Ice tessellation on a hydroxylated silica surface

The adsorption of water on a fully hydroxylated silica surface is studied by using density-functional total-energy and molecular dynamics calculations. The (100) surface of beta(alpha)-cristobalite covered by geminal hydroxyls has been taken as the substrate. A well-ordered and stable two-dimensional ice with quadrangular and octagonal patterns of hydrogen bond (H-bond) networks-an ice tessellation-is found on the surface for the first time. With the vibrational recognition, the four water molecules in the quadrangle are found to be bonded by strong H bonds while the quadrangles are connected to each other by weak H bonds. This configuration is the most stable, because all the water molecules are fully saturated with H bonds either to each other or to the surface hydroxyl groups.     

The adsorption of water on clean and oxygen covered Cu(110)

The water adsorption on clean and oxygen precovered Cu(110) surfaces is studied by means of UPS, LEED, work function measurements and ELS. At 90 K on the clean surface molecular water adsorption is indicated by UPS. The H₂O molecules are bonded at the oxygen end and the H-O-H angle is increased as compared with the free molecule. In the temperature range between 90 and 300 K distorted H₂O molecules and adsorbed hydroxyl species (OH) are detected, which are desorbed at room temperature. On an oxygen covered surface hydroxyl groups are formed by dissociation of adsorbed water molecules at a lower temperature than on the clean surface. Multilayers of condensed water are found below 140 K in both cases.     

The adsorption of oxygen and water on Ca and CaO films studied with MIES, UPS and XPS

Metastable induced electron spectroscopy (MIES), Ultraviolet photoelectron spectroscopy (UPS), and X-ray photoelectron spectroscopy (XPS) are employed to study the adsorption of water on Ca and CaO films as well as the adsorption of oxygen on Ca films. Ca films are prepared by evaporation of Ca onto clean Si(1 0 0) substrates. CaO films are produced by Ca evaporation in an oxygen atmosphere at a substrate temperature of 400 °C. Gas adsorption on the Ca films at room temperature, both for oxygen and water, is initiated by complete dissociation of the impinging molecules leading to the formation of Ca–O bonds. Exposure to water furthermore leads to the formation of hydroxyl groups via hydrogen abstraction from water forming a complete surface layer. Hydroxyl groups are also formed upon exposure of CaO films to water, but to a significantly smaller amount compared to Ca films exposed to water.     

Role of oxygen functional groups for structure and dynamics of interfacial water on low rank coal surface: a molecular dynamics simulation

Molecular dynamics simulations were employed to study the effects of oxygen functional groups for structure and dynamics properties of interfacial water molecules on the subbituminous coal surface. Because of complex composition and structure, the graphite surface modified by hydroxyl, carboxyl and carbonyl groups was used to represent the surface model of subbituminous coal according to XPS results, and the composing proportion for hydroxyl, carbonyl and carboxyl is 25:3:5. The hydration energy with ?386.28 kJ/mol means that the adsorption process between water and coal surface is spontaneous. Density profiles for oxygen atoms and hydrogen atoms indicate that the coal surface properties affect the structural and dynamic characteristics of the interfacial water molecules. The interfacial water exhibits much more ordering than bulk water. The results of radial distribution functions, mean square displacement and local self-diffusion coefficient for water molecule related to three oxygen moieties confirmed that the water molecules prefer to absorb with carboxylic groups, and adsorption of water molecules at the hydroxyl and carbonyl is similar.     

The adsorption and reaction of H2O on clean and oxygen covered Ag(110)

The adsorption and reaction of water on clean and oxygen covered Ag(110) surfaces has been studied with high resolution electron energy loss (EELS), temperature programmed desorption (TPD), and X-ray photoelectron (XPS) spectroscopy. Non-dissociative adsorption of water was observed on both surfaces at 100 K. The vibrational spectra of these adsorbates at 100 K compared favorably to infrared absorption spectra of ice Ih. Both surfaces exhibited a desorption state at 170 K representative of multilayer H₂O desorption. Desorption states due to hydrogen-bonded and non-hydrogen-bonded water molecules at 200 and 240 K, respectively, were observed from the surface predosed with oxygen. EEL spectra of the 240 K state showed features at 550 and 840 cm^?1 which were assigned to restricted rotations of the adsorbed molecule. The reaction of adsorbed H₂O with pre-adsorbed oxygen to produce adsorbed hydroxyl groups was observed by EELS in the temperature range 205 to 255 K. The adsorbed hydroxyl groups recombined at 320 K to yield both a TPD water peak at 320 K and adsorbed atomic oxygen. XPS results indicated that water reacted completely with adsorbed oxygen to form OH with no residual atomic oxygen. Solvation between hydrogen-bonded H₂O molecules and hydroxyl groups is proposed to account for the results of this work and earlier work showing complete isotopic exchange between H₂¹⁶O_(a) and ¹⁸O_(a).     

