锐钛矿相纳米TiO2晶体生长动力学及生长过程控制

研究了采用溶胶-凝胶法经由前驱物钛酸四异丙酯水解制备纳米TiO₂结构相变及锐钛矿晶体生长动力学过程. 研究结果表明,在酸性条件下水解,由于高压热处理温度的变化导致锐钛矿向金红石相的结构相变,锐钛矿相纳米TiO₂生长活化能在250℃以下和以上分别为(15.8±4.5)kJ/mol和(80.2±1.0)kJ/mol;而在碱性条件下水解的活化能值为(3.5±0.4)kJ/mol. 在不发生结构相变的条件下,酸性水解条件下锐钛矿相纳米TiO₂生长速 关键词： 2')" href="#">纳米TiO₂ 锐钛矿 生长动力学 溶胶-凝胶法     

合成氨钌催化剂的晶体和形貌敏感性

哈伯-博施法合成氨反应是高温高压的耗能过程,因此降低该过程的能量消耗及开发温和条件下合成氨反应催化剂具有重要意义. 金属钌是合成氨反应中最有前途的催化剂之一,一直备受广泛关注. 确定金属钌催化剂的结构敏感性并提高其比质量活性是多相催化中亟待解决的重要问题. 氮气(N₂)活化是合成氨反应中的关键步骤. 本文通过第一性原理理论计算和微观动力学模拟方法系统研究了具有六方密排和面心立方晶体结构的钌催化剂上N₂活化过程和N₂解离反应速率. 理论计算研究表明,在六方密排Ru形貌中,{2130}晶面具有最高的N₂解离活性,其次是{0001}台阶面,它们比六方密排Ru其他表面上N₂解离反应速率高3个数量级以上;在面心立方Ru形貌中,{211}和{311}表面上N₂解离活性最高. 这些结果都表明台阶面/台阶位对氮气活化至关重要. 虽然六方密排Ru {2130}晶面具有最低的N₂解离能垒,然而由于面心立方Ru上可以暴露更高密度的活性位点,使得面心立方Ru比六方密排Ru具有更高的N₂转化速率. 本研究深入理解了N₂解离过程中,金属Ru 催化剂形貌和晶相结构敏感性,这为设计和优化高活性的合成氨Ru催化剂提供了理论基础.     

Fluorescence evidence for cholesterol regular distribution in phosphatidylcholine and in sphingomyelin lipid bilayers

Our previous studies indicated that sterols (including cholesterol and dehydroergosterol) can be regularly distributed into hexagonal superlattices in the plane of liquid-crystalline phosphatidylcholine bilayers. It was suggested that regular and irregular regions coexist in the membrane. In the present study, we report supporting evidence for our sterol regular distribution model. We have examined the fractional concentration dependencies of dehydroergosterol (a naturally occurring cholesterol analogue) fluorescence intensity and lifetime in various phosphatidylcholine and sphingomyelin bilayers. Fluorescence intensity and lifetime dips have been observed at specific sterol mole fractions. At those mole fractions, the acrylamide quenching rate constant of dehydroergosterol fluorescence reaches a local maximum. Those mole fractions match the critical sterol mole fractions at which sterol molecules are expected to be regularly distributed into hexagonal superlattices. The results support the idea that the sterols in the regular region are embedded in the bilayer less deep than those in the irregular regions. We have also examined the fractional cholesterol concentration dependencies of diphenylhexatriene (DPH) fluorescence intensity, lifetime, and polarization in DMPC vesicles. DPH fluorescence intensity and polarization also exhibit distinct dips and peaks, respectively, at critical sterol mole fractions for hexagonal superlattices. However, DPH lifetime changes little with sterol mole fraction. As a comparison, the fluorescence properties of DHE and DPH behave differently in response to the formation of sterol regular distribution. Furthermore, finding evidence for sterol regular distribution in both phosphatidylcholine and sphingomyelin membranes raises the possibility that sterol regular distribution may occur within phospholipid/cholesterol enriched domains of real biological membranes.     

钴改性Fe3O4-MnO2催化转化生物质合成气制备液体燃料

本文制备了用于费托合成反应的钴改性Fe₃O₄-MnO₂双功能催化剂,并探究了钴负载量对Fe-Co协同效应的影响以及Fe₁Co_xMn₁催化剂的费托合成反应性能. 实验发现,在Fe₃O₄-Mn催化剂中加入Co可促进铁氧化物的还原、增加反应过程中铁位点的活性. 此外,Co的加入可增强Fe-Co金属间的电子转移,加强两者的协同作用,提高催化性能. Co负载较高的Fe₁Co_xMn₁催化剂可进一步促进加氢反应能力,使产品分布向短链烃方向转移. 在280 ^°C、2.0 MPa和3000 h^-1的最佳工况条件下,Fe₁Co₁Mn₁催化剂的液体燃料收率最高.     

