A_aD_d型氢键流体的统计理论(V):球形微腔中的相平衡

利用密度泛函理论并结合改进的基本度量理论研究了球形微腔中AaDd型氢键流体的相态结构.首先,根据氢键流体在球腔中的吸附-脱附等温线以及相应的巨势等温线获得不同条件下氢键流体的相图.在此基础上,重点讨论了氢键作用、球腔尺寸以及腔壁与流体之间的相互作用等因素对氢键流体相平衡特征的影响.结果表明,流体层化转变和毛细凝聚的临界温度、临界密度和临界相区域等相态特征与这些因素密切相关.研究结果可为进一步揭示几何约束下氢键流体的相平衡及聚集态结构提供可能的理论线索.     

AaDd型氢键流体的统计理论（V）：球形微腔中的相平衡

利用密度泛函理论并结合改进的基本度量理论研究了球形微腔中AaDd型氢键流体的相态结构．首先,根据氢键流体在球腔中的吸附一脱附等温线以及相应的巨势等温线获得不同条件下氢键流体的相图．在此基础上,重点讨论了氢键作用、球腔尺寸以及腔壁与流体之间的相互作用等因素对氢键流体相平衡特征的影响．结果表明,流体层化转变和毛细凝聚的临界温度、临界密度和临界相区域等相态特征与这些因素密切相关．研究结果可为进一步揭示几何约束下氢键流体的相平衡及聚集态结构提供可能的理论线索．     

模拟吸附在狭缝微孔中的丙烷的微观结构

用巨正则系综MonteCarlo（GCEMC）方法模拟了活性碳孔吸附丙烷时的微观结构．在GCEMC模拟中,非极性丙烷分子采用单点LJ球状分子模型,狭缝活性碳孔墙采用10－4-3势能模型．在温度T＝134．3K下,模拟并观察到了丙烷分子在狭缝活性碳孔中的吸附、脱附以及毛细凝聚现象,得到了吸附等温线和孔中流体的局部密度轮廓图．从分子水平出发,详细分析了吸附、毛细冷凝时孔中流体的微观结构,为认识、理解吸附的微观机理提供了工具与借鉴．     

单壁碳纳米管中甲烷吸附的分子模拟

采用巨正则系统MonteCarlo方法研究了甲烷在单壁碳纳米管(Singlewallcarbonnanotube,SWNT)中于低温74.05K下的吸附等温线及吸附机理,发现在两个较小的孔径(1.225nm和1.632nm)下单壁碳纳米管中甲烷的吸附有着明显的微孔所独有的“填充效应”,而在2.04nm以上的孔的吸附中会出现毛细凝聚现象。通过模拟知道发生毛细凝聚的必要条件是孔内能至少容纳下两层粒子,此外还导出在恒定温度下毛细凝聚吸附量与SWNT孔径关系。本文还模拟了常温300K下甲烷在SWNT内的吸附,对比了2.04nm和4.077nm两种孔径的SWNT吸附甲烷的等温线,推荐在4.077nm孔中的适宜吸附存储压力为5.0～6.0MPa,吸附质量分数可达16%～19%.     

活性炭纤维的微孔结构水吸附

测定了两种活性炭纤维（ACF）的氮气、水吸附等温线和XPS,研究了ACF的微孔结构和表面性质,用αs图分析氮吸附等温线获得了ACF的比表面积、微孔容量和微孔径。XPS表明在ACF表面存在多种不同结合状态的氧。水在ACF上的吸附等温线呈V型,具有很大的脱附滞后环。水通过与ACF表面的氧形成氢键发生吸附。ACF表面的初始吸附点多,则在低、中压时的水吸附量就大。     

甲烷在中孔分子筛MCM-41中吸附的计算机模拟

采用巨正则系综Monte Carlo方法研究了甲烷在两个不同孔径的MCM-41中不同温度下的吸附等温线和其在孔中的相行为和排列方式.模拟结果显示,在较小孔径的MCM-41中,流体分子达到毛细凝聚所需的化学位较小,并且观察到两个孔径下计算机模拟得到的亚稳态区域都非常宽,使得层状转变（如果有的话）被包含在这个区域.通过比较两种孔径下达到毛细凝聚后的构型,可以看出,在3.5 nm的孔中流体的分子结构出现非常有序的排列,而在5.0 nm的孔中则没有.在常温300 K时甲烷的吸附的计算机模拟表明,孔壁对流体分子的作用仅仅影响较靠近壁面附近的流体分子的排列,而对孔中间的分子几乎没有影响.     

