低温下二氧化硅介孔内水的振动性质

利用拉曼谱测量了100 K-303 K温度范围内受限于二氧化硅介孔内水的振动性质. 利用水分子在亲水介孔内, 先径向后轴向的吸附生长特点, 改变孔内界面水和位于孔中心水的相对含量. 发现越接近界面, 水低温相的振动谱越偏离体相六角冰的振动谱. 当界面水层减小到小于两个水分子层厚度时, 界面水在降温过程中不具有晶化行为, 其低温相与体相非晶冰相的拉曼谱主峰位在不同的温区内随温度的变化趋势相同、 连续.     

Molecular mechanism of adsorption/desorption hysteresis: dynamics of shale gas in nanopores

Understanding the adsorption and desorption behavior of methane has received considerable attention since it is one of the crucial aspects of the exploitation of shale gas. Unexpectedly, obvious hysteresis is observed from the ideally reversible physical sorption of methane in some experiments. However, the underlying mechanism still remains an open problem. In this study, Monte Carlo (MC) and molecular dynamics (MD) simulations are carried out to explore the molecular mechanisms of adsorption/desorption hysteresis. First, a detailed analysis about the capillary condensation of methane in micropores is presented. The influence of pore width, surface strength, and temperature on the hysteresis loop is further investigated. It is found that a disappearance of hysteresis occurs above a temperature threshold. Combined with the phase diagram of methane, we explicitly point out that capillary condensation is inapplicable for the hysteresis of shale gas under normal temperature conditions. Second, a new mechanism, variation of pore throat size, is proposed and studied. For methane to pass through the throat, a certain energy is required due to the repulsive interaction. The required energy increases with shrinkage of the throat, such that the originally adsorbed methane cannot escape through the narrowed throat. These trapped methane molecules account for the hysteresis. Furthermore, the hysteresis loop is found to increase with the increasing pressure and decreasing temperature. We suggest that the variation of pore throat size can explain the adsorption/desorption hysteresis of shale gas. Our conclusions and findings are of great significance for guiding the efficient exploitation of shale gas.     

Low-n mesoporous silica films: structure and properties

The properties and structure of mesoporous silica films are investigated. Because of their extremely low refractive index (n=1.14), these films are interesting optical waveguide supports. The films have been synthesized by a template-modified sol–gel process using the triblock copolymer Pluronic P123. A significant dependence of the formed structure on the processing conditions has been revealed, allowing an appreciable structure tuning. One set of processing conditions allows the reproducible synthesis of low-n films. They are optically clear, mechanically and chemically resistant, extremely smooth, and sufficiently thick (1 m). Under other processing conditions a novel mesoporous layer structure was synthesized that has very large and well-defined nanoscopic voids. PACS  61.30.Pa; 68.37.Ps; 78.20.Ci     

Raman spectroscopy: Probing dynamics of water molecules confined in nanoporous silica glasses

In order to explore the influence of nanoscopic confinement on the vibrational properties of H-bonded liquids, we performed a detailed Raman scattering study, as a function of temperature, on water confined in 75 ? and 200 ? pores of a Gelsil glass. A detailed evaluation of the observed changes in the O-H stretching profile has been achieved by decomposing the O-H band into individual components, corresponding to those found for bulk water and associated to different levels of water connectivity. As main result, a similar effect produced by enlarging pore diameter and lowering T has been put into evidence. Again, the “structure-breaker” role of the GelSil glass on physisorbed water is confirmed and shown to be enhanced by the diminishing of the pore size.     

CO2 adsorption on branched polyethyleneimine-impregnated mesoporous silica SBA-15

Adsorption of pure CO₂ on SBA-15 impregnated with branched polyethyleneimine (PEI) has been studied. Materials were prepared by impregnating the pore surface of SBA-15 mesoporous silica with different amounts of branched PEI (10, 30, 50 and 70 wt%). Textural properties, elemental analysis and low angle XRD measurements of the prepared samples showed a progressive pore filling of SBA-15 as PEI loading was increased. Pure CO₂ adsorption isotherms on these modified SBA-15 materials were obtained at 45 °C, showing high adsorption efficiency for CO₂ removal at 1 bar. Chemisorption of CO₂ on amino sites of the modified SBA-15 seems to be the main adsorption mechanism. PEI content of impregnated SBA-15 influences the adsorption capacity of the material, being a relevant variable for CO₂ removal by adsorption. Temperature effect on adsorption was also studied in the range 25-75 °C, showing that temperature strongly influences CO₂ adsorption capacity. Adsorption capacity was also tested after regeneration of the PEI-impregnated SBA-15 materials. Our results show that these branched PEI-impregnated materials are very efficient even at low pressure and after several adsorption-regeneration cycles.     

