不同表面活性剂对合成介孔氧化镁晶体性质的影响

采用液相法,以Mg(NO3)2·6H2O为镁源,NH3·H2O为沉淀剂,研究了不同表面活性剂对介孔MgO晶体性质的影响.采用XRD、FT-IR、SEM、BET和CO2-TPD等手段对介孔MgO晶相组成、骨架结构、微观形貌、孔结构及表面化学性质进行了分析表征.研究结果表明,不同表面活性剂对介孔MgO晶体物化性质影响较大.以非离子型PEG-2000为表面活性剂制得产品表面碱强度和碱总量均大于以阴离子型SDS、阳离子型CTAB制得的产品.以非离子型PEG-2000为表面活性剂制备得到的介孔MgO同时具有弱碱、中强碱特征,碱总量为0.192 mmol·g-1,比表面积、孔容和平均孔径分别为145.42 m2·g-1、0.67 cm3·g-1和18.56 nm.     

反应温度和时间对纳米氧化镁形貌和结构的影响

以六水合氯化镁(MgCl2·6H2O)为镁源,水合肼(N2H4·2H2O)为沉淀剂,采用化学共沉淀法制备纳米氢氧化镁前驱体煅烧得到分散性良好的不同纳米结构的氧化镁(MgO)纳米片.通过XRD、SEM、TEM对产物的结构和形貌进行分析,初步研究了反应温度和时间对MgO纳米片的形貌和结构影响,分析了MgO多孔纳米片的生长机理.结果表明:25℃,24h下MgO纳米片大小均一尺寸在20～40 nm;当温度升高到100℃,72 h生长的多孔MgO纳米片缺陷多,是晶粒相互连接起来的,纳米孔洞在10 nm;140℃72 h制备的多孔纳米片尺寸均一在100～200nm.因此可以通过调节反应温度和时间来控制多孔氧化镁纳米片结构.     

沉淀pH值对SAPO-34/CZA复合催化剂物化性质及CO2加氢反应影响

研究了液相沉淀包覆工艺终点pH值对SAPO-34/CZA复合催化剂物化性质和CO2氢还原制低碳烯烃催化性能的影响.借助XRD、SEM、BET、NH3-TPD和CO2-TPD等手段对不同复合催化剂的晶相组成、微观形貌、孔结构及表面酸碱性质进行了分析表征.研究结果表明,沉淀pH值对SAPO-34/CZA复合催化剂物化性质和CO2加氢制低碳烯烃催化性能影响较大.过高或过低的沉淀pH值制得复合催化剂中SAPO-34分子筛结晶度、微孔比表面积及表面碱量均有所下降,呈现以介孔为主的孔结构特征;而当pH值为7时,制得复合催化剂形成了包覆相结构和微-介复合孔结构(微孔比表面积53.1 m2·g-1,介孔比表面积59.8 m2·g-1,总比表面积为112.9 m2·g-1,总孔容0.4 cm3·g-1,平均孔径14.6 nm);在反应温度325℃,还原温度285℃,反应压力3.0 MPa,体积比H2:CO2=3.0,空速3500 mL·g-1·h-1反应条件下,CO2转化率为64.8;,低碳烯烃选择性为49.8;.与pH=9制得催化剂比较,CO2转化率和低碳烯烃选择性分别提高了26.2;和19.2;.     

离子交换树脂均匀沉淀法制备MgO纳米粒子

以(Mg(NO3)2·6H2O, (NH4)2CO3 和NH3·H2O为原料,采用两种离子交换树脂均匀沉淀法分别制备MgO纳米粒子.用热分析、X射线粉末衍射(XRD)、透射电子显微镜(TEM)、高分辨电子显微镜(HR TEM)、选区电子衍射(SAED)和BET等对所制备的MgO粒子进行了表征.结果表明:经700 ℃焙烧后制备的MgO纳米晶体属六方晶系,样品分散性较好,平均粒径约为25 nm;MgO纳米晶体清晰、有序的电子衍射点阵,表明晶体的结晶度较好;纳米粒子a和b的比表面积分别为31 m2/g and 32 m2/g.     

纳米NiCo2O4的两种制备方法比较及其甲醇电氧化性能研究

分别以微乳液法和共沉淀法制备了NiCo2O4纳米棒和纳米片.对比研究了两种方法制备的NiCo2O4纳米材料的物相、形貌、孔道结构及其催化甲醇氧化的性能.结果表明:350℃煅烧5h后,两种方法均能制备出NiCo2O4纳米材料,但共沉淀法制备的纳米片结晶度低于微乳液法制备的NiCo2O4纳米棒.通过扫描电子显微镜、透射电子显微镜和氮气吸脱附测试发现,NiCo2O4纳米棒具有介孔结构,比表面积为116.8 m2·g-1,而NiCo2O4纳米片是六方片状结构,比表面积为36.1 m2·g-1.电化学结果显示,电压为0.6V,扫描速率为50 mV·s-1时,纳米片的电流密度为47.8 mA·cm-2,纳米棒为31.9 mA·cm-2.在0.5V扫描3000 s后,纳米片仍能保持70;的初始电流密度,纳米棒为51;.共沉淀法制备的NiCo2O4纳米片比微乳液法制备的纳米棒具有更好的催化甲醇氧化活性、稳定性.这可能是由于NiCo2O4纳米片的特殊的片层形貌及其一定的无序度导致的.     