用吸附数据对硅胶表面的分形分析

根据一种中孔硅胶对甲酸、乙酸、丙酸和四氯化碳蒸气吸附等温线的单层区域和毛细凝结区域的数据以及自四氯化碳稀溶液中吸附系列脂肪醇的结果计算了该硅胶表面分形维数D.除了由吸附四氯化碳等温线毛细凝结区域所得D值低于2外,由其它吸附数据得出的该硅胶的分维D近似相等(D=2.06±0.05).中孔硅胶低D值可用其孔结构特性解释.     

吸附法研究固体表面的分形性质

介绍用气体和蒸气吸附等温线数据求出的单层饱和吸附量和根据等温线毛细凝结区域数据求算分形固体表面分维值的方法;提出了用固体自溶液中吸附数据计算分维值的方法。讨论了介孔吸附剂的分维和固体表面分形性质在物理化学方面的应用。     

硅胶表面上脂肪酸蒸气吸附膜

应用Gibbs方程由甲酸、乙酸和丙酸蒸气在硅胶上的吸附等温线计算了吸附膜的表面压力(π)与每个吸附分子所占面积(σ)间的关系(π～σ图).所得曲线与不溶物在溶液表面上的结果相似,均表现出有“液态扩张膜”“转变膜”和“液态凝聚膜”.不同的是,不溶物只能形成单分子层膜,而硅胶表面上的脂肪酸吸附膜则是多分子层的.蒸气吸附膜由单层向多层的转变,恰与π～σ图上的“液态扩张膜”向“转变膜”的转变相对应.吸附焓(△H)与吸附熵(△S)的计算结果表明,在此转变附近AH和AS发生急剧变化.     

聚氯乙烯微塑料对典型单羟基菲的吸附机制

为丰富微塑料与有机污染物间的相互作用机制相关数据,以3-羟基菲(3-OHP, C₁₄H₁₀O)为菲单羟基衍生物代表污染物,聚氯乙烯(PVC)微塑料为研究对象,研究了PVC微塑料在水环境中对3-OHP的吸附行为,并就相关吸附机制进行了深入探讨。该研究借助扫描电镜(SEM)、X射线衍射仪(XRD)、傅里叶红外光谱(FT-IR)等仪器对PVC微塑料进行表征,利用紫外分光光度计得出目标污染物的紫外吸收光谱标准曲线,标准曲线拟合相关系数(R²)>0.99。为保证紫外吸收光谱的准确性,污染物浓度梯度设置为吸光度(Abs)大于0.438,之后根据标准曲线方程计算其浓度,结合相关吸附模型(吸附动力学、吸附等温线和吸附热力学)并配合密度泛函理论(density functional theory, DFT)探讨了在水环境中PVC微塑料对3-OHP的吸附机制。结果如下:(1)吸附动力学实验结果显示伪二级动力学模型拟合程度最好,吸附动力学拟合系数R²=0.998。因此,PVC吸附3-OHP可能是以表面吸附和外液膜扩散的吸附方式,吸附发生24 h后的平衡吸附量为36.866 μg/g; (2)吸附等温线实验表明Langmuir和Freundlich等温线模型拟合度较高,吸附等温线拟合系数R ²分别为0.956和0.907,更加适合描述PVC对3-OHP的吸附过程,吸附模式主要为单层吸附,也存在小部分多层吸附,PVC对3-OHP的最大吸附量为408 μg/g; (3)吸附热力学结果显示PVC微塑料对3-OHP的吸附效率随着温度升高而降低,这表明PVC对3-OHP的吸附为自发、放热的吸附反应;(4)盐度实验结果表明,盐度对3-OHP在PVC上的吸附效率影响不大;(5)DFT理论计算结果表明PVC对3-OHP结合能相对较低,因此推测PVC对3-OHP的主要吸附机制可能是疏水作用,还可能存在弱氢键作用、卤素键作用以及π-π共轭作用。研究揭示了PVC微塑料与有机物相互作用方式,明确了PVC微塑料对3-OHP的吸附模式,探讨了PVC微塑料对3-OHP的相互作用机制,有助于更好地了解PVC微塑料在水溶液中的环境行为。该研究为科学评价微塑料的环境影响提供数据参考,并进一步补充了微塑料的毒理学机制数据。     

