低CO2排放的太阳能/甲醇互补系统热力经济性分析

基于品位匹配和多能源综合梯级利用的原则,本文提出了低CO₂排放的太阳能与化石能源互补发电系统LESOLCC,并对其进行了热力经济性能分析。所提系统以甲醇为燃料,中低温太阳能首先提供甲醇重整反应的反应热,从而转化为富氢合成气的化学能,实现品位提升;其次通过燃烧前对CO₂的捕集,实现燃料的清洁燃烧,最终在高效联合循环中实现其热功转换。结果表明:基本工况下,系统当量效率达到55.1%,比投资为833$/kW,发电成本为0.124$/kWh,回收期17年;与相同化石燃料输入及CO₂捕集水平的尾气捕集CO₂的常规燃气-蒸汽联合循环（CC-Post）相比,发电成本下降了10.1%,充分显示其优越性。     

Structure and dynamics of water: from ambient to supercritical

Our recent works on supercritical water are reviewed. In order to elucidate the hydrogen bonding state of supercritical water, the proton chemical shift of the water proton is measured at temperatures up to 400 °C and densities of 0.19, 0.29, 0.41, 0.49, and 0.60 g/cm³. The magnetic susceptibility correction is made in order to express the chemical shift relative to an isolated water molecule in dilute gas. The chemical shift is then related to the average number of hydrogen bonds in which a water molecule is involved. It is found that the hydrogen bonding persists at supercritical temperatures and that the average number of hydrogen bonds is at least one for a water molecule at the densities larger than the critical. The density dependence of the chemical shift at supercritical temperatures is analyzed on the basis of statistical thermodynamics. It is shown that the hydrogen bonding is spatially more inhomogeneous at lower densities. The dipole moment of water at supercritical states is also estimated from the number of hydrogen bonds. The dynamical counterpart of our structural study of supercritical water has been performed by NMR relaxation measurements. Using D₂O, we measured the spin-lattice relaxation time and determined the reorientational relaxation time as a function of the water density and temperature. It is then found that while the reorientational relaxation time decreases rapidly with the temperature in the subcritical condition, it is a weak function of the density in the supercritical conditions.     

铕取代的锆硼钨多金属氧酸盐的制备和发光特性

制备了高发射效率的稀土多金属氧酸盐BPOM:Eu及ZrPOM:Eu荧光体,并对其结构及发光性质进行了研究。结果表明样品具有Keggin结构,Eu在两类样品中均有肉眼可见的在红光区的强发射。但在BPOM:Eu中以⁵D₀→⁷F₁磁偶极跃迁发射为主,在ZrPOM:Eu中以⁵D₀→⁷F₂电偶极跃迁发射为主。铕在ZrPOM:Eu中的对称性低于在BPOM:Eu中的对称性。这种差异也使铕离子的激发光谱具有不同的特征。铕在两种多金属氧酸盐中均有浓度猝灭,在BPOM:Eu中浓度为2.0%时发射强度最大;在ZrPOM:Eu中浓度为2.4%时发射强度最大。在ZrPOM:Eu中有较弱的配体到中心铕离子的能量传递,而在BPOM:Eu中却未观测到能量传递现象。     

稠苯芳杂环及其烷基质子化学位移的计算

本文提出了予测稠苯芳杂环及其烷基链上质子化学位移的计算方法。 将稠苯芳杂环化合物用凯库勒式表示,计算式为为需考虑的苯环内的乙烯基效应。σ_mi,ci为各苯环的环流效应。σ_1,Hc为各芳杂环的屏蔽效应,对杂环上质子它就是该单独芳杂环上相应质子的δ值,对苯环上质子要将它分解为各结构因素的效应,即:σ_1,He=(1/2)^d-1δ_x=y(或σ_z)+σ_c-c·σ_m,H. σ_x-y与σ_z为杂原子或其基团的屏蔽效应,σ_c=c为存在于芳杂环中的乙烯基的效应,σ_m,Hc为芳杂环的环流效应,d为对不同质子所考虑的键数。有取代基时需考虑取代基的效应。计算环上烷基质子的公式为:δ=σ_p,CH3+ασ_c,CH3+βσ_t,CH3+σ_l,G σ_l,G为稠苯芳杂环基的某级效应。     