不同实验条件对锰矿法制备介孔纳米四氧化三锰性能的影响

采用简单易行,成本低廉的锰矿法,以软锰矿焙烧熟料溶出液为原料,氨水为沉淀剂,空气为氧化剂,制备四氧化三锰.研究了不同实验条件对Mn3 O4物相、形貌、比表面积的影响,采用XRD、SEM和BET对产物进行表征.结果表明,不同的实验条件对所得产物物相组成没有明显影响,经过超声处理的样品结晶度更好;不同的实验条件所得产物均为介孔结构的纳米级四氧化三锰,但对产物形貌和比表面积有较大影响.实验最佳条件为:不经过超声,未加任何添加剂,MnSO4反加到NH3·H2 O中的沉淀-氧化两步法.所得产物由球状颗粒和细棒状组成,球状颗粒的粒径最小,大部分小于50 nm,比表面积为35.05 m2/g.     

CoC2O4·2H2O纳米晶形貌可控合成

通过简单调节反应介质热塑性酚醛树脂与乙二醇配比,选择性地制备了CoC2O4·2H2O纳米棒和纳米片晶体或其两种形貌晶体混合物.样品热重和差示扫描量热(TG-DSC)、X射线粉体衍射(XRD)、场发射扫描电镜( FESEM)实验表明:以热塑性酚醛树脂为反应介质得到了COC2O4·2H2O纳米棒;以乙二醇为反应介质得到了CoC2O4·2H2O纳米片;逐渐增大乙二醇和酚醛树脂质量比,实现了CoC2O4·2H2O形貌由纳米棒形貌转变为纳米片形貌.基于不同晶体形貌和实验结果,提出了棒状和片状COC2O4·2H2O可能的形成机理模型以解释两种形貌COC2O4·2H2O纳米晶的生长行为.     

Al2 O3晶型对K2 WO4/Al2 O3物化性质及催化合成甲硫醇的影响

采用等体积浸渍法改性制备了K2 WO4/Al2 O3催化剂,研究了载体Al2 O3晶型对K2 WO4/Al2 O3催化剂物化性质及催化合成甲硫醇的影响.借助XRD、SEM、EDS、BET及NH3/CO2-TPD等手段对不同催化剂的晶相组成、微观形貌、孔结构及表面酸碱性质进行了表征分析.结果表明,Al2 O3晶型对K2 WO4/Al2 O3催化剂晶相组成及微观形貌影响较小,但对孔结构及表面酸碱性质影响较大.与K2 WO4/η-Al2 O3和K2 WO4/θ-Al2 O3催化剂相比,K2 WO4/γ-Al2 O3催化剂具有更大比表面积及孔容(介孔比表面积为226.75 m2·g-1,总孔容为0.557 cm3·g-1),且表面仅有弱酸和弱碱中心(弱酸浓度为0.42521 mmol·g-1,弱碱浓度为0.44184 mmol·g-1).在反应温度370℃,反应压力1.0 MPa,H2 S流速4.9 mL·min-1,CH3 OH流速0.03 mL·min-1反应条件下,K2 WO4/γ-Al2 O3催化剂表现出优良催化性能,甲醇转化率和甲硫醇选择性分别达81.58;和87.05;,与K2 WO4/η-Al2 O3和K2 WO4/θ-Al2 O3催化剂相比,甲醇转化率分别提高了4.23;和19.42;,甲硫醇选择性分别提高了14.68;和7.85;.     

不同形貌的钨酸铋纳米材料的制备及其光催化性能

利用水热法通过调节溶液pH值和表面活性剂CTAB浓度制备了不同结构与形貌的钨酸铋纳米材料,用X射线衍射(XRD)、场发射扫描电镜(FESEM)、透射电镜(TEM)等测试方法对产物进行了结构与形貌的表征,并研究了不同结构与形貌的钨酸铋样品对甲基橙的可见光催化降解性能.结果表明,在低pH值时样品为Bi2WO6相纳米片,随着pH值的增加,样品中出现了Bi3.84W0.16O6.24相八面体纳米颗粒,高pH值时,样品则为纯Bi3.84W0.16O6.24相八面体颗粒.随着表面活性剂浓度的增加,Bi2WO6纳米片有自组装的趋势,最终形成花瓣状结构.光催化甲基橙实验结果表明不同形貌的钨酸铋样品对甲基橙有不同的催化降解活性,片状Bi2WO6相纳米片高于Bi3.84W0.16O6.24相八面体颗粒.     

