单分子层受限冰-水共存界线毛细波与固-液相变动力学

冰-水界面动力学性质在冰形核、生长、表界面熔化中扮演核心角色, 长期以来一直被广泛关注. 然而, 受限水体系中冰-水界面的动力学性质却鲜有报道. 本工作利用平衡态分子动力学模拟方法和受限固-液两相平衡模拟技术, 对两种水模型(恒定偶极矩、可极化)描述的单分子层受限冰-水两相平衡体系中的一维固-液界线开展研究. 通过对一维受限冰-水界线的追踪, 计算了其热涨落波动的振幅与时间自关联函数色散谱, 进而计算一系列固-液界线动力学性质. 冰-水界线波动在短波长区域复合了快、慢两种不同时间尺度的弛豫过程, 在长波长区域则由慢弛豫过程主导. 相比块体冰-水界面体系, 以Rayleigh波为主的高频微观物理过程更多地参与了一维冰-水界线的动力学弛豫. 我们发现冰-水界线波动弛豫特征衰减时间的波矢依赖关系符合现有固-液界面动力学理论, 但一维界线弛豫的特征衰减时间比二维界面体系低了一个数量级左右. 计算了两种水模型体系冰-水界线的动力学系数, 并与块体冰-水界面比较, 发现受限冰-水(固-液)界线动力学系数远高于块体冰-水界面体系. 我们推测水分子转动自由度在受限腔中被强烈压制可能是导致受限体系超快冰-水(固-液)相变速率的主要原因. 本工作将在受限水体系超快相变(储能、传感)器件的设计工作中提供一定的理论指导意义.     

水分子团簇分子力场方法的比较研究

采用传统水分子力场模型(SPC, TIPnP(n=3-5))和极化模型(POL3, AMOEBA, SPC-FQ, TIP4P-FQ)对水分子二聚体团簇性质进行了比较和研究. 以从头计算和实验数据为依据, 分析水分子在外场作用下体系的静电极化, 电荷转移和分子结构变化. 通过水分子二聚体结合能和各分解能量项评价极化静电势能在双分子结合能中的地位和作用, 以及各水分子力场的适用性. 通过水分子团簇多体相互作用能的计算,展示不同极化水分子力场定量计算极化能量的实际能力. 通过对力场模型结果的对比和分析, 为进一步发展极化力场模型, 并应用到其他体系提供借鉴和依据.     

限域单分子层冰-水两相平衡体系的分子动力学模拟

限域水因有极其丰富的结构物相变化而成为近年来水科学研究的一个热点.然而,不同相限域水之间的相平衡结构与性质却鲜有报道.论文提出一套分子动力学模拟技术,可实现纳米尺度限域条件下冰和水的不同结构相间形成的低维固-液界面（线）的平衡态模拟.应用此模拟技术,我们探索了0.65 nm限域尺寸、5000 bar限域压强条件下,单分子层厚度的冰-水（固-液）两相平衡,计算了该平衡体系一系列热力学量在界线附近的分布.平衡态的分子模拟结果直观地展示了粗糙型固-液界线的热毛细涨落、界线固-液结构转变的微观机制、以及缺陷在固-液相变区附近的形成与输运.各种热力学量分布函数呈现了二维限域冰-水共存界面（线）的特殊性质,如：相平衡区域的尺寸异于块体材料固-液界面,固-液界线处于切向压缩状态等.     

几种固体氧化物/水蒸气体系的介电性质的研究

测定了p/p_0为0～0.75、频率为400 Hz～5 MHz范围内MgO、CaO、Ca(OH)_2及TiO_2/水蒸气体系的介电等温线与介电吸收曲线. 用M-W-S界面极化理论讨论了在一定条件下吸附(水)量与体系介电常数ε’的关系。观察到所研究的几种固体氧化物/水蒸气体系在介电性质方面的差异,并初步探讨了产生这些差异的原因。从而从不同角度为我们了解吸附剂的表面状态及其与水分子的相互作用提供了有益的信息。     

浓差极化的介电模型——复合膜/溶液体系的数值模拟

提出了具有电导率和介电常数线性分布的介质的介电模型, 并导出了其内部电的和结构性质的参数与宏观测量的电容和电导之间定量关系的理论表达式, 以模拟复合膜中的多孔层部分的介电弛豫行为. 大量的模拟计算描述并解释了多孔层介电谱随介电常数分布、厚度等性质而变化的规律. 进一步对具有层状构造的复合膜以及复合膜和溶液相组成的多层体系的弛豫行为进行了数值模拟, 比较了三个体系(多孔层、复合膜、复合膜/液相层状体系)的介电谱, 结果揭示了介电谱对各层性质的依赖关系. 所提出的电导率和介电常数线性分布的多孔层的介电模型, 也可用于具有其他电导率、介电常数分布规律的体系.     

