Hydrophobic Monomers Recognize Microenvironments in Hydrogel Microspheres during Free-Radical-Seeded Emulsion Polymerization

The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications.     

Pd/PdO纳米复合微球的合成及催化性能

采用甲基丙烯酸锌加速还原氯化钯(PdCl₂) 溶液中的钯离子(Pd ²⁺)为钯(Pd) 纳米微球, 进而用得到的钯纳米微球直接制备钯/氧化钯(Pd/PdO) 纳米复合微球. 通过扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 粉末X射线衍射分析(XRD)及X射线光电子能谱分析(XPS) 等方法对 Pd/PdO 纳米复合微球进行表征, 结果表明, 制备的纳米复合微球为表面粗糙、 大小均一的纳米微球. 采用紫外-可见吸收光谱(UV-Vis) 等方法考察了 Pd/PdO 纳米复合微球在对硝基苯酚(4-NTP) 还原反应中的催化性能, 发现其具有良好的催化活性和循环稳定性.     

FTIR与XRD的均匀粒度分布Ce-Cu/TiO2空心微球制备机理研究

随着社会经济的发展，环境空气品质已经成为研究热点。TiO₂是一种化学稳定性高，耐腐蚀性强，对人体无毒无害的N型半导体材料。利用TiO₂的光催化性能提高室内环境空气品质已经成为研究焦点，但是由于TiO₂只能在紫外光源下才具有较高的光催化效率，而在可见光源下的光催化效率较低，从而极大的限制了TiO₂在室内环境领域的发展。因此，研发在可见光源下具有良好光催化性能的TiO₂复合材料势在必行。利用元素掺杂改性技术与提高比表面积方法可以改善光催化反应过程中量子效率和对光能的利用率，以加快电子和空穴向表面迁移的速率同时降低光生载流子的复合机率。以二氧化硅SiO₂为模板、聚乙烯吡咯烷酮为成膜剂、硝酸铈Ce(NO₃)₃·6H₂O和硝酸铜Cu(NO₃)₂·3H₂O为改性剂采用溶胶-凝胶法制备均匀粒度分布的Ce-Cu/TiO₂空心微球，并将制备过程分为四个阶段，即纳米SiO₂球模板的制备、Ce-Cu/TiO₂-SiO₂复合微球凝胶的制备、Ce-Cu/TiO₂-SiO₂复合微球的制备和Ce-Cu/TiO₂空心微球的制备。利用傅里叶变换红外光谱仪（FTIR）与X射线衍射仪（XRD）对Ce-Cu/TiO₂空心微球的制备过程各阶段生成物进行测试与分析，即在纳米SiO₂球模板的制备阶段从微观角度研究纳米SiO₂球模板的搭建过程，在Ce-Cu/TiO₂-SiO₂复合微球凝胶的制备阶段研究TiO₂附着于纳米SiO₂球模板的过程，在Ce-Cu/TiO₂-SiO₂复合微球的制备阶段研究煅烧工艺对Ce-Cu/TiO₂-SiO₂复合微球中晶相与结构的影响，在Ce-Cu/TiO₂空心微球的制备阶段研究氢氧化钠溶液对Ce-Cu/TiO₂-SiO₂复合微球中纳米SiO₂球模板洗涤效果的影响。利用紫外-可见分光光度计（UV-Vis）对Ce-Cu/TiO₂空心微球的光响应性能进行测试与分析，以研究Ce-Cu/TiO₂空心微球对可见光源的利用效率。利用激光粒度分析仪（LPSA）与扫描电子显微镜（SEM）对Ce-Cu/TiO₂空心微球的粒度分布与微观形貌进行测试与分析，以研究Ce-Cu/TiO₂空心微球的均匀粒度分布效果。结果表明：以Si-O-Si基团构建非晶体结构的无定形态纳米SiO₂球模板，有利于聚乙烯吡咯烷酮在纳米SiO₂球模板表面附着，从而控制Ce-Cu/TiO₂空心微球的空腔结构。Ce-Cu掺杂基本进入TiO₂晶体，极少进入纳米SiO₂球模板晶体，从而抑制了Ce-Cu/TiO₂-SiO₂复合微球中TiO₂由锐钛矿相向金红石相的转变。Ce-Cu掺杂TiO₂可以促使TiO₂内部形成新的能级，实现能量较小的光子捕获e-和h+，从而提高Ce-Cu/TiO₂空心微球对可见光源的利用效率。Ce-Cu/TiO₂空心微球的表面光滑且不存在明显的缺陷，其形貌呈现良好的球体且粒径分布均匀，即d₉₀为219.54 nm，d₅₀为151.60 nm、d₁₀为103.84 nm，以及d₉₀-d₁₀为115.70 nm。研究结果为进一步获得可见光源下具有良好光催化性能的均匀粒度分布Ce-Cu/TiO₂空心微球提供理论依据和研究基础。     