砷化镓中质子注入之研究

本文中,我们研究了砷化镓中质子注入及退火恢复过程。实验用晶向<100>偏1—3°,掺Sn 5×10¹⁷-1×10¹⁸cm^-3的单晶,室温下质子注入,注入能量E约8×10⁴—2×10⁶eV,用A-B腐蚀剂对注入质子样品的解理面显结,测得质子注入高阻层的纵向深度x_j和径向扩展x_L与注入能量E的定量关系。然后,对注入质子样品,在150—800℃下退火5分钟,用双晶衍射仪研究了样品的应变恢复过程,在静电计上测量了高阻阻值随退火温度的变化。根据实验结果,讨论了砷化镓中质子注入的射程R_p,电子阻止本领S_n(E)和核阻止本领S_e(E),以及质子注入形成高阻和退火恢复的机理。 关键词：     

稠苯芳环及其烷基质子化学位移的计算

本文提出了予测稠苯芳烃及其衍生物的环上和烷基链上质子化学位移的计算方法。 将稠苯芳环化合物用凯库勒式表示,用下式计算: δ=σ_j.c-c+σ_mi.ci σ_j.c-c为各种乙烯基的效应。σ_mi.ci,为各个苯环的六电子π轨道的净环流效应,其计算式为: σ_m.e=(1/2)^m×1,52 m=n-u m为净环流效应级数,等于质子到该苯环相隔的键数n减其中的顺式键数u。 在菲环和类似菲环的4,5位与9,10位质子需考虑菲环效应。蒄环上的质子需考虑蒄环效应。有取代基需考虑取代基的效应。 计算环上烷基质子的公式: δ=σ_p.CH3+ασ_2.CH3+βσ_t.CH3+σ_i.G 此公式在作者以前的文章中己经报道。σ_i,G为稠苯芳基的某级效应。     

硅—二氧化硅界面过渡区的XPS研究

本文报道了用X射线光电子能谱的角度效应研究硅-二氧化硅界面过渡区的结果。样品为(111)取向的硅单晶片上低温(700℃)氧化生成的超薄氧化膜,膜的厚度不大于50?。氧化膜与单晶衬底中Si_2p光电子谱峰之间的化学位移(δ)和强度比(I_0x/I_si)随光电子发射角(θ)的变化明显地偏离理想界面所预期的结果,表明在硅-二氧化硅的界面处存在化学比为SiO_x(0yO_4-y(0≤y≤4)型四面体。比较实验曲线与随机成键模型的计算结果,估计出过渡区的宽度不大于20?,小于Si_2p光电子在二氧化硅中的平均逃逸深度。对改变氧化时间结合Ar⁺刻蚀制得的氧化膜厚度不同的样品所作的测量,得到与角度实验相一致的结果。 关键词：     

Sol–gel preparation and characterisation of dense proton conducting Sr3CaZr0.5Ta1.5O8.75 thin films

