Synthesis and characterization of poly(1-sila-cis-pent-3-enes) substituted with pendant pyridinyl groups

Poly[1-methyl-1-[3-(3-pyridinyl)propyl]-1-sila-cis-pent-3-ene], poly[1-phenyl-1-[3-(3-pyridinyl)propyl)-1-sila-cis-pent-3-ene], and poly[1-phenyl-1-(4-pyridinyl)-1-sila-cis-pent-3-ene] were synthesized by the anionic ring-opening polymerization of 1-methyl-1-[3-(3-pyridinyl)propyl]-1-silacyclopent-3-ene, 1-phenyl-1-[3-(3-pyridinyl)propyl]-1-silacyclopent-3-ene, and 1-phenyl-1-(4-pyridinyl)-1-silacyclopent-3-ene, respectively. These are the first polycarbosilanes which contain heterocyclic pyridine units as side-chain substituents. These polymers were characterized by¹H,¹³C, and²⁹Si NMR as well as by IR and UV spectroscopy. The molecular weight distributions were determined by gel permeation chromatography, glass transition temperatures, by differential seanning calorimetry: (DSC) and thermal behavior, by thermogravimetric analysis. (TGA).     

电气类专业群双创人才培养的探索与实践

针对科技产业发展人才需求和专创融合教育改革中存在的问题,本文从构建双创型人才培养模式、完善实践教学体系、深化校企合作和建立特色创新创业工作室四个方面,对厦门理工学院电气类专业群创新创业人才培养进行探索与实践。实施效果表明,已取得积极成效,具有一定推广价值。     

Engineering Transition Metal Layers for Long Lasting Anionic Redox in Layered Sodium Manganese Oxide

Oxygen-redox-based-layered cathode materials are of great importance in realizing high-energy-density sodium-ion batteries (SIBs) that can satisfy the demands of next-generation energy storage technologies. However, Mn-based-layered materials (P2-type Na-poor Na_y[A_xMn_1−x]O₂, where A = alkali ions) still suffer from poor reversibility during oxygen-redox reactions and low conductivity. In this work, the dual Li and Co replacement is investigated in P2-type-layered Na_xMnO₂. Experimentally and theoretically, it is demonstrated that the efficacy of the dual Li and Co replacement in Na_0.6[Li_0.15Co_0.15Mn_0.7]O₂ is that it improves the structural and cycling stability despite the reversible Li migration from the transition metal layer during de-/sodiation. Operando X-ray diffraction and ex situ neutron diffraction analysis prove that the material maintains a P2-type structure during the entire range of Na⁺ extraction and insertion with a small volume change of ≈4.3%. In Na_0.6[Li_0.15Co_0.15Mn_0.7]O₂, the reversible electrochemical activity of Co³⁺/Co⁴⁺, Mn³⁺/Mn⁴⁺, and O^2-/(O₂)^n- redox is identified as a reliable mechanism for the remarkable stable electrochemical performance. From a broader perspective, this study highlights a possible design roadmap for developing cathode materials with optimized cationic and anionic activities and excellent structural stabilities for SIBs.     

Comprehensively Strengthened Metal-Oxygen Bonds for Reversible Anionic Redox Reaction

Introducing anionic redox in layered oxides is an effective approach to breaking the capacity limit of conventional cationic redox. However, the anionic redox reaction generally suffers from excessive oxidation of lattice oxygen to O₂ and O₂ release, resulting in local structural deterioration and rapid capacity/voltage decay. Here, a Na_0.71Li_0.22Al_0.05Mn_0.73O₂ (NLAM) cathode material is developed by introducing Al³⁺ into the transition metal (TM) sites. Thanks to the strong Al–O bonding strength and small Al³⁺ radius, the TMO₂ skeleton and the holistic TM–O bonds in NLAM are comprehensively strengthened, which inhibits the excessive lattice oxygen oxidation. The obtained NLAM exhibits a high reversible capacity of 194.4 mAh g^-1 at 20 mA g^-1 and decent cyclability with 98.6% capacity retention over 200 cycles at 200 mA g⁻¹. In situ characterizations reveal that the NLAM experiences phase transitions with an intermediate OP4 phase during the charge–discharge. Theoretical calculations further confirm that the Al substitution strategy is beneficial for improving the overlap between Mn 3d and O 2p orbitals. This finding sheds light on the design of layered oxide cathodes with highly reversible anionic redox for sodium storage.     

Aqueous solution of Oxone as new oxidizing agent for multi-walled carbon nanotube functionalization

In this work, multi-wall carbon nanotube (MWCNT) was successfully modified using aqueous solution of Oxone as a new oxidant. The effect of oxidation temperature on various characteristics of the treated MWCNTs was also investigated. FTIR and titration analysis proved the formation of carboxyl, carbonyl and epoxide groups at the surface of MWCNTs. The concentration of the functional groups increased as the modification temperature increased. The presence of such oxygen containing groups at the surface of MWCNTs justified the long time stability of the treated MWCNTs suspensions in water and methanol. The modified MWCNTs showed higher entanglement compared to row MWCNT due to the cross-links adjacent effect of pendant functional groups. Finally, it was concluded that Oxone oxidation process destroys the structure of the MWCNTs, but not severe enough to unzip the MWCNTs.     