Large‐scale production of nitrogen‐ and oxygen‐containing activated carbon microspheres for supercapacitors

A main issue in the production of robust supercapacitors is the creation of efficient and cost‐effective electrodes. We present here the realization of a kind of nitrogen‐ and oxygen‐containing activated carbon microspheres made from divinylbenzene, diallyl phthalate, and acrylonitrile monomers, which can be produced on a large scale for use in supercapacitors. The supercapacitor's performance is optimized by adjusting the carbonization temperature of the microspheres. Our preliminary result shows that the supercapacitor displays a maximum capacitance of 300 F/g at the current density of 1.0 A/g and retains ~82% of the capacitance after 10,000 charge–discharge cycles.     

Preparation and adsorption property of novel inverse-opal hierarchical porous N-doped carbon microspheres

The design of pore structure is the key factor for the performance of porous carbon spheres.In this wo rk,novel micron-sized colloidal crystal microspheres consisting of fibrous silica(F-SiO_2) nanoparticles are firstly prepared by water-evapo ration-induced self-assembly of F-SiO_2 nanoparticles in the droplets of an inverse emulsion system to be used as sacrificial templates.Acrylonitrile(AN) was infiltrated in the voids of the F-SiO_2 colloidal crystal microspheres,and in-situ induced by ~(60)Co y-ray to polymerize into polyacrylonitrile(PAN).After the PAN-infiltrated F-SiO_2 colloidal crystal microspheres were carbonized and etched with HF solution,novel micron-sized inverse-opal N-doped carbon(IO-NC) microspheres consisting of hollow carbon nanoparticles with a hierarchical macro/meso-porous inner surface were obtained.The IO-NC microspheres have a specific surface area as high as 266.4 m~2/g and a molar ratio of C/N of 5.They have a good dispersibility in water,and show a high adsorption capacity towards rhodamine B(RhB) up to 137.28 mg/(g microsphe re).This work offers a way to obtain novel micron-sized hierarchical macro/meso-porous N-doped carbon microspheres,which opens a new idea to prepare high-performance hierarchical porous carbon materials.     

SiO2@Fe2O3核-壳结构催化剂的制备及表征

采用优化的Stöber法制备了平均粒径为230 nm的单分散球形SiO₂颗粒,并以此为内核,通过水解沉积法制备了不同壳层厚度的核-壳结构SiO₂@Fe₂O₃催化剂。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N₂物理吸附和X射线衍射分析(XRD)等手段对催化剂进行表征,探讨了不同制备条件对SiO₂@Fe₂O₃催化剂形貌的影响。结果表明,通过水解沉积法制备的SiO₂@Fe₂O₃催化剂具有明显的核-壳结构,并且保持了原始SiO₂核的球形形貌,Fe₂O₃纳米粒子通过-OH的氢键作用连接在SiO₂表面,形成了2~10 nm厚的Fe₂O₃均匀连续包覆层。     