Structure of rutile TiO2 (1 1 0) in water and 1 molal Rb at pH 12: Inter-relationship among surface charge, interfacial hydration structure, and substrate structural displacements

The rutile (1 1 0)-aqueous solution interface structure was measured in deionized water (DIW) and 1 molal (m) RbCl + RbOH solution (pH 12) at 25 °C with the X-ray crystal truncation rod method. The rutile surface in both solutions consists of a stoichiometric (1 × 1) surface unit mesh with the surface terminated by bridging oxygen (BO) and terminal oxygen (TO) sites, with a mixture of water molecules and hydroxyl groups (OH⁻) occupying the TO sites. An additional hydration layer is observed above the TO site, with three distinct water adsorption sites each having well-defined vertical and lateral locations. Rb⁺ specifically adsorbs at the tetradentate site between the TO and BO sites, replacing one of the adsorbed water molecules at the interface. There is no further ordered water structure observed above the hydration layer. Structural displacements of atoms at the oxide surface are sensitive to the solution composition. Ti atom displacements from their bulk lattice positions, as large as 0.05 Å at the rutile (1 1 0)-DIW interface, decay in magnitude into the crystal with significant relaxations that are observable down to the fourth Ti-layer below the surface. A systematic outward shift was observed for Ti atom locations below the BO rows, while a systematic inward displacement was found for Ti atoms below the TO rows. The Ti displacements were mostly reduced in contact with the RbCl solution at pH 12, with no statistically significant relaxations in the fourth layer Ti atoms. The distance between the surface 5-fold Ti atoms and the oxygen atoms of the TO site is 2.13 ± 0.03 Å in DIW and 2.05 ± 0.03 Å in the Rb⁺ solution, suggesting molecular adsorption of water at the TO site to the rutile (1 1 0) surface in DIW, while at pH 12, adsorption at the TO site is primarily in the form of an adsorbed hydroxyl group.     

Adsorption of water molecules on yttrium barium cuprate superconductors

Gravimetry and thermogravimetric analysis were used to study the adsorption of water molecules on the high temperature superconductor YBa₂Cu₃O₇ at room temperature. It was found that water adsorption subdivides into surface adsorption and bulk adsorption, which starts after the formation at the surface of a physically bound water layer no less than 65–100 Å thick. During bulk adsorption, H₂O molecules diffuse from this surface layer to the lattice, where they form four bound states with desorption temperatures of ～208, 330, 370, and 775°C and heats of formation of 38, 99, 72, and 68 kJ/mol, respectively, and mainly occupy interstitial sites of the intermediate layers. The presence of molecules in the lattice does not affect either the superconducting transition temperature or resistance to direct current; however, it results in an increase in the surface resistance. The resistance to direct current increases due to the formation of dielectric inclusions of other phases.     

CO2 adsorption and reaction on Fe(111): An angle resolved photoemission (ARUPS) study

Molecular CO₂ adsorption is observed on an Fe(111) surface at 85 K. For the main fraction of molecules the relative binding energies of the valence ion states as determined by ARUPS are consistent with those in the gas as well as in the condensed phase, and indicate that the electronic structure of that fraction of adsorbed molecules is only slightly distorted upon adsorption. There is a fraction of adsorbed molecules at 85 K that can be identified as bent, anionic CO₂⁻ species. While the weakly adsorbed, linear CO₂ molecules desorb at low temperature, the CO₂⁻ species is stable up to 160–180 K. The latter is proposed to be a precursor to dissociation. Above this temperature adsorbed carbon monoxide and oxygen are observed on the surface, and at room temperature the CO₂⁻ signals have disappeared. Heating above room temperature dissociates the CO molecules into carbon and oxygen.     

双酚A在氧化石墨烯表面吸附的分子动力学模拟

双酚A(bisphenol A,BPA)是一种内分泌干扰物,会对机体多方面产生不良影响,包括生殖系统、神经系统、胚胎发育等.因此,在水环境中如何检测和去除BPA显得尤为重要.实验研究表明,氧化石墨烯(graphene oxide,GO)对BPA具有优异的吸附去除性能,但在分子层面的吸附机制尚不清楚.分子动力学模拟,能提供BPA在GO表面的动态吸附过程以及吸附构象等详细信息,可以弥补实验的不足.本文利用GROMACS分子动力学模拟软件,系统模拟了BPA在含GO的水溶液中的吸附过程,并计算了吸附自由能.结果显示:所有的BPA均被吸附在GO两侧,通过分析BPA的吸附构象以及与GO的相互作用,发现π-π疏水作用对吸附起主导作用,且显示出很好的稳定性,而静电和氢键作用增加了GO的吸附能力.通过自由能计算,BPA在GO表面的结合能达30 k J/mol,远大于水分子的5 k J/mol.这些结果进一步证实GO对BPA具有很强的吸附能力以及GO作为吸附剂在水溶液中去除BPA的可行性.     