介电法研究溶液中分子间的缔合作用(I)

磷酸三丁酯(TBP)是一种重要的萃取剂,它已广泛地应用于许多金属的提取工艺中。在萃取过程中,水在两相间的转移对萃取过程产生重要影响。一些实验表明,TBP分子是通过氢键与水生成1∶1缔合物形式萃取水分子。但对该缔合物的物理化学性质研究尚未见报导。我们运用静态介电研究法,通过测定溶液介电常数,并应用向无限稀释外推手段,进一步证明TBP与H_2O的缔合作用,并测得TBP·H_2O缔合物的摩尔极化度、偶极矩和缔合平衡常数,进而求得缔合反应的自由能。     

受限于不同螺旋性的纳米碳管中水的分子动力学模拟

近年来将纳米碱米碳管引入到与生命过程息息相关的离子通道膜的研究逐渐成 为热点，而其中的关键就是要了解受限于膜孔道（碳管）中水分子的行为。采用分 子动力学模拟在300 K和1.01 * 10~5 Pa下对受限于（6，6）armchair型和（10， 0）zigzag型纳米碳管中的水进行了研究，得到了水分子在碳管中的局部密度分布 等静态性质以及水分子在碳管中的传递等动态性质，并对不同势能模型的模拟结果 作了比较。结果表明选择不同的势能模型并没有改变此体系的固有性质，即水分子 不仅能够进入到憎水性的（6，6）碳管中而且能形成一条稳定的由氢键相连的纵列 （single file），而且在管中以纵列的形式进行同歇传递。此外，碳管螺旋性对 受限水的静态性质影响不大但对动态性质则有一定程度的影响，水分子在（10，0 ）zigzag型碳管中的传递能力要强于在（6，6）armchair型碳管中的能力。     

单分子器件电子输运性质的理论研究

对当前单分子器件的理论和实验的研究进展作了简短评述,并简要介绍电子输运理论,最后给出一个基于非平衡态格林函数电子输运理论的全自洽方法,研究单个水分子在Au(111)电极之间的输运性质的计算实例.研究结果表明由于水分子与电极之间存在较强的杂化作用,水分子的分立能级间距大,在小偏压范围内,水分子的特征已经被淹没在杂化能级之中.体系的电势变化主要发生在水分子局域区间,其电子输运行为主要是一个单通道过程.     

双层氧化石墨烯纳米体系中受限水的介电常数

为了深入了解孔径和氧化程度对介电性能的影响, 通过分子动力学模拟的方法, 探究了水在不同孔径和氧化程度的双层石墨烯纳米通道中的介电行为. 实验结果表明, 在较窄的通道环境中, 水分子会表现出更强的有序取向, 受限水的介电常数随纳米通道空间的减小而减小. 随着氧化程度的增加, 较宽的层间距对介电常数的影响大于较窄的纳米通道. 对于最宽的通道(d=1.2 nm), 石墨烯双分子层内水的介电常数随氧化程度的增加而降低, 而对于相对较窄的通道(d=0.6, 0.9 nm), 介电行为呈现出非单调的趋势. 为了理解其背后的物理原因, 分别计算了3个纳米通道的氢键数量. 结果表明, 氢键数量以及动态稳定性（对应最快的衰减率）最低的是1.2 nm宽的纳米通道, 这表明水分子在大的纳米通道中更不稳定, 同时也比在0.6和0.9 nm的纳米通道中更无序.     

介电失配度对沸石电流变液界面极化的影响

利用介电谱方法研究了NaA沸石/硅油和NaA沸石/煤油两种电流变液的介电行为, 测量发现两体系在10⁵ Hz处均出现明显的弛豫现象. 采用单弛豫Cole-Cole函数拟合各体系的介电参数, 结果表明在相同体积分数条件下硅油体系具有较大的介电增量(?ε), 且两体系的介电增量与体积分数(φ)均服从?ε＝4ε_mφ的函数关系. 通过计算和分析粒子与介质间介电失配程度, 阐明了油介质的介电常数(ε_m)对于沸石电流变液界面极化强度的贡献. 此外研究了吸附水对沸石电流变液界面极化的影响, 结果发现水的吸附对于体系的?ε值没有影响, 但明显降低了弛豫时间, 证明吸附水对沸石电流变液的界面极化率具有增强作用.     

