on some conductive substrates to produce high-performance SC. In this paper, the conductive two-dimensional (2D) transition metal carbides, nitrides and carbonitrides (called MXene) were explored as the substrate to directly deposit NiFe-LDH nanosheets by a one-step hydrothermal method, then a three-dimensional (3D) porous NiFe-LDH/MXene electrode was obtained. The morphology and electrochemical performance of the composite electrodes were analyzed and investigated. The results show that the NiFe-LDH/MXene electrode has larger specific capacitance (720.2 F/g) than NiFe-LDH (465 F/g), and the capacitance of the composite electrode retained 86% after 1000 cycles (only 24% for NiFe-LDH), showing excellent cycle stability. The improved electrochemical performance of the composites is caused by the stable sheet-like structure of NiFe-LDH during charge-discharge time and the conductive network formed by the MXene, which can accelerates electron transport. In addition, the asymmetric SC based on NiFe-LDH/MXene positive electrode display a power density of 758.27 W/kg at an energy density of 42.4 Wh/Kg. These results indicate the NiFe-LDH/MXene composites can be applied as the novel candidate of high-performance SC electrodes.     

3d transitional-metal single atom catalysis toward hydrogen evolution reaction on MXenes supports

Single atom catalysis involving atomically dispersed metal active sites on the appropriate supports is the effective way to magnify the catalytic efficiency and reduce the cost. By performing the first-principles calculations, we studied the anchoring of 3d transitional-metal single atoms M (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) on the surfaces of MXenes Cr₂CO₂ and Mo₂CO₂ and the catalytic activity of the single atom sites for hydrogen evolution reaction (HER). Sixteen single atom sites, M-Cr₂CO₂ (M = Sc, Ti, V, Cr, Mn, Fe, Co, Cu and Zn) and M-Mo₂CO₂ (M = Sc, Ti, V, Cr, Mn, Fe and Zn) have been chosen via examining the energetical and thermal stability of the isolated M atoms on the substrates. More importantly, we have calculated the Gibbs free energy change (ΔG_H) of H adsorption on the surface of M anchored Cr₂CO₂ and Mo₂CO₂ and find that Cr, Fe, Zn on Cr₂CO₂ and Sc, V on Mo₂CO₂ are the promising single atom active sites toward HER. Additionally, our results show that M atoms adsorbing turns the nearby sites to be active for catalyzing HER. MXenes Cr₂CO₂ and Mo₂CO₂, in terms of the supporting not only stabilize but also works together with the anchored single atom M as active catalyst toward HER.