MnS掺杂多孔碳复合材料的制备及电化学性能（两张发票1000+2500）

褐煤作为低级煤资源利用率不高，但褐煤中具有腐植酸成分，将褐煤中提取的腐植酸作为化肥原料，提取后剩余残渣作为碳源，与MnS纳米粒子制备了MnS@C复合材料。采用XRD、拉曼光谱、XPS、N2吸附-脱附、SEM和TEM对样品进行了表征。将该复合材料应用于锂离子电池负极材料，对其电化学性能进行了测试。结果表明，MnS@C复合材料的比表面积和孔容分别为117.19m2/g和0.044mL/g，该电极在0.1 A/g电流密度条件下循环200次后比容量高达830 mA‧h/g，且电极容量保持率为99%左右。在0.2、0.4、0.8、1.0、1.2和1.6 A/g电流密度下比容量分别为644、522、427、399、373和348mAh/g，展现出良好的倍率性能。MnS@C复合材料优异的电化学性能得益于碳基体的存在，不仅可以缓解MnS纳米粒子在嵌锂/脱锂过程中的体积膨胀，而且展示了锂离子电池高性能的巨大潜力，为褐煤的高值化利用作出巨大贡献。     

Molecularly imprinted macroporous polymer monolithic layers for L-phenylalanine recognition in complex biological fluids

In present work, the development of macroporous monolithic layers bearing the artificial recognition sites toward L-phenylalanine has been carried out. The set of macroporous poly(2-aminoethyl methacrylate-co-2-hydroxyethyl methacrylate-co-ethylene glycol dimethacrylate) materials with average pore size ranged in 340–1200 nm was synthesized. The applicability of Hildebrand's and Hansen's theories for the prediction of polymer compatibility with porogenic solvents was evaluated. The dependences of average pore size on theoretically calculated parameters were plotted. The linear trend detected for Hansen's theory has indicated the high suitability of this approach to select appropriate porogens. The synthesized monolithic MIP layers were tested toward the ability to rebind phenylalanine-derivative in microarray format. The influence of such factors as average pore size of the material, the concentration of template molecule in polymerization mixture, interaction time of analyte with its imprinted sites on binding efficiency were studied. The developed materials demonstrated good analyte rebinding from buffer solution with recognition factors 2.5–3.4 depending on the MIP sample. The comparable rebinding efficiency was also detected when the analysis was carried using complex biological media. The selectivity of phenylalanine binding from the equimolar mixture of structural analogues was 81.9% for free amino acid and 91.2% for labeled one.     

Bio-Based,Self-Crosslinkable Eucommia ulmoides Gum/Silica Hybrids with Body Temperature Triggering Shape Memory Capability

At present, the synthesis of body temperature triggering shape memory polymers usually requires elaborate structural design, which limits their wide application. Herein, starting from bio-based Eucommia ulmoides gum (EUG), a series of EUG/silica hybrids (ESHs) are prepared through a facile one-pot process, in which EUG is epoxied and then self-crosslinked with SiO₂ by epoxy ring-open reaction. Varying the amount of H₂O₂, the shape memory transition temperature (T_trans) of ESHs is adjusted to 47.4–36.6 ℃, which is close to human body temperature (37 ℃). Among them, ESH-17 exhibited the best body temperature triggering shape memory ability (T_trans = 36.6 ℃), which can restore the permanent shape within 60 s at 37 ℃ with a shape fixity ratio of 99% and shape recovery ratio near 100%. In addition, the shape memory mechanism is discussed and shows some application scenarios of ESHs. The as-produced materials can be used as smart biomaterials such as self-tightening sutures, self-sealing root canal filling materials, and so on.     

Stable Radicals with Protective Umbrellas Integrated on the Surface of 2D Layered Materials

Radicals are closely related to human life and health and have been widely used in biology, chemistry, functional materials, etc. However, the high reactivity, disorder, and short half-lives limit their wide applications. Therefore, it remains a great challenge to prepare stable and ordered radicals. Herein, radicals are prepared with protective umbrellas (diethylmethyleneamine, DEMA) that are integrated on the surface of 2D layered materials to isolate water and oxygen and enhance the stability of radicals. Taking 2D black phosphorus (BP) as an example: triethylamine reacts with dichloromethane to form quaternary ammonium salts with further Hoffmann elimination to produce DEMA radicals that could react with one electron of a lone pair electrons in P on the surface of BP to produce P radicals, which shows a prolonged half-life of 21 days at room temperature. First-principle calculations and electron paramagnetic resonance fitting confirm that the steric hindrance constructed by dense DEMA passivation layer acts as a protective umbrella and the 2D coupling of P radicals and other P atoms in 2D BP plane to enhance the stability and strong superexchange interaction of P radicals. Furthermore, it is a general strategy to produce stable radicals integrated on the 2D plane.     