从物质本原到干水:水的概念的发展史

在古代哲学中,水被视为一种物质本原。17世纪化学学科形成后,水被定义成一种化学元素。18世纪的化学革命中,水被发现是氢氧化合物。19世纪原子分子论的创立,使水的概念得到微观表征。至20世纪,重水的发现和干水的发明使水的概念有了新的发展。总之,水的概念的发展史,反映了化学思想的发展和科学技术的进步,对化学研究和化学教育均有重要的启示。     

A model study on the mechanism and kinetics for the dissociation of water anion

Quantum chemical computations using both density functional theory (B3LYP functional) and wavefunction (MP2 and CCSD(T)) methods, with the 6-311++G(3df,2p) and aug-cc-pVnZ (n = D,T,Q) basis sets, in conjunction with a polarizable continuum model (PCM) method for treating structures in solution, were carried out to look again at a series of small negatively charged water species [(H₂O)_n]^•–. For each size n of [(H₂O)_n]^•– in aqueous solution with n = 2, 3, and 4, two distinct structural motifs can be identified: a classical water radical anion formed by hydrogen bonds and a molecular pincer in which the excess electron is directly interacting with H atoms. In aqueous solution, both motifs have comparable energy content and likely coexist and compete for the ground state. Some water anion isomers can dissociate when interaction with a water molecule, [(H₂O)_n]^•– + H₂O → H^•(H₂O)_m + OH^–(H₂O)_n–m, through successive hydrogen transfers with moderate energy barriers. This reaction can also be regarded as a water-splitting process in which the H transfers involved take place mainly within a water trimer, whereas other water molecules tend to stabilize transition structures through microsolvation rather than direct participation. Calculated absolute rate constants for the reversed reaction H^•(H₂O)₂ + OH^–(H₂O)₂ → [(H₂O)₄]^•־ + H₂O with both H and D isotopes agree well with the experimentally evaluated counterpart and lend a kinetic support for the involvement of a tetramer unit.     

Determination of freezable water content of beef semimembranous muscle DSC study

The freezable water contents of samples obtained from previously chilled semimembranous muscle of middle-aged beef carcasses after a 24 h cooling period a room at in 5±1C were determined by differential scanning calorimetry (DSC) at –5, –10, –15, –20, –30, –40, –50 and –65C. This was accomplished by freezing the samples at the above-mentioned temperatures, followed by thawing to 35C, and measuring the melting peaks of freezable water. The areas of these peaks were determined by using the peak integration method programs through a computer linked to the DSC, and they were then used to determine the latent heat of melting (H _m) in kJ kg^–1 at each freezing temperature. The resultant latent heat of melting per sample was divided by the latent heat for pure water to determine the amount of freezable water present in these samples. This amount of freezable water was divided by the total water content of the meat sample to determine the percentage of freezable water in the sample. The percentage of freezable water was subtracted from 100 to determine the percentage of bound water present in the sample.     

Determination of differences in free and bound water contents of beef muscle by DSC under various freezing conditions

The differences in bound water content of beef semimembranous muscle samples obtained from previously chilled (24 h at +4°C) middle-aged beef carcasses were determined by the use of DSC. Initially, samples obtained from fresh, unprocessed meat were frozen at –40, –50 or –65°C to determine their melting peaks for freezable water (free water) content with the use of DSC. The samples were then subjected to an environment with an ambient temperature of –30, –35, –40 or –45°C, with no air circulation, or with an air circulation speed of 2 m s^–1, until a thermal core temperature of –18°C was attained; this was followed by thawing the samples until a thermal core temperature of 0°C was reached. This process was followed by subjecting the samples to the ambient temperatures mentioned above, to accomplish complete freezing and thawing of the samples, with DSC, and thereby determination of the freezable water contents, which were then used to determine the peaks of melting. The calculated peak areas were divided by the latent heat of melting for pure water, to determine the freezable water contents of the samples. The percentage freezable water content of each sample was determined by dividing its freezable water content by its total water content; and the bound water content of each sample was determined by subtracting the percentage free water content from the total. In view of the fact that the free water content of a sample is completely in the frozen phase at temperatures of –40°C and below, the calculations of free and bound water contents of the samples were based on the averages of values obtained at three different temperatures.     

