Alkylation of catechol with methanol to guaiacol over sulphate-modified zirconia solid acid catalysts

A series of sulphate-promoted ZrO₂ solid acid catalysts with different contents of SO₄ ²⁻ were calcined at 450°C in air for 4 h and tested for the liquid-phase alkylation of catechol to guaiacol in a fixed-bed down-flow reactor. The 5 wt.% SO₄ ²⁻ on ZrO₂ showed the best conversion (82%) and selectivity for guaiacol (84%) at 200°C and 1 bar pressure. A smooth correlation was observed between the catalytical activity and surface acidity of sulphated zirconia. Based on our results, a surface mechanism is proposed.     

Statistical Optimization for Succinic Acid Production from E. Coli in a Cost-Effective Medium

Response surface methodology (RSM) was employed for optimization of medium components and cultural parameters in cost effective cane molasses based medium for attaining high yield of succinic acid. The important factors obtained by “one-variable-at-a-time-approach” (cane molasses, corn steep liquor, sodium carbonate, and inoculum density) were further optimized by RSM. The optimum values of the parameters obtained through RSM (cane molasses 12.5%, corn steep liquor 7.5%, and sodium carbonate 25 mM) led to almost double yield of succinic acid (15.2 g/l in 36 h) as against “one-variable-at-a-time-approach” (7.1 g/l in 36 h) in 500-ml anaerobic bottles containing 300-ml cane molasses based medium. Subsequently, in 10-l bioreactor succinic acid production from Escherichia coli was further improved to 26.2 g/l in 30 h under conditions optimized through RSM. This fermentation-derived succinic acid will definitely help in replacing existing environmentally hazardous and cost-intensive chemical methods for the production of succinic acid.     

Effect of specific adsorption of anions on the kinetics of the current relaxation after pulsed anodic activation of dissolution of hydrophilic metals

Based on the model of spatial separation of the dissolution and passivation of hydrophilic metals, the effect of strong specific adsorption of anions on the shape of curves for the relaxation of anodic current of metals in acid solutions after switching an anodic activation pulse off is considered by using iron as an example.     

模板沉淀法制备高比表面积MnOx-CeO2催化剂及其CO低温氧化活性

以十六烷基三甲基溴化铵(CTAB)为模板剂, Ce(NO3)3和Mn(NO3)2为前驱体, 通过沉淀法制备了一系列晶粒小于5 nm的高比表面积MnOx-CeO2催化剂, 并考察了催化剂的CO氧化反应性能. 采用XRD、Raman光谱、TPR和N2气吸附脱附等手段对催化剂的比表面积、晶粒大小和物相组成进行了表征. 当Mn摩尔分数≤34%时, 催化剂的比表面积在160~170 m2/g之间; 当锰含量进一步提高后, 催化剂的比表面积呈下降趋势. 当Mn摩尔分数≤34%时, XRD只检测到CeO2物相, 而Raman光谱则检测到α-Mn2O3的存在. 催化剂上表现出较好的CO氧化活性, 这主要归因于高比表面积. 随着锰含量的增加, 催化剂的轻化频率(TOF)下降, 表明高分散、小晶粒的氧化锰物种是催化剂的活性物种. H2-TPR结果表明, 催化剂的CO氧化活性还与催化剂中高价锰物种有关. 焙烧温度升高使催化剂的晶粒增大、比表面积减小, 同时催化剂中锰的平均价态降低, 导致CO氧化活性下降.     

纳米CaCO3的改性、表面结构与流变行为研究

采用铝锆偶联剂和棕榈酸改性纳米CaCO₃ 粉体. 借助 XRD, FTIR, 接触角及流变学等测试方法对纳米CaCO₃ 的表面结构进行表征. XRD 分析表明: 改性纳米 CaCO₃保持原样品完整的体相结构, 为方解石型纳米微晶. FTIR 分析证明: 表面改性剂与纳米 CaCO₃ 表面是以化学键合和物理吸附方式相结合, 粒子表面存在羧基等有机官能团的红外吸收特征. 通过测定苯和水在改性纳米CaCO₃粉末压片上的接触角, 计算了改性纳米 CaCO₃的表面能和极性分量, 并与未改性纳米CaCO₃ 进行比较. 结果表明, 经表面改性, 纳米 CaCO₃ 的表面能和极性分量明显降低, 其在有机溶液中的吸附功增大, 界面张力大大降低; 经棕榈酸改性的纳米 CaCO₃ 表现出较好的亲油疏水性, 而铝锆偶联剂改性的纳米 CaCO₃ 同时具有亲水性和亲油性. 以液体石蜡为溶剂, 研究了表面改性对纳米CaCO₃悬浮液流变行为的影响. 实验发现: 经过表面处理, 纳米 CaCO₃ 粉体悬浮液流变行为发生较大的变化, 稳态剪切黏度大大降低, 表现出较小的动态弹性储能模量和黏性损耗模量, 而损耗因子较大.     