ATP synthase: from single molecule to human bioenergetics

ATP synthase (F_oF₁) consists of an ATP-driven motor (F₁) and a H⁺-driven motor (F_o), which rotate in opposite directions. F_oF₁ reconstituted into a lipid membrane is capable of ATP synthesis driven by H⁺ flux. As the basic structures of F₁ (α₃β₃γδε) and F_o (ab₂c₁₀) are ubiquitous, stable thermophilic F_oF₁ (TF_oF₁) has been used to elucidate molecular mechanisms, while human F₁F_o (HF₁F_o) has been used to study biomedical significance. Among F₁s, only thermophilic F₁ (TF₁) can be analyzed simultaneously by reconstitution, crystallography, mutagenesis and nanotechnology for torque-driven ATP synthesis using elastic coupling mechanisms. In contrast to the single operon of TF_oF₁, HF_oF₁ is encoded by both nuclear DNA with introns and mitochondrial DNA. The regulatory mechanism, tissue specificity and physiopathology of HF_oF₁ were elucidated by proteomics, RNA interference, cytoplasts and transgenic mice. The ATP synthesized daily by HF_oF₁ is in the order of tens of kilograms, and is primarily controlled by the brain in response to fluctuations in activity.     

The influence of reactor core parameters on effective breeding coefficient Keff

The values of effective breeding coefficient Keff in a reactor core of nuclear power plant are calculated for different values of parameters （core structure, fuel assembly component） by using the Monte Carlo method. The obtained values of Keff are compared and analysed, which can provide theoretical basis for reactor design.     

Synthesis and properties of Au-Fe3O4 and Ag-Fe3O4 heterodimeric nanoparticles

Monodisperse Au-Fe 3 O 4 heterodimeric nanoparticles (NPs) were prepared by injecting precursors into a hot reaction solution.The size of Au and Fe 3 O 4 particles can be controlled by changing the injection temperature.UV-Vis spectra show that the surface plasma resonance band of Au-Fe 3 O 4 heterodimeric NPs was evidently red-shifted compared with the resonance band of Au NPs of similar size.The as-prepared heterodimeric Au-Fe 3 O 4 NPs exhibited superparamagnetic properties at room temperature.The Ag-Fe 3 O 4 heterodimeric NPs were also prepared by this synthetic method simply using AgNO 3 as precursor instead of HAuCl 4.It is indicated that the reported method can be readily extended to the synthesis of other noble metal conjugated heterodimeric NPs.     

锂-亚硫酰氯电池储存寿命研究

锂-亚硫酰氯电池作为一种免维护、高比能、长储存寿命电池,目前已经在以国防领域为代表的国民经济中得到了广泛应用;其储存寿命的考核在行业内尚属难题;通过广泛、深入地调研和对前期锂-亚硫酰氯电池储存数据的收集整理,研究了锂-亚硫酰氯电池的储存寿命影响因素及其试验评估方法;通过研究得知,锂-亚硫酰氯电池的储存寿命试验应尽早备样,若时间紧迫可通过加速试验方法;提出了通过等效储存试验时间来评估电池储存寿命及其可靠度的方法,指出当等效储存试验时间不足时,应安排样本进行容量回归分析,得出其退化规律;此外,还要对电池储存末期热性能进行分析;在以上工作基础上对电池储存寿命进行综合评估;最后,通过案例分析,进行了工程演算;为后续锂-亚硫酰氯电池储存寿命评估提供了参考。     

利用天然磁铁矿简易绿色合成磁性Fe3C@C纳米材料

采用改进的溶胶凝胶法，以天然磁铁矿为铁源，开发出一种制备过程简单且环境友好且低成本的磁性Fe₃C@C纳米材料制备策略. 其中，柠檬酸作为多元羧酸络合剂，不但可以有效地溶解不同铁源，例如Fe、Fe₃O₄或天然磁铁矿，形成柠檬酸铁盐络合物；还可以在热解过程中作为碳源，形成包裹碳层. 通过控制高温热解过程可以直接形成特殊的核-壳结构形态. Fe₃C@C纳米材料具有超顺磁性特性(38.09 emu/mg).     