Phase Equilibria of Hydrogen Bonding Fluid in a Slit Pore with Broken Symmetry

Phase equilibria of hydrogen bonding (HB) fluid confined in a slit pore with broken symmetry were investigated by the density functional theory incorporated with modified fundamental measure theory, where the symmetry breaking originated from the distinct interactions between fluid molecules and two walls of the slit pore. In terms of adsorption-desorption isotherms and the corresponding grand potentials, phase diagrams of HB fluid under various conditions are presented. Furthermore, through phase coexistences of laying transition and capillary condensation, the effects of HB interaction, pore width, fluid-pore interaction and the broken symmetry on the phase equilibrium properties are addressed. It is shown that these factors can give rise to apparent influences on the phase equilibria of confined HB fluid because of the competition between intermolecular interaction and fluid-pore interaction. Interestingly, a significant influence of broken symmetry of the slit pore is found, and thus the symmetry breaking can provide a new way to regulate the phase behavior of various confined fluids.     

_f-A_aD_d氢键体系的统计特征

基于氢键的形成和缩聚反应机理在统计意义下的相似性,利用高分子反应统计理论和反应动力学理论对氢键溶液的一个模型体系进行了相关讨论.给出了体系的溶胶分数和发生溶胶-凝胶相变的条件,指出质子受体基团间的竞争作用对溶胶凝胶相变点的影响,进而讨论了体系的数量分布函数和相关问题.     

Density functional theory study of the nematic-isotropic transition in an hybrid cell

We have employed the density functional theory formalism to investigate the nematic-isotropic capillary transitions of a nematogen confined by walls that favor antagonist orientations to the liquid crystal molecules (hybrid cell). We analyze the behavior of the capillary transition as a function of the fluid-substrate interactions and the pore width. In addition to the usual capillary transition between isotropiclike to nematiclike states, we find that this transition can be suppressed when one substrate is wet by the isotropic phase and the other by the nematic phase. Under this condition the system presents interfacelike states which allow us to continuously transform the nematiclike phase to the isotropiclike phase without undergoing a sharp phase transition. Two different mechanisms for the disappearance of the capillary transition are identified. When the director of the nematiclike state is homogeneously planar-anchored with respect to the substrates, the capillary transition ends up in a critical point. This scenario is analogous to the observed in Ising models when confined in slit pores with opposing surface fields which have critical wetting transitions. When the nematiclike state has a linearly distorted director field, the capillary transition continuously transforms in a transition between two nematiclike states.     

_f-A_aD_d氢键体系的统计特征

基于氢键的形成和缩聚反应机理在统计意义下的相似性 ,利用高分子反应统计理论和反应动力学理论对氢键溶液的一个模型体系进行了相关讨论 .给出了体系的溶胶分数和发生溶胶 -凝胶相变的条件 ,指出质子受体基团间的竞争作用对溶胶凝胶相变点的影响 ,进而讨论了体系的数量分布函数和相关问题 .     

Layering, condensation, and evaporation of short chains in narrow slit pores

The phase behavior of short-chain fluids in slit pores is investigated by using a nonlocal-density-functional theory that takes into account the effects of segment size, chain connectivity, and van der Waals attractions explicitly. The layering and capillary condensation/evaporation transitions are examined at different chain length, temperature, pore width, and surface energy. It is found that longer chains are more likely to show hysteresis loops and multilayer adsorptions along with the capillary condensation and evaporation. Decreasing temperature favors the inclusion of layering transitions into the condensation/evaporation hysteresis loops. For large pores, the surface energy has relatively small effect on the pressures of the capillary condensation and evaporation but affects significantly on the layering pressures. It is also observed that all phase transitions within the pore take place at pressures lower than the corresponding bulk saturation pressure. The critical temperature of condensation/evaporation is always smaller than that of the bulk fluid. All coexistence curves for confined phase transitions are contained within the corresponding bulk vapor-liquid coexistence curve. As in the bulk phase, the longer the chain length, the higher are the critical temperatures of phase transitions in the pore.     