Analysis of Fischer-Tropsch by-product waters by gas chromatography

This paper describes a quantitative technique for the determination of organic constituents in Fischer-Tropsch by-product waters. Temperature-programmed gas chromatography on derivatized bonded polar capillary columns provides the required separation that permits reliable quantitation of individual compounds. A preliminary combined gas chromatographic–mass spectrometric survey to identify the components present in Fischer-Tropsch by-product waters is presented. The elution order of 58 identified components is tabulated. Components identified in a typical Fischer-Tropsch by-product water include C₁–C₉ linear and branched alcohols, C₃? C₈ ketones, C₂? C₆ carboxylic acids, and C₂? C₄ linear aldehydes.     

Transport properties of chitosan membranes: Influence of crosslinking

A chitosan film with acetylation degree close to 2% was crosslinked with glutaraldehyde. The consequences of this chemical modification were studied on the polymer gas and water transport properties. The crystalline domains were not affected by the crosslinking reaction and the modification of the amorphous phase did not induce variation of the gas permeability at anhydrous state. A crosslinking of 5 h, leading to a theoretical amine conversion of 60% in the amorphous phase induced only small changes of the polymer water sorption capacity at relative pressures less than 0.5. The main modification of the transport properties induced by this treatment occurred at a relative pressure equal to one with a significant reduction of the water sorption and water permeation and with the impossibility to measure the gas permeability coefficient in these conditions due to the brittleness of the membrane. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1521–1529, 2000     

Interaction of water with the regenerated cellulose membrane studied by DSC

One to three endothermal peaks atributted to melting of bulk and interfacial water were observed by DSC in the regenerated cellulose — water system. The profiles of thermal effects depend on water content, time of conditioning, film pretreatment and the conditions applied during the preceding freezing-thawing cycles. The occurrence might be deduced of melting-crystallisation processes. A large amount of non-freezable strongly bounded water was also detected. Although cellulose absorbs water quickly after immersion, the structural changes consisting on ordering of polymer fraction occur during further conditioning due to increase in strength of water binding. Using the membranes in the separation module at 90°C causes weakening of these bonds. Differences between interaction of particular cellulose films with water can be detected during the first, the second and the third heating. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effects of Amplitude of the Radiofrequency Electromagnetic Radiation on Aqueous Suspensions and Solutions

The effects of radiofrequency (RF) (1–4) and magnetic fields (5–9) on the behavior of aqueous solutions and suspensions have been a popular subject in recent years. The mechanism of the magnetic “water memory” effect, though, is still largely unknown (5). In this work, we present evidence that the primary “receptor” of the electromagnetic radiation is a gas/liquid interface. Gas can be either already present in water or produced by the effects of electromagnetic fields. Perturbed gas/liquid interfaces require hours to equilibrate. Certain RF and magnetic signals also produce reactive oxygen and hydrogen species (superoxide, hydrogen peroxide, hydrogen, atomic hydrogen). The perturbed gas/liquid interface modifies the hydrogen bonding networks in water and also the hydration of ions and interfaces. Careful outgassing removes all of the effects of the electromagnetic fields, including the magnetic memory effect. The amplitude of the applied field influences the observed effects. Different amplitudes of RF radiation perturb the interfacial water in different ways and consequently affect the behavior of colloids and ions in specific manners. For instance, the bulk and template precipitation of calcium carbonate, zeta potentials of suspended colloids, rate of dissolution of colloidal silica, and attachment of colloidal silica to metal surfaces are modified in specific ways with the low amplitude or high amplitude RF treatments described in this paper. The solubility/diffusivity of gas species is also modified in a different manner, and it is probably at the core of the specificity of the RF amplitude effects.     

多金属氧酸盐催化的水氧化研究进展

氢气以其清洁无污染、燃烧值高等优点成为未来最具潜力的可再生能源之一,而清洁生产氢气的最佳选择之一即为裂解水. 利用太阳能模拟光合作用实现水的全分解产生氢气和氧气是目前最为理想的能源转化方式,并且已经引起了众多研究者的关注. 水分解的半反应之一--水氧化反应由于其过程复杂,一直是制约水分解的瓶颈. 所以寻找高效、稳定的水氧化催化剂便成为了突破该瓶颈的关键. 多金属氧酸盐是一类以前过渡金属氧簇为基本单元形成的多金属氧簇化合物. 由于多金属氧酸盐在物理、化学性质方面具有无法比拟的特性,使得其在催化、药物、纳米科技和材料科学等方面已被广泛地应用. 多金属氧酸盐的全无机配体可很好地抵御水氧化反应的强氧化性环境,故将其作为水氧化催化剂越来越引起研究者们的注意,并且已有多种多金属氧酸盐被设计为水氧化催化剂. 本文详细介绍了各种不同过渡金属取代的多金属氧酸盐水氧化催化剂的研究进展.