碳模板诱导生长Fe-Nx活性位点

能源危机和环境恶化是当今社会面临的巨大挑战. 燃料电池作为一种高效、清洁的发电装置,受到了社会各界特别是新能源行业的高度关注. 尤其是, 日本丰田推出Mirai燃料电池汽车量产上市计划, 把燃料电池及其关键技术发展推向了一个新的发展纪元. 然而, 制约燃料电池走向大规模商业化的核心问题依然是其综合性能不具竞争力. 其中, 氧电极的缓慢动力学以及贵金属Pt的有限资源、高昂成本等是关键所在, 因此, 亟待实现高性能非贵金属催化剂的突破.近年来, 大量研究表明, Fe-Nx掺杂的碳催化剂具有极大的代Pt潜力, 研究者们尝试各种手段进行开发,如: 调控Fe化合物及N前驱体的类型与添加量, 改变温度、压力等合成条件, 采用轴向配位体连接、共价接枝、球磨等非热解路线, 构建核壳、有序介孔碳、阵列、类石墨烯薄片、多孔碳等碳纳米结构, 制备石墨烯/碳纳米管、石墨烯/碳黑、碳纳米带/碳纳米管、碳纳米颗粒/碳纤维、碳球/碳纳米管/石墨烯等复合材料, 进行酸洗、造孔、二次加热等后处理, 调控不同类型Fe物种相生成等. 此外, EXAFS及M?ssbauer等谱学技术已经证实Fe-Nx特别是Fe-N4为强活性位点. 因此, 有待提出合理策略以促进非贵金属碳催化剂中Fe-Nx强活性位点的高密度掺杂.本文提出了一种碳模板诱导Fe-Nx活性位点生长的方法即通过高温热解含有Fe盐的三聚氰胺前驱体混合物, 成功制备 了Fe-Nx掺杂的碳催化剂, 并结合多种表征技术证实了碳模板对制备碳催化剂结构组成及电化学性能的影响. 形貌结果说明, 碳模板的引入有利于Fe、N化合物的均匀吸附以至于Fe基纳米颗粒的均一成核, 促使竹状碳纳米管在碳模板表面以及中间均一生长; 氮气吸脱附及孔径分布曲线显示, 引入碳模板形成的复合材料较单一的碳纳米管和碳黑材料具有提高的比表面积和总孔体积, 说明复合材料中存在两种单体的有效协同; M?ssbauer、XPS及XRD测试数据证实, 碳模板可以调控Fe、N两种元素的耦合方式, 能够抑制金属Fe和Fe碳化物等非活性Fe物种的生成、诱导Fe-N4和其它Fe氮化物等强活性Fe-Nx物种的生长. 电化学测试数据表明, 复合材料具有提升的面积活性和质量活性, 且TOF值明显提高, 说明碳模板的引入增强了Fe-Nx位点的本征活性; 此外, 复合材料的氧还原过程为高效的4e-途径, 且较商业Pt/C催化剂表现出了优异的循环稳定性和甲醇耐受性.     

Dinuclear Dy2 Single‐Molecule Magnets: Functional Modulation on the Bridging Ligand and Different Relaxation Performances within the Single‐Crystal to Single‐Crystal System

Crystal structures, single‐molecule magnetic behavior, and ab initio calculations of four new phenoxo‐bridged dinuclear dysprosium complexes and their gadolinium(III) analogues are explored. Complexes [Dy₂(DMOMP)₂(DBM)₄]₂ ? CHCl₃ ( 1 ; DMOMP=1‐methyl‐3,5‐dimethoxy‐4‐hydroxybenzene, DBM=1,3‐diphenylpropane‐1,3‐dione); [Dy₂(DMOAP)₂(DBM)₄]₂ ? CHCl₃ ( 2 ; DMOAP=syringaldehyde); Dy₂(DMOEP)₂(DBM)₄ ( 3 ; DMOEP=methyl syringate); and solvent‐free Dy₂(DMOMP)₂(DBM)₄ ( 4 ), which is obtained by the transformation of single crystal into single crystal from 1 , have nearly identical core structures and only differ in the substituents at the para position of the phenol moieties of the bridging ligand. In this system, the electronic effects are efficiently implemented to significantly modify the ligand field strength and exchange coupling by modulating the substituents on the phenol backbone. The effective energy barrier (U_eff) of magnetization reversal is improved significantly to fivefold magnitude, at most, and the hysteresis temperature up to 3.5 K by deliberately using the electron‐withdrawing substituent to replace the electron‐donating one. The origin of the two relaxation processes in 1 is mostly attributed to the existence of two molecules in one unit, which is illuminated by means of the transformation of single crystal into single crystal.     

Metal–Organic Framework (MOF) Nanorods,Nanotubes, and Nanowires

New mechanisms for the controlled growth of one‐dimensional (1D) metal–organic framework (MOF) nano‐ and superstructures under size‐confinement and surface‐directing effects have been discovered. Through applying interfacial synthesis templated by track‐etched polycarbonate (PCTE) membranes, congruent polycrystalline zeolitic imidazolate framework‐8 (ZIF‐8) solid nanorods and hollow nanotubes were found to form within 100 nm membrane pores, while single crystalline ZIF‐8 nanowires grew inside 30 nm pores, all of which possess large aspect ratios up to 60 and show preferential crystal orientation with the {100} planes aligned parallel to the long axis of the pore. Our findings provide a generalizable method for controlling size, morphology, and lattice orientation of MOF nanomaterials.     