Hydrogen bonds at silica–CO2 saturated water interface under geologic sequestration conditions

To investigate the effects of sequestration condition on hydrogen bonds between mineral and water, molecular dynamics simulations have been performed. The simulations were conducted at conditions related with geologic sequestration sites: pressure (3.1–32.6 MPa), temperature (318 and 383 K), salinity (0–3 M), salt (NaCl and CaCl₂) and silica surface models Q² (geminal), Q³ (isolated) and amorphous Q³. The hydrogen bonds were classified into four types: silica–silica, silica–dissolved CO₂, silica–water as donors and silica–water as acceptors. The mean numbers of hydrogen bonds for each type were analysed. The results show that: (1) silica surface silanol groups do not form H-bonds with dissolved CO₂ molecules in water (brine); (2) The mean number of hydrogen bonds between silanol groups follows the order: Q² > amorphous Q³ > Q³; (3) The mean number of hydrogen bonds between silanol and water molecules follows the order: Q³ > amorphous Q³ > Q².     

Structures of water molecular nanotube induced by axial tensile strains

Five well-ordered nano-ice structures embedded in carbon nanotubes are obtained in this study. These five nano-ice phases all exhibit single walled tubular morphologies, including the pentagon, hexagon ice nanotubes whose structures are quite different from bulk ice. Our simulation results indicate that water molecules tend to rearrange into surface ring structures to reduce the number of free OH groups. The structural behavior of these ice nanotubes inside CNTs subject to axial stress is also investigated. The ice nanotubes tend to be drawn to ice nanorings or ice nanospring during the mechanical stretching. The distribution function exhibits typical order-to-disorder transition of the water network confined in carbon nanotube during the stretching. By analysis, we suggest that it is unlikely that additional water molecules will enter the tubes because of the increased volume available if the tubes are stretched at contact with a water reservoir.     

Molecular beam studies of ethanol oxidation on Pd(110)

The adsorption and decomposition of ethanol on Pd(110) has been studied by use of a molecular beam reactor and temperature programmed desorption. It is found that the major pathway for ethanol decomposition occurs via a surface ethoxy to a methyl group, carbon monoxide and hydrogen adatoms. The methyl groups can either produce methane (which they do with a high selectivity for adsorption below 250 K) or can further decompose (which they do with a high selectivity for adsorption above 350 K) resulting in surface carbon. If adsorption occurs above 250 K a high temperature (450 K) hydrogen peak is observed in TPD, resulting from the decomposition of stable hydrocarbon fragments. A competing pathway also exists which involves C---O bond scission of the ethoxy, probably caused by a critical ensemble of palladium atoms at steps, defects or due to a local surface reconstruction. The presence of oxygen does not significantly alter the decomposition pathway above 250 K except that water and, above 380 K, carbon dioxide are produced by reaction of the oxygen adatoms with hydrogen adatoms and adsorbed carbon monoxide respectively. Below 250 K, some ethanol can form acetate which decomposes around 400 K to produce carbon dioxide and hydrogen.     

Anomalous behavior of proton zero point motion in water confined in carbon nanotubes

The momentum distribution of the protons in ice Ih, ice VI, high density amorphous ice, and water in carbon nanotubes has been measured using deep inelastic neutron scattering. We find that at 5 K the kinetic energy of the protons is 35 meV less than that in ice Ih at the same temperature, and the high momentum tail of the distribution, characteristic of the molecular covalent bond, is not present. We observe a phase transition between 230 and 268 K to a phase that does resemble ice Ih. Although there is yet no model for water that explains the low temperature momentum distribution, our data reveal that the protons in the hydrogen bonds are coherently delocalized and that the low temperature phase is a qualitatively new phase of ice.     

Entropy-controlled site occupation of CO adsorbed on Ni(100)

The adsorption of CO on a Ni(100) surface has been studied by FT-IRAS in the temperature range from 85 K to 300 K. At 300 K and for =0.5, the CO molecules are predominantly adsorbed in on-top sites with only a minor fraction located at two-fold bridge sites. Measurements on a Ni(100) surface pre-covered with sulphur, oxygen and carbon indicate that the occupation of bridge sites may be caused by small amounts of surface impurities. The relative broadness of the infrared bands is explained by CO molecules occupying intermediate positions at domain walls. Upon lowering the temperature, the bridge sites are increasingly occupied at the expense of terminal sites. This process is completely reversible and is explained by a contribution of the hindered translations of the adsorbed CO molecules to the entropy. At 85 K and for low initial coverages, we observe an unusual high CO stretching frequency at 2205 cm^–1 which cannot be explained at present.     