Dense proton conducting Sr₃CaZr_0.5Ta_1.5O_8.75 films (1.25 μm, with grain size in the 200–400 nm range) were deposited, using the sol–gel method, on Al₂O₃–8%Y₂O₃-stabilised ZrO₂ plates. The obtained gels were characterised by differential and thermogravimetric thermal analysis (DTA–TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results of a study of the structural and electrical properties of Sr₃CaZr_0.5Ta_1.5O_8.75 films deposited on the mentioned substrates are presented herein. The structural data for the gels and films were compared with those obtained for the same material prepared by solid state synthesis. Electrical properties of the sandwich-type structure were investigated by AC impedance conductivity measurements at different temperatures, in both dry and wet 5% H₂/Ar atmospheres. A careful analysis of the impedance spectra for this complex structure was performed, using a model with a series of five electrical circuits, having resistance and capacitance coupled in parallel. The specific responses observed in the impedance spectra were assigned to the corresponding substrate and layer contributions. A significant improvement, by an order of magnitude, in the electrode response was observed in the presence of the interleaving Sr₃CaZr_0.5Ta_1.5O_8.75 proton conducting layer, between the electrode and electrolyte. This enhancement is lost at temperatures above that at which the Sr₃CaZr_0.5Ta_1.5O_8.75 dehydrates and its protonic conductivity diminishes. Considering the structural and electrical characterisation results, these Sr₃CaZr_0.5Ta_1.5O_8.75 sol–gel derived films have a potential use for proton conducting electrolyte or intermediate layer in fuel cells.     

Molecular dynamics of polycrystalline cellobiose studied by solid-state NMR

Molecular motions of polycrystalline cellobiose have been investigated by measuring proton spin–lattice relaxation times, T₁ and T_1ρ, and the second moment, M₂, in both protonated and D₂O exchanged forms over the temperature range 120–380 K. T₁ relaxation is dominated by the motions of hydroxyl groups between 150 and 380 K, characterised by an activation energy of about 8.74 kJ/mol, whereas T_1ρ relaxation is driven by the motions of the same groups between 120 and 300 K. T_1ρ results suggest that hydroxyl groups have a distribution of dynamics. Motion of methylene groups was detected in the second-moment experiments at about 350 K, characterised by activation energy of about 40 kJ/mol. Consideration of the calculated and observed rigid-lattice second moments suggests that the reported X-ray data are incorrect for the inter-proton distance on C6′. ¹³C CPMAS spectra of both protonated and deuterated cellobiose have also been measured. Spectra of the deuterated material showed the existence of a second crystalline form in addition to the normal form.     

用多元统计分析研究黄冶窑白瓷的原料特征

黄冶窑文化内涵丰富,其创烧于隋,兴盛于唐代中期,停烧于唐代晚期。为探讨不同时期黄冶窑白瓷的胎料来源和釉料配方是否相同,选取黄冶窑隋、早唐、中唐、晚唐四个时期的80个白瓷样品,利用质子激发X射线荧光分析(PIXE)测定各样品胎、釉中9种化学成分(Na₂O、MgO、Al₂O₃、SiO₂、P₂O₅、K₂O、CaO、TiO₂、Fe₂O₃)的含量,用多元统计分析中的Fisher判别分析处理PIXE数据,并计算各样品釉的木灰釉式系数b来划分瓷釉类型。结果表明:黄冶窑四个时期的胎料取自同一或相近的地点,都是就地取材;四个时期的釉料配方比较相似,而四期白瓷的釉料配方最为稳定,且与二期釉料配方最相似,而与一期釉料配方已有明显不同;黄冶窑白瓷釉大部分为钙釉,存在少量钙碱釉和碱钙釉。     

One- and two-dimensional solid-state magic angle spinning NMR studies on the hydration process of layered sodium disilicate SKS-6

Three different kinds of silanols, which include isolated silanol, silanol I (with the hydroxyl proton bonded to an oxygen atom in the adjacent layer) and silanol II (with the hydroxyl proton bonded to the non-bridging oxygen at the same silicon atom), are generated during the hydration process of SKS-6 (δ-Na₂Si₂O₅). ¹H–¹H nuclear Overhauser enhancement spectroscopy reveals that the proton of silanol I has an effective chemical exchange or spin diffusion with the proton of hydrogen-bonded water, while the proton of silanol II is likely far away from the other proton-containing species. ²⁹Si magic angle spinning, ¹H→²⁹Si CP/MAS NMR and ¹H–²⁹Si phase-modulated Lee–Goldburg decoupled correlation experiments demonstrate that the local environments of the silicon sites in the final hydrated sample are mainly composed of Q² [(SiO)₂Si(OH)O⁻Na⁺], Q³ [(SiO)₃Si(OH) and (SiO)₃SiO⁻Na⁺] and Q⁴ [Si(OSi)₄] groups.     