Casimir amplitudes and capillary condensation of near-critical fluids between parallel plates: renormalized local functional theory

We investigate the critical behavior of a near-critical fluid confined between two parallel plates in contact with a reservoir by calculating the order parameter profile and the Casimir amplitudes (for the force density and for the grand potential). Our results are applicable to one-component fluids and binary mixtures. We assume that the walls absorb one of the fluid components selectively for binary mixtures. We propose a renormalized local functional theory accounting for the fluctuation effects. Analysis is performed in the plane of the temperature T and the order parameter in the reservoir ψ(∞). Our theory is universal if the physical quantities are scaled appropriately. If the component favored by the walls is slightly poor in the reservoir, there appears a line of first-order phase transition of capillary condensation outside the bulk coexistence curve. The excess adsorption changes discontinuously between condensed and noncondensed states at the transition. With increasing T, the transition line ends at a capillary critical point T=T(c) (ca) slightly lower than the bulk critical temperature T(c) for the upper critical solution temperature. The Casimir amplitudes are larger than their critical point values by 10-100 times at off-critical compositions near the capillary condensation line.     

Theoretical prediction of multiple fluid-fluid transitions in monocomponent fluids

The authors use the analytical equation of state obtained by the discrete perturbation theory [A. L. Benavides and A. Gil-Villegas, Mol. Phys. 97, 1225 (1999)] to study the phase diagram of fluids with discrete spherical potentials formed by a repulsive square-shoulder plus an attractive square-well interaction (SS+SW). This interaction is characterized by the usual energy and size parameters plus three dimensionless parameters: two of them measuring the widths of the SS and the SW and the third the relative height of the SS. The matter of interest is that, for certain values of the interaction parameters, the SS+SW systems exhibit more than one first-order fluid-fluid transition. The evidence that several real substances (such as water, phosphorus, carbon, and silica, among others) exhibit an extra liquid-liquid transition has drawn interest into the study of interactions responsible for this behavior. The simple SS+SW fluid is one of the systems that, in spite of being spherically symmetric, shows multiple fluid-fluid transitions. In this work the authors investigate systematically the effect on the phase diagram of varying the interaction parameters. The use of an analytical free-energy equation gives a clear thermodynamic picture of the emergence of different types of critical points, throwing new light on the phase behavior of these fluids and thus clarifying previous results obtained by other techniques. The interplay of attractive and repulsive forces with several scale lengths produces very rich phase diagrams, including cases with three critical points. The region of the interaction-parameter space where multiple critical points appear is mapped for various families of interactions.     

高分子链在球内表面上的吸附/排空转变

应用自洽场理论(SCFT)研究了受限于球内的高分子溶液的结构,重点关注高分子链在受限壁附近的行为.根据自洽场理论数值计算结果,讨论了球半径、高分子与球限制壁的相互作用、高分子平均浓度等因素对球内高分子浓度分布的影响.从高分子浓度分布和吸附/排空层厚度可以发现,在一定的条件下,受限的高分子在受限壁上会发生吸附/排空转变.吸附/排空转变与受限球大小、高分子链长和平均浓度,以及高分子链与受限壁之间相互作用都有关系.理论预测发生吸附/排空转变时的高分子与球限制壁的临界相互作用参数与链长的倒数成线性关系,且斜率与球半径有关.限制球越小,要发生吸附/排空转变,需要高分子与球之间有更大的临界吸引能.     

Extension of the Steele 10-4-3 potential for adsorption calculations in cylindrical, spherical, and other pore geometries

Simplified fluid-substrate interaction models derived from the Lennard-Jones potential are widely used in the simulation of gas physisorption phenomena. In this paper, we reinterpret the well known Steele 10-4-3 potential for a gas molecule interacting with a planar surface, and use the resultant scheme to derive new potentials for cylindrical and spherical pore geometries. These new potentials correctly recover the Steele result in the limit of infinite pore radius, a useful improvement over existing models. We demonstrate the new cylindrical Steele 10-4-3 potential in calculations of argon adsorption via fluid density functional theory. This potential yields markedly different adsorption behavior than existing cylindrical potentials, which follow from small but significant differences in both the strength and the shape of the fluid-surface interaction. These differences cannot be fully reconciled simply by reparameterizing (scaling) the existing models; the new potential is more realistic in design, and is especially to be preferred in studies where comparison with planar substrates is made. Finally, we discuss extensions of this approach to more complicated pore geometries, yielding a family of Steele-like potentials that all satisfy the correct planar limit.