大规模合成具有氧空位的多孔Bi2O3用于有效降解亚甲基蓝

光催化降解有机污染物由于其具有低能耗和绿色环保的特点，已经成为研究的热点. 氧化铋纳米晶体的带隙在2.0∽2.8 eV之间，利用它催化可见光降解有机污染物具有较高的活性，从而引起了越来越多的关注. 尽管近年来已经开发了几种制备Bi₂O₃基半导体材料的方法，但是仍然难以用简单的方法大规模地制备高活性的Bi₂O₃催化剂. 因此，开发简单可行的大规模制备Bi₂O₃纳米晶体的方法对于工业废水处理的潜在应用具有重要意义. 本文通过蚀刻商用BiSn粉末，然后进行热处理，成功地大规模制备了多孔Bi₂O₃. 获得的多孔Bi₂O₃在亚甲基蓝(MB)的光催化降解中表现出优异的活性和稳定性. 对该机理的进一步研究表明，多孔Bi₂O₃合适的能带结构允许生成活性氧物种，例如O₂^-·和·OH，可有效降解MB.     

内掺过渡金属富勒烯衍生物Ni@C20H20几何结构、成键和电磁性质的密度泛函计算研究

采用密度泛函理论中的广义梯度近似对Ni@C₂₀H₂₀的几何结构、成键和电磁性质进行密度泛函计算研究.结构优化发现位于偏离笼子中心三种位置处的Ni原子优化之后均回到笼子中心.结合能和能隙分析表明C₂₀H₂₀的中心位置是Ni原子热力学和动力学最稳定的位置.成键分析表明：Ni原子位于C₂₀H₂₀中心时,和C原子之间几乎没有相互作用,保持自己的孤立状态.电磁分析表明：原子磁矩为2关键词： 20H₂₀')" href="#">C₂₀H₂₀ 20H₂₀')" href="#">Ni@C₂₀H₂₀ 几何结构 成键 电磁性质 密度泛函理论     

可聚合型溶致液晶单体3,4,5-三(11-十一烷氧丙烯酰氧基)苯甲酸钠的自组装及紫外光固化性能

以3,4,5-三羟基苯甲酸为原料,依次经过酯化、醚化、酰氯化和钠盐化四步反应合成一种可聚合型溶致液晶单体3,4,5-三(11-十一烷氧丙烯酰氧基)苯甲酸钠,并对其结构进行了傅里叶变换红外与1H核磁表征. 在室温下研究了该单体在水中的自组装行为,组装体结构通过偏光显微镜与X射线衍射仪进行表征. 研究表明,单体与水比例为80:20时可自组装为层状(La)相,92:8时组装为反六方(H_II)相,这与临界堆积参数的理论计算相吻合,表明单体浓度是影响组装体结构的重要因素. 在组装的基础上研究了含不同光引发剂的溶致液晶体系的双键转化率及固化后组装体结构的保留. 经实时红外表征及溶胶-凝胶法的验证发现在光强为30 mW/cm²的365 nm下曝光30 min,含引发剂Darocur2959的溶致液晶体系双键转化率可达78%. 聚合之后La相与H_II相的纳米结构都得到了保留.     

Technical and economic evaluation of a methane solid oxide fuel cell

Solid oxide fuel cells offer the possibility of high temperature synthesis of chemical products with cogeneration of electricity, a process known as chemical cogeneration. This research primarily addresses the likelihood of upscaling present bench-scale experimental results of methane fuelled SOFCs. Methane coupling, i.e. production of C₂ hydrocarbons, is one of the possibilities of chemical cogeneration. In evaluating the co-generating SOFC, the methane-coupling design was compared to two other possible competing designs, namely, a regular SOFC plant (complete oxidation of methane to CO₂ and H₂O) and an SOFC plant coproducing synthesis gas. It was found that the rate of return for the regular fuel cell exceeded 25% whereas that for the ethylene plant was about 21%. The synthesis gas plant was well behind at about 17%. The reasons that have so far prohibited large-scale application of such systems are discussed. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995.     

Study of the use of ionizing radiation for the modification of CoO/Co0.65Zn0.35 nanostructures

The paper presents the results of a study of the influence of heavy ions Xe²²⁺ on the morphology, phase composition, structural and conductive characteristics of CoO/Co_0.65Zn_0.35 nanowires obtained by the method of electrochemical synthesis. As a result of the research, it was established that an increase in the irradiation fluence leads to a change in the phase composition, due to the decomposition of the oxide phase CoO and the predominance of Co_0.65Zn_0.35 substitution in the structure of the cubic phase of solid solution. It has been established that an increase in the irradiation fluence and a decrease in the oxide phase in the structure leads to a decrease in the concentration of dislocations and vacancies in the nanowires, which indicates a partial relaxation of defects as a result of irradiation. It is established that a change in dislocation and vacancy density leads to an increase in the value of specific conductivity and a decrease in resistance.     