Exploring proton rich systems and Coulomb induced instabilities

The thermodynamic properties of proton rich systems are explored in a mean field approach which is generated from a Skyrme interaction. The addition of Coulomb interactions result in asymmetries which modify the chemical and mechanical instability of the system and its equilibrium properties. These properties are studied for systems with proton fraction y on the proton richer side of the valley of β-stability as well as the neutron rich side. Coulomb induced instabilities lead to proton diffusion processes on the proton richer side and also large asymmetries in chemical and mechanical instabilities and coexistence curves. Considering the whole range of 0y1, we can study how the symmetry about y=1/2 is broken by asymmetric interaction and we can also explicitly show that the role between proton and neutron is exchanged around y_E which is the point where the liquid and gas have the same proton fraction. It is shown that there are two asymmetric coexistence surfaces in (y,P,T) space, one for y<y_E and another for y>y_E and touching each other at y_E. These asymmetries in instabilities show up as new branches, one for y<y_E and one for y>y_E, and thus form a closed loop in pressure versus ρ for both chemical instability and coexistence regions. The branch of y>1/2>y_E was not previously investigated since only the y<1/2 region is usually considered. In our simplified model, mechanical instability is still symmetric around a point y_E≠1/2 even with Coulomb forces present.     

A Lower Bound on Longitudinal Structure Function at Small x from a Self-Similarity Based Model of Proton

Self-similarity based model of proton structure function at small x was reported in the literature sometime back. The phenomenological validity of the model is in the kinematical region 6.2 × 10-7 ≤ x ≤ 10-2 and 0.045 ≤ Q2 ≤ 120 GeV2. We use momentum sum rule to pin down the corresponding self-similarity-based gluon distribution function valid in the same kinematical region. The model is then used to compute bound on the longitudinal structure function FL（X, Q2） for A1tarelli-Martinelli equation in QCD and is compared with the recent HERA data.     

Medium-range structural order in liquid Ni20Al80 alloy: Experimental and molecular dynamics studies

In this Letter, structural properties of liquid Ni₂₀Al₈₀ have been studied through molecular dynamics (MD) simulations, and results agree well with X-ray experiments. The prepeak in the structure factor manifests the existence of medium-range structural order (MRSO) in liquid Ni₂₀Al₈₀. Analyses in MRSO reveal the dominance of ideal icosahedra and defective icosahedra which, furthermore, form clusters and share common atoms.     

水平螺旋管内超临界CO2冷却换热的数值模拟

采用RNG k-ε 湍流模型对超临界CO₂流体在内径为4 mm, 长度2000 mm, 节距为10 mm, 曲率为0.1的水平螺旋管内的冷却换热进行了数值模拟.研究了质量流量、热流量以及压力对换热系数的影响, 并和超临界CO₂在水平直管内的冷却换热进行了对比.研究结果表明, 超临界CO₂在水平螺旋管内流动产生的二次流强于水平直管内的二次流, 前者的换热系数大于后者; 换热系数随质量流量的增加而增大; 在似气体区, 换热系数随着热流量的增加而增大, 而在似液体区, 热流量对换热系数几乎没有影响; 换热系数峰值点随着压力的升高而下降, 并向高温区偏移.     

Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand

Excited-state double proton transfer (ESDPT) in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol (HYDRAVH₂) ligand was studied by the density functional theory and time-dependent density functional theory method. The analysis of frontier molecular orbitals, infrared spectra, and non-covalent interactions have cross-validated that the asymmetric structure has an influence on the proton transfer, which makes the proton transfer ability of the two hydrogen protons different. The potential energy surfaces in both S₀ and S₁ states were scanned with varying O-H bond lengths. The results of potential energy surface analysis adequately proved that the HYDRAVH₂ can undergo the ESDPT process in the S₁ state and the double proton transfer process is a stepwise proton transfer mechanism. Our work can pave the way towards the design and synthesis of new molecules.     