基于第一性原理的石墨吸附一氧化碳倾向性研究

利用基于量子力学的第一性原理计算方法,从微观角度研究煤层对一氧化碳气体的吸附机理.根据煤层的基本成分及结构特点,用结构类似的石墨模拟复杂的煤层,建立石墨吸附一氧化碳分子的模型,讨论石墨表面的三种高对称吸附位置,分别是顶位（top位）、桥位（bridge位）、洞位（hollow位）对一氧化碳分子的吸附.结果表明：当一氧化碳分子垂直于石墨表面,且碳原子端靠近碳层时,在石墨（001）表面的桥位（bridge位）有较强的吸附能.     

Density functional theory investigation of carbon monoxide adsorption on the kaolinite(001) surface

Carbon monoxide(CO) is a gaseous pollutant with adverse effects on human health and the environment. Kaolinite is a natural mineral resource that can be used for different applications, including that it can also be used for retention of pollutant gases. The adsorption behavior of carbon monoxide molecules on the(001) surface of kaolinite was studied systematically by using density-functional theory and supercell models for a range coverage from 0.11 to 1.0 monolayers(ML). The CO adsorbed on the three-fold hollow, two-fold bridge, and one-fold top sites of the kaolinite(001) was tilted with respect to the surface. The strongest adsorbed site of carbon monoxide on the kaolinite(001) surface is the hollow site followed by the bridge and top site. The adsorption energy of CO decreased when increasing the coverage, thus indicating the lower stability of surface adsorption due to the repulsion of neighboring CO molecules. In addition to the adsorption structures and energetics, the lattice relaxation, the electronic density of states, and the different charge distribution have been investigated for different surface coverages.     

Interaction of water molecules with defective carbonaceous clusters: An ab initio study

First-principle calculations are used to study the interaction of water molecules with carbonaceous clusters containing single carbon atom vacancy, similar to those which may be found in soot nanoparticles. It is shown that the dissociative adsorption of one water molecule at the vacancy site may lead to the formation of a “ketone-like” structure which can then act as a nucleation center for additional water molecules. Such a mechanism can thus participate in the hydrophilic behavior of soot primary particles although it appears less favorable than water nucleation around more hydrophilic sites such as carboxyl or hydroxyl groups.     

Structural Evolution of Compressing Amorphous Ice

Molecular dynamics simulation is employed to study structural evolution during compressing low density amorphous ice from one atmosphere to 2.5 GPa. The calculated results show that high density amorphous ice is formed under intermediate pressure of about 1.0GPa and O-O-O angle ranges from about 83°to 113° and O-H…O is bent from 112° to 160°The very high density amorphous ice is also formed under the pressure larger than 1.4 GPa and interstitial molecules are found in 0.3-0.4 A just beyond the nearest O-O distance. Low angle O-H… O disappears and it is believed that these hydrogen bonds are broken or re-bonded under high pressures.     

Photoelectron spectroscopy for probing surface reactions at the CO/K/Cu(1 1 5) interface

The adsorption of carbon monoxide on the potassium modified Cu(1 1 5) surface was investigated using photoelectron spectroscopy based on synchrotron radiation. From detailed analysis of the 1s core levels in combination with existing knowledge, the assignment of surface species is performed. It is demonstrated that in dependence of the alkali coverage, several adsorption states of CO are present on the interface at 135 K. From the temperature dependence of the C 1s and O 1s profiles it is established that surface reactions based on CO dissociation start from 223 K over an interface with a potassium coverage close to half a complete K overlayer. The role of potassium as a reordering environment of adsorbed CO, leading to molecule dissociation and disproportionation is proposed. It is observed that a higher density of potassium on the substrate surface blocks adsorption sites for incoming CO molecules and no dissociation takes place.     

分子动力学模拟方解石和白云石润湿性

利用分子动力学模拟研究油水分子在方解石和白云石表面的吸附,分析体系的平衡构型、相对浓度、径向分布函数和吸附能,研究方解石和白云石的亲水性并对比二者差异.根据油水分子吸附规律分析方解石/白云石-油水体系作用机理.研究表明：白云石-油水体系更易达到热力学稳定状态并且体系更加稳定;方解石和白云石表面均能够优先吸附水分子并在表面形成双层结构的水膜.其中,白云石表面对水分子吸附强度大于方解石;稳定吸附过程分为两步：范德华力、静电力和O（CaCO₃,CaMg（CO₃）₂）-H（H₂O）氢键共同影响下水分子向晶体表面移动并吸附形成紧密吸附层;O（H₂O）-H（H₂O）氢键作用下游离的H₂O向晶体表面靠近形成扩散层.从分子尺度解释方解石/白云石亲水特性,为碳酸盐岩储层润湿性研究奠定理论基础.