ZIF‐8@SiO2 core–shell microsphere extraction coupled with liquid chromatography and triple quadrupole tandem mass spectrometry for the quantitative analysis of four plant growth regulators in navel oranges

Monodisperse silica spheres that comprised a rhombic‐dodecahedral zeolitic imidazolate framework core–shell microsphere were applied in the sample pretreatment of navel orange. A rapid and efficient liquid chromatography with triple quadrupole tandem mass spectrometry method was established for simultaneously quantifying four plant growth regulators, 6‐benzylaminopurin, indole‐3‐acetic acid, indolepropionic acid, 3‐indolebutyric acid, in navel oranges. A satisfactory result was obtained, i.e., the peak area of the four plant growth regulators against concentration was linear with good correlation coefficients of 0.99987–0.99991. Under optimized conditions, the limits of detection were 3.0–59.4 μg/L for the four plant growth regulators. This method was applied to the simultaneous analysis of the four plant growth regulators in commercial samples, and all the detections were confirmed by acquiring transitions for each pesticide in the samples.     

Asymptotic properties of the growth curve model with covariance components

We consider a multivariate regression (growth curve) model of the form , where and are unknown scalar covariance components. In the case of replicated observations, we derive the explicit form of the locally best estimators of the covariance components under normality and asymptotic confidence ellipsoids for certain linear functions of the first order parameters {B _ij} estimating simultaneously the first and the second order parameters.     

Influence of substrate temperature on the electrical behaviour of zinc stannate thin films deposited by electron beam evaporation technique

Summary  A series of zinc stannate (Zn₂ SnO₄) thin films were prepared at four different substrate temperatures; namely, room-temperature (25°C), 50°C, 100°C and 200°C. Direct-current resistivity measurements were performed on these samples in the temperature range from room temperature (∼290 K) up to about 500 K. A phase transition (of positive temperature coefficient (PTC) of resistance) was observed in the thin film grown at room temperature at about 385 K. Other investigated samples showed a semiconducting behaviour of three distinct conduction mechanisms extending from intrinsic to thermal freeze-out conduction. The width of the band gapE _g was found to depend on the substrate temperature and was discussed in terms of a formation of a band tailing. Thermal freeze-out was dominant at the lower temperature region. On leave from Department of Physics, Faculty of Science, Alexandria University, Alexandria, Egypt.     

Growth morphology of perfect and twinned face-centered-cubic crystals by Monte Carlo simulation

The effect of the relative growth rate between {1 1 1} and {1 0 0} faces on the growth morphology of perfect and twinned face-centered-cubic crystals was investigated with a Monte Carlo simulation considering both first-nearest-neighbor (FNN) and second-nearest-neighbor (SNN) interactions. When the bond energy ratio of SNN to FNN interactions is close to zero, the {1 1 1} twin planes make a reentrant edge, which enhances the growth rate on this plane, leading to a tabular growth shape. When the ratio is 0.25, the ridge side face of a tabular shape has the {1 0 0}/{1 0 0}/{1 1 1} structure instead of the {1 1 1}/{1 1 1} reentrant edge. In spite of disappearance of the reentrant edge, the side face has a higher growth rate than the top face because the {1 0 0} face still grows faster than the {1 1 1} face.     

Growth of SiGe bulk crystals with uniform composition by utilizing feedback control system of the crystal–melt interface position for precise control of the growth temperature

We developed an automatic feedback control system of the crystal–melt interface position to keep the temperature at the interface constant during growth, and demonstrate its successful application to grow Ge-rich SiGe bulk crystals with uniform composition. In this system, the position of the crystal–melt interface was automatically detected by analyzing the images captured using in situ monitoring system based on charge-coupled-devices camera, and the pulling rate of the crucible was corrected at every 1 min. The system was found to be effective to keep the crystal–melt interface position during growth even when the variation of the growth rate is quite large. Especially, the interface position was kept for 470 h during growth of Ge-rich SiGe bulk crystal when we started with a long growth melt of 80 mm. As a result, a 23 mm-long Si_0.22Ge_0.78 bulk crystal with uniform composition was obtained thanks to the constancy of the growth temperature during growth through the control of the interface position. Our technique opens a possibility to put multicomponent bulk crystal in a practical use.     

掺铒硼酸钙镧晶体的合成、生长及光谱特性

本文合成并以CaO-L i2O-B2O3为助熔剂体系生长得到了掺铒硼酸钙镧(Er3 :La2CaB10O19,Er:LCB)的晶体。X射线粉末衍射分析表明,Er:LCB和LCB具有相同的晶体结构,均属于单斜晶系,C2空间群。Er:LCB晶体的熔点大约为1048℃。测试了Er:LCB晶体的吸收光谱和荧光光谱。Er:LCB晶体在790nm和970nm附近存在的吸收,对应于A lGaAs和InGaAs激光二极管输出波长,其吸收截面分别为1.94×10-20和2.39×10-20cm2。Er:LCB在1531nm附近有发射峰最强,峰宽为16nm。其荧光寿命为0.37m s。     

Growth kinetics of CaF2 in a pH-stat fluidized-bed crystallizer

In this study, experiments were first conducted in a stirred vessel to establish the metastable region of calcium fluoride, using a pH-stat apparatus for controlling the pH value of solution. The effects of pH value on the solubility and metastable region were observed. Then, operating variables, including supersaturation, superficial velocity, pH value, seed size, and types of seed and solution, that influenced the crystal growth of the same system were investigated in a fluidized-bed crystallizer. The crystal growth rates were determined from the consumption rates of fluoride ions. The growth kinetics was explored by using the two-step growth model. The effectiveness factor was used to judge whether a controlling step was existing. The kinetics of crystal growth in a lean bed and a dense bed was also discussed.