铌锰锆钛酸铅铁电陶瓷电滞回线的温度和频率响应

研究了Pb［(Zr052Ti048)095(Mn1/3Nb2/3)005］O3 (PMnN_PZT) 铁电陶瓷电滞回线的温度和频率响应,结果显示在高频和室温条件下测试铁电特性时,电滞回线呈现“束腰”形状,而不是通常所看到的方形回线 . 在低频和高温条件下测试时才能观察到正常的方形回线,同时,诸如矫顽场、极化强度、 内偏场这些重要的铁电参数也会随频率和温度发生显著的变化. 剩余极化强度随频率和温度 的大幅增长表明“束腰” 电滞回线有可能是由于缺陷偶极子引起的. 电滞回线形状与温度 和频率存在较强的相关性说明缺陷偶极子存在一特征弛豫时间,缺陷偶极子反转响应速度由 此弛豫时间决定. 关键词： 电滞回线 氧空位 频率响应 温度响应     

Insignificant influence of the matrix on the melting of ice confined in decorated mesoporous silica

For a critical examination of matrix effect on the melting of confined ice, mesoporous silica (SBA-15) are synthesised and decorated with n-Alkyl and aminopropyl groups to tune the surface hydrophobicity. Water contact angle to these decorated surfaces are estimated to be about 100° and 60°, respectively. By examining the melting of ice confined in these decorated samples, we find that the influence of the matrix is indeed not significant. The reported apparent matrix effect is more likely method effect in the determination of pore diameters as was demonstrated in our previous studies (Philos. Mag. 93 (2013), p. 1827).     

One-step synthesis of hydrophobic mesoporous silica and its application in nonylphenol adsorption

Highly CH₃-functionalized mesoporous silica with nearly spherical morphology was synthesized under acidic conditions by co-condensation of two different silica precursors polymethylhydrosiloxane (PMHS) and tetraethoxysilane (TEOS) in the presence of triblock copolymer P123 as template. XRD, N₂ adsorption–desorption, HRTEM, SEM and ²⁹Si MAS NMR were used to identify its highly-ordered mesopore array structure, nearly spherical particle morphology and CH₃ functionalization of the as-synthesized material. The resulting hydrophobic mesoporous silica possessed regular mesochannel arrays, indicating that the introduction of PMHS had little impact on the formation of an ordered mesostructure. Also, PMHS played an important role in morphology control and organic functionalization, ensuring nearly spherical particle morphology and high CH₃ functionalization degree of the obtained mesoporous silica material. As compared with pristine mesoporous silica SBA-15, the hydrophobic mesoporous silica showed the higher adsorption performance when they were used as adsorbents to remove organic pollutant nonylphenol at a very low concentration from aqueous solution.     

Exchange bias of hysteresis loop in the Ising two-dimensional ferromagnet-antiferromagnet structure

A simple analytical model is developed to explain the phenomenon of exchange bias of the hysteresis loop in a two-dimensional ferromagnet-antiferromagnet bilayer. A solution of the magnetic relaxation equation is obtained within the framework of the generalized mean field theory, which describes the shape of the hysteresis loop and shows its dependence on the properties of a model interface in the system under consideration.     

Influence of the intrinsic dynamics of the magnetisation on the hysteresis loop

We present numeric simulations of switching processes in small ferromagnetic particles. The dynamics of these processes and the influence of the dynamics of the applied and internal fields on the magnetization reversal are studied. In particular, the derivative in time of the effective fields influences the hysteresis of these particles. It is shown that fast switching, as is required in high-speed data storage, reduces the coercive field. A dynamically corrected Stoner–Wohlfarth dependence of the nucleation field is introduced for the limit of high-field rates and low damping. Implications of these findings are discussed for both, numerical simulation of hysteretic properties and the interpretation of experimental data.     