Three distinct optical-switching states in phase-change materials containing impurities:From physical origin to material design

Ge2Sb2Tes is the most widely utilized chalcogenide phase-change material for non-volatile photonic applications,which undergoes amorphous-cubic and cubic-hexagonal phase transition under external excitations.However,the cubic-hexagonal optical contrast is negligible,only the amorphous-cubic phase transition of Ge2Sb2Te5 is available.This limits the optical switching states of traditional active dis-plays and absorbers to two.We find that increasing structural disorder difference of cubic-hexagonal can increase optical contrast close to the level of amorphous-cubic.Therefore,an amorphous-cubic-hexagonal phase transition with high optical contrast is realized.Using this phase transition,we have developed display and absorber with three distinct switching states,improving the switching perfor-mance by 50％.Through the combination of first-principle calculations and experiments,we reveal that the key to increasing structural disorder difference of amorphous,cubic and hexagonal phases is to intro-duce small interstitial impurities(like N)in Ge2Sb2Tes,rather than large substitutional impurities(like Ag)previously thought.This is explained by the formation energy and lattice distortion.Based on the impurity atomic radius,interstitial site radius and formation energy,C and B are also potential suit-able impurities.In addition,introducing interstitial impurities into phase-change materials with van der Waals gaps in stable phase such as GeSb4Te7,GeSb2Te4,Ge3Sb2Te6,Sb2Te3 will produce high optical con-trast amorphous-metastable-stable phase transition.This research not only reveals the important role of interstitial impurities in increasing the optical contrast between metastable-stable phases,but also proposes varieties of candidate matrices and impurities.This provides new phase-change materials and design methods for non-volatile optical devices with multi-switching states.     

High-Throughput Screening for Phase-Change Memory Materials

Phase change memory (PCM) is an emerging non-volatile data storage technology concerned by the semiconductor industry. To improve the performances, previous efforts have mainly focused on partially replacing or doping elements in the flagship Ge-Sb-Te (GST) alloy based on experimental “trial-and-error” methods. Here, the current largest scale PCM materials searching is reported, starting with 124 515 candidate materials, using a rational high-throughput screening strategy consisting of criteria related to PCM characteristics. In the results, there are 158 candidates screened for PCM materials, of which ≈68% are not employed. By further analyses, including cohesive energy, bond angle analyses, and Born effective charge, there are 52 materials with properties similar to the GST system, including Ge₂Bi₂Te₅, GeAs₄Te₇, GeAs₂Te₄, so on and other candidates that have not been reported, such as TlBiTe₂, TlSbTe₂, CdPb₃Se₄, etc. Compared with GST, materials with close cohesive energy include AgBiTe₂, TlSbTe₂, As₂Te₃, TlBiTe₂, etc., indicating possible low power consumption. Through further melt-quenching molecular dynamic calculation and structural/electronic analyses, Ge₂Bi₂Te₅, CdPb₃Se₄, MnBi₂Te₄, and TlBiTe₂ are found suitable for optical/electrical PCM applications, which further verifies the effectiveness of this strategy. The present study will accelerate the exploration and development of advanced PCM materials for current and future big-data applications.     

Chromium-promoted preparation of forsterite refractory materials from ferronickel slag by microwave sintering

The chromium-promoted preparation of forsterite refractory materials from ferronickel slag was investigated by microwave sintering of the slag with the additions of sintered magnesia and 0–10 wt% chromium oxide (Cr₂O₃). The thermodynamic calculations revealed that the addition of Cr₂O₃ can promote the formations of spinel and liquid phase and maintain high content of forsterite below 1500 °C. The experimental results showed that there existed a stronger promoting effect of Cr₂O₃ additive on the properties of refractory materials in the microwave field than that in conventional sintering. It was attributed to the preferential formation and growth of spinel with stronger microwave absorption than other phases (e.g., enstatite), the existence of more forsterite, and the enhanced densification in association with the presence of more liquid phase at the same temperature. By microwave sintering of the mixture of ferronickel slag, 25 wt% sintered magnesia, and 4 wt% Cr₂O₃ at 1350 °C for 20 min, a superior refractory material with refractoriness of 1801 °C, thermal shock resistance of 6 times, bulk density of 2.97 g/cm³, apparent porosity of 1.4%, and compressive strength of 197 MPa was obtained. Compared with that prepared by conventional sintering at 1350 °C for 2 h, the refractoriness and thermal shock resistance were increased by 175 °C and 100%, respectively. The present study provided a novel method for preparing high-quality refractory materials from ferronickel slag and relevant industrial wastes.