钨酸锌微纳米材料的水热合成及发光性能研究

以Zn(NO3)2·6H2O和Na2WO4·2H2O为原料,草酸为沉淀剂,采用水热法在180℃反应4h制备了ZnWO4粉体,并考察了前驱体溶液pH值对ZnWO4发光性能的影响.通过X射线衍射(XRD),场发射扫描电子显微镜(SEM)和荧光光谱(PL)等测试手段对样品的物相、微观形貌和发光性能进行表征.结果表明:pH值为7～9时适宜合成ZnWO4粉体,pH =7、8时,得到的是星状结构ZnWO4粉体;pH =9时分别得到的是由长度为500 nm,直径为100 nm的纳米棒交叉组装而成的镂空结构ZnWO4粉体.相比之下,由纳米棒交叉组装而成的镂空片的发光性能最佳.     

Relationship of Morphological Types of Dynamic Forms of Crystals

Crystallography Reports - The relationship of morphological spectra (sets of data on the morphological types of real polyhedral crystals and their probabilities under current physicochemical...     

Development of Pauling's concepts of geometric characteristics of atoms

The evolution of the geometric characteristics introduced by Pauling and their dependence on the specific features of the structure and chemical bonds have been considered. The values of the covalent and van der Waals radii are given as well as their relationships and mutual transitions.     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

A SAXS study of kinetics of aggregation of silica sols

SAXS in situ experiments on the evolution of TMOS solutions during hydrolysis and polycondensation lead to power laws with scaling exponents ≈ 2. It is suggested that this could be the result of the polydispersity of the samples and that only an apparent fractal dimension can be obtained in this way. Kinetic studies tend to indicate that agglomeration in the sol is the result of a diffusion-controlled process.     

Generation of crystal structures of heteromolecular compounds by the method of discrete modeling of packings

Within the method of discrete modeling of packings, an algorithm of generation of possible crystal structures of heteromolecular compounds containing two or three molecules in the primitive unit cell, one of which has an arbitrary shape and the other (two others) has a shape close to spherical, is proposed. On the basis of this algorithm, a software package for personal computers is developed. This package has been approved for a number of compounds, investigated previously by X-ray diffraction analysis. The results of generation of structures of five compounds—four organic salts (with one or two spherical anions) and one solvate—are represented.     

Investigation of the Mechanism of Influence of Stress Corrosion on the Development of Macroplastic Instabilities of Aluminum–Magnesium Alloy

Crystallography Reports - Macroscopic jumps of plastic deformation (few percent in amplitude) on creep curves of aluminum–magnesium alloy, caused by a local effect of concentrated solution of...     

Study of the possibility of interactive control of the surface profile of X-ray optical elements

We investigate the possibility of controlling the curvature parameters of parabolic mirrors that are modular elements of two types consisting of a base and thin inserts placed at the opposite side of the work surface. In the first type of modular elements, bending is controlled by the difference in the coefficients of the thermal expansion of the base and inserts. In the second type of elements, the profile is changed by the piezoelectric straining of the inserts under an electric field. A correlation is established between the parameters of modular elements and their surface curvature profile.     

Mechanism of thermal expansion of structural modifications of zinc pyrovanadate

Crystal chemical characteristics of the α and β modifications of Zn₂V₂O₇ are calculated based on in situ high-temperature X-ray measurements. The expansion of the structure is found to be strongly anisotropic up to the negative volumetric thermal expansion of the α-Zn₂V₂O₇ unit cell in the temperature range of 300–600°С, α _V =–17.94 × 10^–6 1/K. The transformations of the “hard” and “soft” sublattices with an increase temperature and at the phase transition are considered in detail. It is shown that the negative volumetric thermal expansion of α-Zn₂V₂O₇ is due to the degeneracy of the zigzag-like shape of zinc–oxygen columns at constant distances between their vertices.     

Dependence of the parameters of equations of viscous flow on chemical composition of silicate melts

The temperature dependence of viscosity of silicate melts is discussed in the framework of the Avramov–Milchev (AM) equation. The composition is described by means of two parameters: the molar fraction, x, and the “lubricant fraction”, l. The molar fraction is the sum of the molar parts x_i of all oxides dissolved in SiO₂, the molar fraction of the latter being 1 ? x. It is shown that, with sufficient precision, two of the parameters of the AM equation can be presented as unique functions of the molar fraction. On the other hand, x is not sufficient to determine properly the reference temperature T_r , at which viscosity is η_r = 10¹³ [dPa.s]. Therefore, additional parameter, “lubricant fraction” l, is introduced. For each of the components, l_i is a product of molar part x_i and a specific dimensionless coefficient 0 ≤ k_i ≤ 1 accounting for the specific contribution of this component to the increased mobility of the system. It is demonstrated that, for l > 0, the reference temperature is related to the “lubricant fraction” l through the reference temperature T_r,SiO2 of pure SiO₂.     

Comparative analysis of two methods of calculation of the orientation of domain walls in ferroelastics

Two types of domain-wall equations are analyzed: the equations derived by the Sapriel method and the equations obtained by interface matching of the thermal-expansion tensor. It is shown that, for W-type domain walls, these methods yield the same equations. For W′-type domain walls, the equations obtained by different methods coincide for proper ferroelastics and differ for improper ferroelastics.