Electrogenerated Fe(I) Porphyrins: Efficient Electrocatalysts for Reductive Dechlorination of DDT in N,N′‐Dimethylformamide

Two iron(I) porphyrins were electrogenerated and then utilized as catalysts for the reductive dechlorination of 1,1‐bis(4‐chlorophenyl)‐2,2,2‐trichloroethane (DDT) in N,N′‐dimethylformamide. No reaction is observed between DDT and the Fe(III) or Fe(II) forms of the porphyrin, but the electrogenerated Fe(I) porphyrin efficiently catalyzes the electroreduction of DDT to give (1,1‐bis(4‐chlorophenyl)‐2,2‐dichloroethane) DDD, (1,1‐bis(4‐chlorophenyl)‐2,2‐dichloroethylene) DDE and (1,1‐bis(4‐chlorophenyl)‐2‐dichloroethane) DDMU as determined by GC‐MS analysis. The reductive dechlorination was monitored by electrochemistry, controlled potential electrolysis and spectroelectrochemistry and a mechanism for the reaction involving the reduced porphyrins and DDT is proposed. Comparisons are also made between the catalytic properties of metalloporphyrins containing iron, cobalt and manganese central metal ions under the same solution conditions.     

Pd-catalyzed assembly of phenanthridines from aryl ketone O-acetyloximes and arynes through C–H bond activation

Pd-catalyzed annulation of aryne and aryl ketone O-acetyloxime via C–H bond activation was realized. Through the C–H bond activation/insertion/cyclization/elimination reaction sequence, phenanthridines are successfully constructed, providing an attractive strategy to approach substituted heterocycle without preactivation of starting materials.     

3D amorphous carbon and graphene co-modified LiFePO4 composite derived from polyol process as electrode for high power lithium-ion batteries

Amorphous carbon and graphene co-modified LiFePO_4 nanocomposite has been synthesized via a facile polyol process in connection with a following thermal treatment.Various characterization techniques,including XRD.Mossbauer spectra,Raman spectra,SEM,TEM,BET,O_2-TPO,galvano charge-discharge,CV and EIS were applied to investigate the phase composition,carbon content,morphological structure and electrochemical performance of the synthesized samples.The effect of introducing way of carbon sources on the properties and performance of LiFePO_4/C/graphene composite was paid special attention.Under optimized synthetic conditions,highly crystalized olivine-type LiFePO_4was successfully obtained with electron conductive Fe_2P and FeP as the main impurity phases.SEM and TEM analyses demonstrated the graphene sheets were randomly distributed inside the sample to create an open structured LiFePO_4 with respect to graphene,while the glucosederived carbon mainly coated over LiFeP04 particles which effectively connected the graphene sheets and LiFePO_4 particles to result in a more efficient charge transfer process.As a result,favorable electrochemical performance was achieved.The performance of the amorphous carbon-graphene co-modified LiFePO_4 was further progressively improved upon cycling in the first 200 cycles to reach a reversible specificcapacity as high as 97 mAh·g~(-1) at 10 C rate.     

Synthesis and self-assembly behavior of thermoresponsive poly(oligo(ethylene glycol) methyl ether methacrylate)-POSS with tunable lower critical solution temperature

This article reports on the synthesis of a novel amphiphilic polyhedral oligomeric silsesquioxane (POSS) end-capped poly(2-(2-methoxyethoxy)ethyl methacrylate)-co-oligo(ethylene glycol) methacrylate) (POSS-P(MEO₂MA-co-OEGMA)). These thermoresponsive organic–inorganic hybrid polymers exhibit critical phase transition temperature in water, which can be finely tuned by changing the feed ratio of OEGMA and MEO₂MA. The lower critical solution temperature (LCST) of POSS-P(MEO₂MA-co-OEGMA) increases from 31 to 59 °C with the increasing of OEGMA content. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) studies show that these polymers can self-assemble into spherical micelles with the thermosensitive block into the corona and the POSS forming the core, and larger aggregates are formed when the temperature values are above their LCSTs. These thermoresponsive polymers POSS-P(MEO₂MA-co-OEGMA) with self-assembly behavior and tunable tempetature-responsive property have the potential applications in material science and biotechnology.     

对正负一级能量之比测量光栅参量方法的改进

提出利用同一波长的入射光在双面入射时两个能量之比的比值对光栅的参量进行测量,进一步提高准确度。首先从理论上比较正弦面形光栅在单一面入射及双面入射时各种衍射效率对光栅表面粗糙度的敏感程度;然后模拟测量出该正弦面型光栅在双面入射情况下的光栅参量;最后成功反演出体积相位全息光栅的三个参量,其测量结果为0.080μm,1.452μm,20.5μm准确度比单一入射面情况(0.080μm,1.451μm,20.1μm)时要高。同时该法继承了原来方法的无损伤、操作简便、可重复、易推广、成本低等优点。     

Thermal Conductance of Graphene-Titanium Interface: A Molecular Simulation

Titanium is a commonly used material in aviation, aerospace, and military applications, due to the outstanding mechanical properties of titanium and its alloys. However, its relatively low thermal conductivity restricts its extended usage. The use of graphene as a filler shows great potential for the enhancement of thermal conductivity in titanium-based metal-matrix composites (MMCs). We used classical molecular dynamics (MD) simulation methods to explore the thermal conductance at the titanium–graphene (Ti/Gr) interface for its thermal boundary conductance, which plays an important role in the thermal properties of Ti-based MMCs. The effects of system size, layer number, temperature, and strain were considered. The results show that the thermal boundary conductance (TBC) decreases with an increasing layer number and reaches a plateau at n = 5. TBC falls under tensile strain and, in turn, it grows with compressive strain. The variation of TBC is explained qualitatively by the interfacial atomic vibration coupling factor. Our findings also provide insights into ways to optimize future thermal management based on Ti-based MMCs materials.     

硅溶胶-硅微粉对层状托贝莫来石物化性质的影响

以硅溶胶和硅微粉为混合硅源,采用动态水热合成法成功制备了层状托贝莫来石催化剂,借助XRD、BET和NH3/CO2-TPD等手段对托贝莫来石进行分析表征,研究了不同硅源比例对托贝莫来石晶相结构、比表面积、孔结构性质及表面酸碱性质的影响.结果 表明:随非晶态硅溶胶占比增大,托贝莫来石比表面积和孔容呈逐渐增大趋势,但结晶度和表面酸碱量及弱酸弱碱强度逐渐下降.硅溶胶占比增至20;,托贝莫来石结晶度由81.65;下降至73.66;,总酸量由0.18 mmol·g-1降至0.14 mmol·g-1,总碱量由0.47 mmol·g-1降至0.40 mmol·g-1,比表面积由65 m2·g-1增至174 m2·g-1,孔容由0.15cm3·g-1增至0.60 cm3·g-1,出现介孔-大孔特征;硅溶胶占比增至30;,制得托贝莫来石产物出现少量SiO2晶相.