Ultrafast proton transfer dynamics of 2-(2'-hydroxyphenyl)benzoxazole dye in different solvents

The excited-state intramolecular proton transfer of 2-(2-hydroxyphenyl)benzoxazole dye in different solvents is investigated using ultrafast femtosecond transient absorption spectroscopy combined with quantum chemical calculations.Conformational conversion from the syn-enol configuration to the keto configuration is proposed as the mechanism of excited-state intramolecular proton transfer.The duration of excited-state intramolecular proton transfer is measured to range from 50 fs to 200 fs in different solvents.This time is strongly dependent on the calculated energy gap between the N-S;and T-S;structures in the S;state.Along the proton transfer reaction coordinate,the vibrational relaxation process on the S;state potential surface is observed.The duration of the vibrational relaxation process is determined to be from8.7 ps to 35 ps dependent on the excess vibrational energy.     

化合物(Et4N)2[Pd2(mp)2(μ-mpH)2]的NMR研究

采用¹H-¹H COSY,HMQC、HMBC等2D NMR技术对化合物(Et₄N)₂[Pd₂(mp)₂(μ-mpH)₂]进行¹H、¹³C NMR谱数据分析与归属,表明它在DMSO溶液中仍保持原有固体状态的分子结构.     

超临界二氧化碳类液-类气区边界线数值分析

超临界二氧化碳(S-CO₂)因在萃取、沉淀、热力循环及化学反应等方面有着十分广阔的应用前景,逐渐成为学术界的重要研究课题.由于在近临界区,可以观察到随温度或压力变化出现大量的物性异变现象,使得各国学者对流体临界点附近区域的研究产生了浓厚兴趣.随着分子动力学模拟技术的快速发展,该技术可辅助传统实验方法用于研究近临界流体的相关物性.为确定S-CO₂在近临界区Widom线范围及类液-类气区的分子结构特征,本文通过分子动力学模拟技术结合聚类分析,研究了温度和压力范围分别在300—350 K和5.5—18.5 MPa下,CO₂密度时间序列变异系数及偏度同Widom线和类液-类气区间的关系.结果表明:S-CO₂在近临界区Widom线的确定可通过连接密度时间序列曲线变异系数极大值点来确定,Widom线沿着临界点开始延伸直到350 K时停止;S-CO₂类液区和类气区的分子分布结构可以用数密度分布的偏度来区分,偏度在类气态时为正值,在类液态时为负值,而在Widom线上达到最大值.     

超临界二氧化碳类液-类气区边界线数值分析

超临界二氧化碳(S-CO₂)因在萃取、沉淀、热力循环及化学反应等方面有着十分广阔的应用前景,逐渐成为学术界的重要研究课题.由于在近临界区,可以观察到随温度或压力变化出现大量的物性异变现象,使得各国学者对流体临界点附近区域的研究产生了浓厚兴趣.随着分子动力学模拟技术的快速发展,该技术可辅助传统实验方法用于研究近临界流体的相关物性.为确定S-CO₂在近临界区Widom线范围及类液-类气区的分子结构特征,本文通过分子动力学模拟技术结合聚类分析,研究了温度和压力范围分别在300—350 K和5.5—18.5 MPa下,CO₂密度时间序列变异系数及偏度同Widom线和类液-类气区间的关系.结果表明:S-CO₂在近临界区Widom线的确定可通过连接密度时间序列曲线变异系数极大值点来确定,Widom线沿着临界点开始延伸直到350 K时停止;S-CO₂类液区和类气区的分子分布结构可以用数密度分布的偏度来区分,偏度在类气态时为正值,在类液态时为负值,而在Widom线上达到最大值.