密度泛函理论方法研究填料表面对聚合物摩擦化学的影响

采用超声分散法制备出氧化铝、高岭土、氧化硅/聚四氟乙烯复合材料, 使用线性往复摩擦磨损试验机对比三种复合材料的摩擦学性能. 结果表明 质量分数10%的氧化铝、高岭土能将聚四氟乙烯的磨损率降低约4个数量级, 而氧化硅仅能降低约3个数量级. 对金属对偶表面形成的转移膜的形貌和化学成分进行分析发现 氧化铝、高岭土/聚四氟乙烯在金属对偶面上形成了高度羧酸盐化的转移膜. 用密度泛函理论对三种填料表面上碳氟分子吸附过程进行模拟, 结果显示氧化铝、高岭土表面的路易斯酸性位点促进了碳氟分子的脱氟过程, 产生了更多的羧酸螯合物的中间产物; 氧化硅缺少路易斯酸性位点, 因此不能促进高度羧酸盐化的转移膜形成.     

Nanocomposite thin film structures based on polyarylenephthalide with SWCNT and graphene oxide fillers

Investigations of nanocomposite thin films based on polyarylene- phthalide, single-walled carbon nanotubes and graphene oxide have been carried out. Using these films as a transport layer, field-effect transistors were assembled and their output and transfer characteristics were measured. The mobility of charge carriers was estimated and the obtained values are as follows: μ_PAP/GO = 0.020 cm² V^?1 s^?1 and μ_PAP/SWCNT = 0.071 cm² V^?1 s^?1.     

Superconductivity and unconventional density waves in vanadium-based kagome materials AV3Sb5

Recently, the discovery of vanadium-based kagome metal AV₃Sb₅ (A= K, Rb, Cs) has attracted great interest in the field of superconductivity due to the coexistence of superconductivity, non-trivial surface state and multiple density waves. In this topical review, we present recent works of superconductivity and unconventional density waves in vanadium-based kagome materials AV₃Sb₅. We start with the unconventional charge density waves, which are thought to correlate to the time-reversal symmetry-breaking orders and the unconventional anomalous Hall effects in AV₃Sb₅. Then we discuss the superconductivity and the topological band structure. Next, we review the competition between the superconductivity and charge density waves under different conditions of pressure, chemical doping, thickness, and strains. Finally, the experimental evidence of pseudogap pair density wave is discussed.     

High-efficient surface tailoring via reverse atom transfer radical polymerization and reversible addition-fragmentation chain-transfer polymerization in an aqueous system initiated by a monocenter redox pair

The commonly used multi-center initiation methods always lead to the formation of quantities of homopolymer in the surface tailoring based on reverse atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. In this study, a monocenter redox pair constructed of silica bearing tert-butyl hydroperoxide groups and ascorbic acid (SiO₂-TBHP/AsAc) was applied to substitute the commonly used initiation method of R-supported RAFT grafting polymerization. All the propagating radicals were restricted on the surface of solid particles during the whole procedure theoretically, resulting in a higher grafting efficiency of 95.1% combined with the “controllable” feature at 10 h. This redox pair was also used to initiate the reverse ATRP in miniemulsion successfully with a grafting efficiency of 86.3% at 10 h. The grafting efficiency obtained under this monocenter initiation method was significantly higher than that of the frequently reported surface modification by reverse ATRP and RAFT polymerization. In addition, the high-efficient surface tailoring was traced and confirmed by nuclear magnetic resonance, Fourier transform infrared, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission electron microscopy, and other analysis tests. The advantage of this monocenter redox pair will open a new avenue for the potential “high-efficient” surface tailoring of various materials.     

Visible light-driven acridone catalysis for atom transfer radical polymerization

Acridone as a new kind of visible light photocatalyst has been developed to catalyze metal free atom transfer radical polymerization (ATRP). The photocatalyst possess low excited state potential as can undergo an oxidative quenching pathway to initiate ATRP of vinyl monomers. Kinetic study and light on/off reaction demonstrate the “living”/controlled nature of the polymerization by light. Block copolymers can be achieved by using PMMA as macroinitiator to reinitiate polymerization of other vinyl monomers, which shows highly preserved Br chain-end functionality in the synthesized polymers. Moreover, the polymerization can be conducted under air atmosphere as most photocatalysts need anaerobic condition, which may give inspiration of further application of this kind of photocatalyst.     

Monitoring the Thiol/Thiophenol Molecule-Modulated Plasmon-Mediated Silver Oxidation with Dark-Field Optical Microscopy

Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts.     

Visible-Light Augmented Lithium Storage Capacity in a Ruthenium(II) Photosensitizer Conjugated with a Dione-Catechol Redox Couple

Controlling redox activity of judiciously appended redox units on a photo-sensitive molecular core is an effective strategy for visible light energy harvesting and storage. The first example of a photosensitizer - electron donor coordination compound in which the photoinduced electron transfer step is used for light to electrical energy conversion and storage is reported. A photo-responsive Ru-diimine module conjugated with redox-active catechol groups in [Ru(II)(phenanthroline-5,6-diolate)₃]⁴⁻ photosensitizer can mediate photoinduced catechol to dione oxidation in the presence of a sacrificial electron acceptor or at the surface of an electrode. Under potentiostatic condition, visible light triggered current density enhancement confirmed the light harvesting ability of this photosensitizer. Upon implementation in galvanostatic charge-discharge of a Li battery configuration, the storage capacity was found to be increased by 100 %, under 470 nm illumination with output power of 4.0 mW/cm⁻². This proof-of-concept molecular system marks an important milestone towards a new generation of molecular photo-rechargeable materials.     

New Palladium – ZrO2 Nano-Architectures from Thermal Transformation of UiO-66-NH2 for Carbonylative Suzuki and Hydrogenation Reactions

The new nanocomposites, Pd/C/ZrO₂, PdO/ZrO_2, and Pd/PdO/ZrO₂, were prepared by thermal conversion of Pd@UiO-66-Zr−NH₂ (MOF) in nitrogen or air atmosphere. The presence of Pd nanoparticles, uniformly distributed on the ZrO₂ or C/ZrO₂ matrix, was evidenced by transmission electron microscopy, scanning electron microscopy (SEM), Raman and X-ray Photoelectron Spectroscopy (XPS) methods. All pyrolysed composites retained the shape of the MOF template. They catalyze carbonylative Suzuki coupling under 1 atm CO with an efficiency significantly higher than the original Pd@UiO-66-Zr−NH₂. The most active PdO/ZrO₂ composite, formed benzophenone with TOF up to 1600 h⁻¹, while by using Pd@UiO-66-Zr−NH₂, much lower TOF values, 51–95 h⁻¹, were achieved. After the reaction, PdO/ZrO₂ was recovered with the same composition and catalytic activity. Very good results were also obtained in the transfer hydrogenation of benzophenones to alcohols with Pd/C/ZrO₂ and PdO/ZrO₂ catalysts under microwave irradiation.