Anionic Regulated NiFe (Oxy)Sulfide Electrocatalysts for Water Oxidation

The construction of active sites with intrinsic oxygen evolution reaction (OER) is of great significance to overcome the limited efficiency of abundant sustainable energy devices such as fuel cells, rechargeable metal–air batteries, and in water splitting. Anionic regulation of electrocatalysts by modulating the electronic structure of active sites significantly promotes OER performance. To prove the concept, NiFeS electrocatalysts are fabricated with gradual variation of atomic ratio of S:O. With the rise of S content, the overpotential for water oxidation exhibits a volcano plot under anionic regulation. The optimized NiFeS‐2 electrocatalyst under anionic regulation possesses the lowest OER overpotential of 286 mV at 10 mA cm^?2 and the fastest kinetics being 56.3 mV dec^?1 to date. The anionic regulation methodology not only serves as an effective strategy to construct superb OER electrocatalysts, but also enlightens a new point of view for the in‐depth understanding of electrocatalysis at the electronic and atomic level.     

A Phase‐Separation Route to Synthesize Porous CNTs with Excellent Stability for Na+ Storage

Porous carbon nanotubes (CNTs) are obtained by removing MoO₂ nanoparticles from MoO₂@C core@shell nanofibers which are synthesized by phase‐segregation via a single‐needle electrospinning method. The specific surface area of porous CNTs is 502.9 m² g^?1, and many oxygen‐containing functional groups (C? OH, C?O) are present. As anodes for sodium‐ion batteries, the porous CNT electrode displays excellent rate performance and cycling stability (110 mA h g^?1 after 1200 cycles at 5 A g^?1). Those high properties can be attributed to the porous structure and surface modification to steadily store Na⁺ with high capacity. The work provides a facile and broadly applicable way to fabricate the porous CNTs and their composites for batteries, catalysts, and fuel cells.     

阴离子聚合制备PA6/12共聚物的研究

以己内酰胺(CL)和十二内酰胺(LL)为单体,采用阴离子开环共聚制备尼龙6/12(PA6/12)共聚物,主要研究了LL添加量对共聚物热性能、结晶性能、力学性能和断面形貌的影响。研究结果表明,LL的添加量由0%增加到30%时,PA6/12共聚物熔融温度从218.0℃降低到182.6℃,结晶温度由168.9℃降至117.8℃,晶型结构未发生明显变化,但其结晶度由22.88%降低至13.58%,拉伸性能和弯曲性能都有一定程度降低,断裂伸长率由60%增大到325%,并在共聚物拉伸断面观察到大量直径为100nm、长度为1μm左右的纳米纤维状物质。     

Wave Groups in Uni-Directional Surface-Wave Models

Uni-directional wave models are used to study wave groups that appear in wave tanks of hydrodynamic laboratories; characteristic for waves in such tanks is that the wave length is rather small, comparable to the depth of the layer. In second-order theory, the resulting Nonlinear Schrödinger (NLS) equation for the envelope of the wave group contains the dispersion of the group velocity multiplying the linear term and a gen-coefficient that results from mode generation multiplying the nonlinear term. The signs of these coefficients determine whether experimentally relevant wave groups are possible or not. If the dispersion is modelled in such a way that it is correct for all wave lengths for infinitesimal waves, relevant wave groups are obtained consisting of constituent waves with a certain maximal wave length; other models for the dispersion (such as in the KdV-equation) lead to different results.     

Alkylation of phenol with 1-propanol and 2-propanol over catalysts derived from hydrotalcite-like anionic clays

Vapour phase alkylation of phenol with 1-propanol and 2-propanol was carried out in a fixed-bed flow reactor over calcined magnesium aluminium hydrotalcites (MgAl-CHT) with Mg/Al atomic ratios 2, 3 and 4. MgAl 3.0-CHT showed higher phenol conversion (80% at 350C, in the alkylation of phenol with 1-propanol. Both O- and C-alkylations were found to be taking place without any skeletal isomerization of the propyl moiety, suggesting an S_N2 type mechanism. Isomorphous substitution of Mg²⁺ by Cu²⁺ or Ni²⁺ in the hydrotalcite framework resulted in the predominant C-alkylation to give 2-n-propylphenol (60–70%) with nearly 40–50% phenol conversion at 350C. When 2-propanol was used as an alkylating agent, the phenol conversion decreased over all these catalysts and the alkylation was noticed exclusively at C-centers. Comparison of the product selectivity at constant phenol conversion revealed that CuAl 3.0-CHT is more selective for 2-n-propylphenol and 2-isopropylphenol in the reaction of phenol with 1-propanol and 2-propanol respectively. The participation of a pair of acid-base sites in the calcined hydrotalcites for the alkylation reaction has been proposed. The acid-base properties of these catalysts have been examined by the decomposition of cyclohexanol as a test reaction. Analysis of the spent catalysts revealed that Cu²⁺ in CuO gets reduced into Cu¹⁺ and metallic copper during the reaction in the case of CuAl-CHT, while MgO and NiO phases of MgAl-CHT and NiAl-CHT are retained.