Fe3O4磁性纳米粒子的超声包金及其表征

超声条件下, 在乙醇分散的3-氨丙基三乙氧基硅烷(APTES)功能化的磁性Fe₃O₄纳米粒子和四氯合金酸的混合溶液中滴加柠檬酸钠, 成功地制备了磁性Fe₃O₄/Au复合纳米粒子. 采用X射线粉末衍射仪(XRD)、紫外吸收可见光谱(UV-Vis)、带有电子能谱仪(EDS)的扫描电子显微镜(SEM)、透射电子显微镜(TEM)、光电子能谱(XPS)、超导量子干涉仪(SQUID)等方法, 对复合粒子的形态、结构、组成以及磁学性质进行了表征. 结果表明: 在此条件下制得的复合粒子粒径在30 nm左右, 室温下磁化强度可达63 emu/g.     

PREPARATION OF POLYMER MICROSPHERES WITH PYRIDYL GROUP AND THEIR STABILIZED GOLD METALLIC COLLOIDS

Narrow disperse poly(ethyleneglycol dimethacrylate-co-4-vinylpyridine)(poly(EGDMA-co-4-VPy))microspheres were prepared by distillation-precipitation copolymerization of ethyleneglycol dimethacrylate(EGDMA)and 4-vinylpyridine (4-VPy)with 2,2'-azobisisobutyronitrile(AIBN)as initiator in neat acetonitrile.The polymer microspheres containing pyridyl group were then utilized as stabilizer for gold metallic colloids with the diameter around 7 nm,which were prepared by the in situ reduction of gold chloride trihydrate with sodium borohydride through the coordination of the pyridyl group on the gel layer and surface of the microsphere with the gold metallic nano-particles.The catalytic properties of the pyridyl- functionalized microsphere-stabilized gold metallic colloids and the behavior of the stabilized-catalyst for the recycling were investigated with reduction of 4-nitrophenol to 4-aminophenol as a model reaction.     

Surface disordering of classic and superionic crystals: A description in the framework of the stern model

The surface potential (φ_S) in ionic crystals: binary compounds of the type NaCl and superionic oxygen conductors of the type M _{1 ? c} ^IV Me _c ^III O_{2 ? c/2} are calculated with the aid of the Stern model. Effect of the energy of formation of defects, concentration of accessible sites (N _S), and concentration of admixtures on the temperature dependences of φ_S(T) is studied. Instances of high and low potentials are analyzed. It is demonstrated that the surface potential increases proportionally to the difference between the adsorption energies of individual defects, provided the absolute value of |ΔG _i| (ΔG _i < 0) and concentration N _S are sufficiently large. Values of isoelectric temperatures in NaCl crystals doped with admixtures of other valence are calculated. An attempt is undertaken to describe experimental data for silver halides with the aid of the model. Calculations of the surface potential in superionic oxygen conductors show that increasing concentration of surface vacancies is accompanied by segregation of the admixture cations in the surface layer.     

金属锂二次电池锂负极改性

本文综述了金属锂二次电池中提高锂负极性能的研究进展。分别介绍了以下改性方法:对金属锂表面进行预处理,使其表面预先形成性能良好的固体电解质界面膜,或直接在其表面制备保护膜;在电解液中加入添加剂对锂电极进行表面改性;采用新型有机溶剂、离子液体、聚合物电解质、玻璃态固体电解质、塑晶固体电解质等电解质体系提高界面相容性;改进金属锂电极的制备工艺,如制备金属锂粉末多孔电极和电沉积锂电极、制备全固态薄膜锂电池以及利用物理方法处理锂电极。并在此基础上对今后的发展趋势进行了展望。     

化学/电化学腐蚀法快速制备超疏水金属铝

提出一种金属铝超疏水表面的快速制作方法. 先以化学腐蚀在铝表面形成微米级粗糙结构, 再通过电化学腐蚀构筑纳米结构, 在20 min内完成了超疏水表面所需粗糙结构的制备. 这种化学腐蚀/电化学腐蚀两步法比单独化学或电化学腐蚀方法在时间上缩短了1~2个数量级, 且不受铝材晶形限制, 同时电化学腐蚀所用电流密度也降低了1个数量级, 降低了对电源设备的要求, 可望大规模应用于工业生产和其它金属的超疏水表面制备.