Probing the phase transition behavior of acetonitrile confined in mesoporous silica by FT Raman spectroscopy

Phase transitions of acetonitrile confined in mesoporous silica SBA‐15 and mesocellular silica foam (MCF) having different pore diameters of 39.0, 39.9, 28.4, 8.7, and 4.6 nm with corresponding pore openings of 20.9, 12.1, 10.0, 8.7, and 4.6 nm were investigated by FT Raman spectroscopy. Melting and freezing temperature depressions were found for acetonitrile confined in mesoporous silica with pore opening sizes of 20.9, 12.1, 10.0 and 8.7 nm. A thermal hysteresis between the cooling and heating cycles was also observed. It appears that the smaller the pore opening, the larger the depression of melting or freezing temperature. Although two solid ( and ) phases exist in bulk acetonitrile, only the liquid →β phase transition was detected for acetonitrile confined in the nanopores of mesoporous silica. The solid‐to‐solid phase transition was not observed. For the mesoporous silica with the smallest pore size of 4.6 nm, neither the liquid nor the transition was observed for the confined acetonitrile. The results demonstrate that FT Raman spectroscopy is a useful technique for studying the phase transition behavior of organic compounds confined in silica‐based hosts. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface structure effects in the adsorption and desorption of nitric oxide on rhodium

The adsorption, desorption and decomposition of NO on Rh surfaces have been investigated using field electron microscopy (FEM) and thermal desorption spectroscopy (TDS). At 77 K NO is molecularly adsorbed on all surfaces of Rh. At room temperature, however, about 30% of NO adsorbed on the rough surfaces is dissociated. The work function change Δφ due to NO adsorption increases as the surface becomes rougher. The results suggest the following order in Δφ: 0.93 eV = (100) < (111) < (511) < (410) < (331), (533) < (321) < (110) < (650) < (531), (210) = 1.4 eV. Upon heating the tip covered with molecular NO the FEM results suggest that the (321) surface is most active in the NO bond scission. The smooth surfaces are least effective in NO dissociation. The most likely interpretation of the FEM results is that the activity in NO bond scission increases in the following order: (111), (110) < (100), (511) < (650) < (410) < (210) < (331), (533) < (321). These results are discussed in relation to literature data concerning the dissociation of NO on the noble metals of Group VIII.     

Influence of side electric potential on hysteresis loop parameters and electric permittivity in the Rochelle salt

It has been shown that the application of an electric potential to relatively narrow side electrodes of a thin perpendicular parallelepiped Rochelle salt sample plate leads to the disappearance of the hysteresis loop. The effect is permanent and can be observed after the side potential disconnection. Moreover, a reduction of both zero-field longitudinal permittivity maxima at the critical points is visible then. A non-zero remanent polarization and a non-zero coercive field are then able to be observed only at temperatures higher than that of the lower critical point and lower than that of the upper critical one. No corresponding temperature shift in reduced permittivity maxima has been noticed. A transition to below the lower critical point for the next few hours does not lead to restoration of the original properties formerly lost during the side potential application in the ferroelectric phase. Such restoration is possible by annealing the sample above the upper critical temperature.     

Influence of framework silica-to-alumina ratio on the water adsorption and desorption characteristics of MHI-CaX/CaY zeolite

The influence of the framework SiO₂/Al₂O₃ ratio from 2.0 to 10.0 of commercial faujasite-type CaX/CaY zeolite produced by Mitsubishi Heavy Industries Ltd. (MHI) on the water adsorption and desorption characteristics was investigated. Not only the change in electronegativity of the zeolite but the change in pore-size distribution of the zeolite affects the water adsorption and desorption characteristics of the zeolite. We found great differences in isotherms of water between CaY7.0 (SiO₂/Al₂O₃=7.0) and CaY10.0. The differences are mainly caused by the considerable change in pore-size distribution. A step-wise variation was observed in the desorption isotherm of water from CaY10.0 at approximately P/P₀=0.4. This is due to the pore distribution of CaY10.0 being relatively poor in smaller micropores in zeolite structure, since a similar phenomenon is observed in the case of argon adsorption on CaY10.0. In the experiments using a fixed bed, an apparent dependency of HTO dehydration ratio on the flow rate of the purge gas is measured with the CaY10.0 zeolite, while the water desorption from other tested CaX/CaY zeolite is independent of the flow rate of helium purge gas. This indicates that the transfer step of water diffusion through a laminar film appeared as one of the rate-controlling steps in the water desorption from CaY10.0.     