反相悬浮聚合法制备硫氰酸根阴离子印迹微球及其离子识别性质

利用反相悬浮聚合法, 成功制备了微米级硫氰酸根(SCN^-)阴离子印迹微球。 以溶有分散剂Span-60的环已烷为分散介质, 以溶有模板阴离子SCN^-、阳离子单体丙烯酰氧乙基三甲基氯化铵(DAC)及交联剂N, N'-亚甲基双丙烯酰胺(MBA)的水溶液为分散相, 构成反相悬浮聚合体系, 在水相液滴中使DAC发生交联聚合, 成功制备了粒径约为200 μm的离子印迹微球(IIPMs)。 以同为一价阴离子的NO₃^-和I^-为对比离子, 深入考察研究了该离子印迹微球的离子识别与结合特性。 研究结果表明, 凭借强静电相互作用, 在水相液滴中, 阳离子单体DAC与模板阴离子SCN^-紧密相结合, 故在DAC交联聚合的同时, 实现了阴离子SCN^-的印迹。 所制备的阴离子印迹微球IIPMs对模板阴离子SCN^-具有很高的结合能力(结合容量为3.3 mmol/g(192 mg/g))和特异的识别选择性。 该印迹微球可选择性地识别与结合离子混合溶液中的SCN^-离子, 相对于NO₃^-和I^-阴离子, IIPMs对SCN^-阴离子的选择性系数分别为3.24和6.78。 该印迹微球还具有优良的重复使用性能。     

一种温敏型超大孔生物分离介质的制备及表征

采用改性琼脂糖对超大孔聚苯乙烯微球进行亲水化修饰(Agap-PS),通过酰基化反应在微球表面引入溴乙酰基(Agap-PS-Br),然后利用原子转移自由基聚合(ATRP)反应在Agap-PS-Br表面接枝温敏聚合物刷,得到一种温敏型超大孔生物分离介质(Agap-PS-PNIPAM).考察了配体、催化剂、溶剂和温度对N-异丙基丙烯酰胺ATRP反应的影响,在优化条件下PNIPAM的接枝量达到了15.07 mg/m2.采用红外光谱(FTIR)、扫描电镜(SEM)、压汞分析、激光共聚焦和蛋白吸附等手段对温敏型超大孔生物分离介质进行一系列表征,结果表明接枝温敏聚合物刷后Agap-PS-PNIPAM具有良好的温敏性,没有堵塞微球的超大孔,微球对蛋白的非特异性吸附大大降低.由于温敏聚合物刷发生了从亲水到疏水构象的转变,40℃时Agap-PS-PNIPAM对蛋白的吸附量是25℃时的2.69倍.压力流速实验表明Agap-PS-PNIPAM柱具有背压低、渗透性和机械稳定性好的优点,同样地由于PNIPAM链在40℃时收缩,此时Agap-PS-PNIPAM柱的床层渗透系数比25℃时提高了15.7％.     

Synthesis and characterization of magnetic polymer microspheres with a core-shell structure

Non-porous magnetic polymer microspheres with a core-shell structure were prepared by a novel micro-suspension polymerization technique. A stable iron oxide ferrofluid was used to supply the magnetic core, and the polymeric shell was made of glycidyl methacrylate （GMA monomer） and ethylene dimethacrylate （cross-linker）. In the preparation, polyvinyl alcohol was used as the stabilizer, and a lauryl alcohol mixture as the dispersant. The influence of various conditions such as aqueous phase volume, GMA and initiator amounts, reaction time and stirring speed on the character of the microspheres was investigated. The magnetic microspheres were then characterized briefly. The results indicate that the microspheres with active epoxy groups had a narrow size distribution range from 1 to 10 μm with a volume-weighted mean diameter of 4.5 μm. The saturation magnetization reached 19.9 emu/g with little coercivity and remanence.     

Rectifying resistance switching behaviors of SnO2 microsphere films modulated by top electrodes

Based on the bipolar resistive switching (RS) characteristics of SnO₂ films, we have fabricated a new prototypical device with sandwiched structure of Metal/SnO₂/fluorine-doped tin oxide (FTO). The SnO₂ microspheres film was grown on FTO glass by template-free hydrothermal synthesis, which was evaporated with various commonly used electrodes such as aluminium (Al), silver (Ag), and gold (Au), respectively. Typical self-rectifying resistance switching behaviors were observed for the RS devices with Al and Au electrodes. However, no obvious rectifying resistance switching behavior was observed for the RS device with Ag electrode. Above results were interpreted by considering the different interface barriers between SnO₂ and top metal electrodes. Our current studies pave the ways for modulating the self-rectifying resistance switching properties of resistive memory devices by choosing suitable metal electrodes.