基于钽酸锂晶体的太赫兹波参量振荡器运转特性的研究

基于晶格振动模受激电磁耦子散射过程的基本原理,对由LiTaO₃（LT）晶体组成的太赫兹波参量振荡器（TPO）的输出调谐特性、增益和吸收损耗特性,以及基于硅棱镜阵列耦合装置的THz波输出特性等方面进行了详细的理论研究和分析.研究结果表明,基于LiTaO₃晶体A₁对称性晶格振动的特点以及自身优异的非线性光学特性,通过利用短波长抽运光、适当提高抽运能量以及缩短TPO谐振腔腔长等方法,完全可以实现LT-TPO的高性能运转,证明了LiTaO₃晶体是一种性能优良的TPO工作介质.理论计算结果及方法为以后的LT-TPO实验工作提供了详实的理论依据和实验指导. 关键词： 非线性光学 THz辐射 3晶体')" href="#">LiTaO₃晶体 电磁耦子     

HIGH-PRESSURE SYNTHESIS OF MgB2 SUPER-CONDUCTOR WITH Tc ABOVE 39 K

We report on the high-pressure synthesis and superconductivity of MgB₂ intermetallic compounds. The compounds have been obtained through high-pressure sintering of the mixtures of magnesium and boron fine powders under 5.0 GPa and at ～1000℃ for 30 min. Magnetic measurements using a SQUID magnetometer show the sharp bulk superconducting transition above 39 K; the four-probe dc resistivity measurements indicate the highly-conductive normal state and sharp superconducting transition. The results highlight that high-pressure synthesis would be a promising way to promote the studies of this new kind of intermetallic superconductors.     

C72,La2@C72几何结构和电子性质的计算研究

采用密度泛涵理论(density functional theory, DFT)中的广义梯度近似(generally gradient approximation, GGA)对富勒烯C₇₂和内掺金属La富勒烯La₂@C₇₂三种同分异构体的几何结构和电子结构进行研究.发现在C₇₂的三种同分异构体中，满足独立五边形规则(isolated-pentagon-rule，IPR)的C₇₂(D_{6d< 关键词： 72}')" href="#">C₇₂ 2@C₇₂')" href="#">La₂@C₇₂ 密度泛涵理论 几何结构 电子结构     

从可溶性单源分子前驱体采用溶胶凝胶法制备ZnO/TiO2 纳米复合物

合成了单源分子前驱体Cl₂TiZn(dmae)₄ (dmae为2-二甲基乙醇胺),并以乙醇为溶剂,加入等摩尔量的水对其进行可控水解得ZnO/TiO₂纳米复合凝胶,经pH=9沉淀,在200、400和600 oC 烧结得到不同的产物T₂₀₀、T₄₀₀、T₆₀₀. XRD分析表明未烧结产物为无定形粉末并随着烧结温度升高晶型改善. ZnO呈纤锌矿结构(六方晶系),TiO₂呈板钛矿型结构(正交). BET分析和扫描电镜表明颗粒的大小随着烧结温度的提高而增加. 红外光谱证明Zn-O和Ti-O的特有的振动频率,OH基团烧结后的产物中被去掉. 所有的样品都显示良好的光催化活性, 且T₆₀₀活性最高.     

Density functional calculations on the geometric structure and properties of the 3d transition metal atom doped endohedral fullerene M@C20F20（M=Sc-Ni）

This paper uses the generalised gradient approximation based on density functional theory to analyse the geometric structure and properties of the 3d transition metal atom doped endohedral fullerene M@C20F20(M=Sc-Ni).The geometric optimization shows that the cage centre is the most stable position for M,forming the structure named as M@C 20 F 20-4.The inclusion energy,zero-point energy,and energy gap calculations tell us that Ni@C 20 F 20-4 should be thermodynamically and kinetically stablest.M@C 20 F 20-4(M = Sc-Co) possesses high magnetic moments varied from 1 to 6 μ B,while Ni@C 20 F 20-4 is nonmagnetic.The Ni-C bond in Ni@C 20 F 20-4 contains both the covalent and ionic characters.