Photo-induced bias of the hysteresis loop in ferrites at room temperature with long-time memory

New photo-magnetic effects with an indefinitely long-time memory are found at room temperature in the epitaxial Mg_0.75Mn_0.21Co_0.04Fe₂O₄ ferrite film. Illumination of the ferrimagnetic material with low-intensity (0.4 W cm⁻²) circularly polarized light with or without a static magnetic field in the Faraday effect geometry results in a number of nonlinear effects in both space and time. In a uniform crystal with cubic symmetry, the long-lived photo-induced magnetization (PIM) with a unidirectional anisotropy appears along the direction of the incoming light. The effects depend on a combination of magnetic field H and the helicity of circularly polarized light σ. Two combinations H⁺,σ⁺ and H⁻,σ⁻ lead to a photo-induced unidirectional anisotropy with a shift of the hysteresis loop along an applied field and a change in loop parameters. The loop contracts by a factor of two, the shift of the mid-point H_sh increases by factor of five surpassing the coercivity H_c, the coercivity H_c1 and remanence M_r1 (for decreasing applied field) reverse the sign, increasing by 9 Oe and reducing by a factor of 4.5, respectively. The effects cannot be erased by a conventional demagnetization (using an AC current that is reduced to zero amplitude), but can be removed using an illumination with two other combinations (H⁺,σ⁻ and H⁻,σ⁺) as well as by heating at temperatures higher than the Curie temperature. This long-lived room-temperature memory effect may arise from the formation of complex photo-induced defects including photo-induced magnetic polarons. The possible mechanisms responsible for the appearance of a room-temperature photo-induced unidirectional anisotropy with a long-lived memory are discussed. These new photo-magnetic effects may find an application in magneto-optical memory devices.     

解吸温度对吸附式制冷系统性能影响的实验研究

吸附式制冷系统作为一种节约型制冷系统受到国内外专家学者的探索研究,以期提高制冷循环COP,加快吸附制冷技术的实用化。本文采用了4A分子筛与铝丝混合吸附剂,与无水乙醇组成吸附工质对,通过实验探究不同解吸温度下的COP以及循环周期的变化情况。实验表明,在实验温度(74~98℃)范围内,随着解吸温度的升高,系统循环COP逐渐增加,但增加的趋势逐渐减小,最大达到0.36;制冷循环周期随着解吸温度的升高而逐渐减小。     

Influence of preliminary treatment of polycrystalline barium titanate on the shape of its hysteresis loop

The relation between the hysteresis loop area of polycrystalline barium titanate and preliminary sample processing is examined. It is shown that the loop area decreases after prolonged action of a dc electric field at increased temperature. This indicates that the dielectric loss tangent is reduced in a sample subjected to this treatment. It would seem that the presence of a large space charge, accumulated in the sample during its polarization at increased temperature, affects and changes its ferroelectric properties.     

Theoretical study of cisplatin adsorption on silica

The adsorption of cisplatin and its complexes, cis-[PtCl(NH₃)₂]⁺ and cis-[Pt(NH₃)₂]²⁺, on a SiO₂(1 1 1) hydrated surface has been studied by the Atom Superposition and Electron Delocalization method. The adiabatic energy curves for the adsorption of the drug and its products on the delivery system were considered. The electronic structure and bonding analysis were also performed. The molecule-surface interactions are formed at expenses of the OH surface bonds. The more important interactions are the Cl-H bond for cis-[PtCl₂(NH₃)₂] and cis-[PtCl(NH₃)₂]⁺ adsorptions, and the Pt-O interaction for cis-[Pt(NH₃)₂]²⁺ adsorption. The Cl p orbitals and Pt s, p y d orbitals of the molecule and its complexes, and the s H orbital and, the s and p orbitals of the O atoms of the hydrated surface are the main contribution to the surface bonds.     

Influence of MgO on structure and optical properties of alumino-lithium-phosphate glasses

MgO doped lithium alumino phosphate glasses (PLA: P₂O₅+Li₂O+Al₂O₃+MgO) were prepared by melt quenching technique. Raman spectra display three significant peaks at 698, 1164 and 1383 cm⁻¹ attributed to: symmetric stretching vibrations of the bridging oxygen (BO) in the P–O–P chains, symmetric stretching vibrations of the PO₂ groups, and the asymmetric vibrations vas(PO₂) of the non-bridging oxygen (NBO) atoms, respectively. Also, the density, molar volumes and ion concentration have been discussed and correlated with the structural changes within the glassy matrix. Some optical constants such as refractive index and dispersion parameters (E_o: single-oscillator energy and E_d: dispersive energy) of the glasses were determined. Finally, the values of the optical band gap for direct and indirect allowed transitions have been determined from the absorption edge studies. It is deduced that the values of E_opt increase with increasing MgO content. It was assigned to structural changes induced from the formation of non-bridging oxygen. The Urbach energy (ΔE) was found to decrease from 0.578 to 0.339 eV with increasing MgO content from 0.5 to 2 mol.