Chemieal Strueturcs and Adsorptive Behaviors of Superplastieizers on β-C2S

The chemical structures of four types of superplasticizers （SPs） and their adsorptive behaviors on β-C2S were investigated. The adsorption properties of SPs on β-C2S were measured and the relationship between the adsorption quantity and the specific surface of β-C2S was analyzed. The experimental results show that the adsorption quantity increases with the surface area increase of β-C2S, but the adsorption quantity per surface area is similar, which means that the main adsorbent is β-C2S itself. Polycarboxylic ester （PCE） showed the highest adsorption amount on β-C2S, followed by β-naphthalene sulfonates （NSF） and formaldehyde-acetone condensates sulfonates （FAS）, amino sulphonate （AS） showed the least adsorption amount on β-C2S. PCE affected the surface potential of β-C2S particles in water differently in comparison with other types of SPs. The adsorption capacity of SPs on β-C2S is determined by factors such as molecular structure, functional groups and molecular weight of SPs.     

Thermodynamics and density functional theory study of potassium dichromate interaction with galena

The adsorption heat and reaction rate constant of potassium dichromate on the surface of galena were studied. The results indicate that potassium dichromate tends to adsorption on the galena surface. The reaction order is only 0.08385, suggesting that the concentration of potassium dichromate has little influence on its adsorption on the galena surface. In addition, the simulation of CrO2 4- adsorption on the PbS （100） surface in the absence and presence of O2 was carried out by density functional theory （DFT）. The calculated results show that CrO2 4- species adsorb energetically at the Pb-S bond site, and the presence of O2 can enhance this adsorption.     

Calculation of electron structure by density function theory and electrochemical process of surface （100） of FeS2

The electron structure of FeS2 surface (100) was computed by DFT (density function theory) and the process of electron transfer in sulfide flotation was simulated through ab-initio calculation. The results show that the interaction between xanthate and FeS2 is controlled by the energy of valence band. The products and degree of the reaction depend on the density of state of valence band and concentration of positive hole in valence band. Interaction between xanthate and pyrite can be changed by modifying the election structure of the surface of pyrite. Xanthate is adsorbed on the surface of intrinsic pyrite. But the amount of xanthate adsorbed on the surface of the pyrite with sulfur vacancy is more than that on the surface of the intrinsic pyrite due to the higher electron and vacancy density. Xanthate is not adsorbed on the surface of pyrite with Fe vacancy because of its high Fermi energy.     

Surface modification of magnesium hydroxide by γ-aminopropyltriethoxysilane

Magnesium hydroxide (MH), which is commonly used as a halogen-free flame retardant filler in composite materials, was modified by silanization reaction with γ-aminopropyltriethoxysilane (γ-APS) in aqueous solution at different pH values (pH range from 8.0 to 12.0). The surface properties of grafted γ-APS on MH surface as a function of solution pH value were studied using elemental analysis, Fourier transform infrared spectroscopy and zeta potential measurement. The results show that hydrolysis and condensation of γ-APS are activated in alkaline solution and lead to multilayer adsorption of γ-APS molecules on the surface of MH. The type of adsorption orientation of γ-APS on MH surface is a function of coverage density that is altered by changing solution pH value. At low coverage density (e.g.55nm-2), γ-APS molecules are preferentially adsorbed to the surface with the silicon moiety towards the surface, and increasing coverage density (e.g.90nm-2) leads to parallel orientation. At an even higher coverage density(e.g.115nm-2), γ-APS molecules bond to the surface with the amino moiety towards the surface.     

Water vapor adsorption in activated carbon modified with hydrophilic organic salts

Five different kinds of hydrophilic organic salts were used to modify commercial activated carbon in order to prepare hydrophilic carbon materials. Properties of the samples were analyzed by surface area analyzer and SEM-EDX. The hydrophilic organic salts with different properties were introduced into activated carbon and significantly affected the properties of the samples.During adsorption experiments, the water vapor adsorption amount in modified samples increases by 0.57-17.12 times in temperature range from 303 to 323 K and at relative pressure below 0.50. Water molecules combined with surface hydrophilic groups through H-bonding exhibit good thermo stability. The effects of temperature, oxygen content and properties of the hydrophilic organic salts on water vapor adsorption were studied. It is indicated that water vapor adsorption in modified samples is mainly affected by the surface oxygen content. The carboxylate radicals in the hydrophilic organic salts greatly affect the micropore structure of the modified samples, while the metal ions in them exhibit limited influence. Different adsorption capacity of modified samples can be explained with the electronegativity of elements presented by Pauling.     

Electronic structure and flotation behavior of monoclinic and hexagonal pyrrhotite

Electronic structures of monoclinic and hexagonal pyrrhotite were studied using density functional theory method,together with their flotation behavior. The main contribution of monoclinic pyrrhotite is mainly from Fe 3d, while that of hexagonal pyrrhotite is from Fe 3d, Fe 3p and S 3s. The hexagonal pyrrhotite is more reactive than monoclinic pyrrhotite because of large density of states near the Fermi level. The hexagonal pyrrhotite shows antiferromagnetism. S—Fe bonds mainly exist in monoclinic pyrrhotite as the covalent bonds, while hexagonal pyrrhotite has no covalency. The main contributions of higest occupied molecular orbital(HOMO) and lowest unoccupied molecular obital(LUMO) for monoclinic pyrrhotite come from S and Fe. The main contribution of HOMO for hexagonal pyrrhotite comes from Fe, while that of LUMO comes from S. The coefficient of Fe atom is much larger than that of S atom of HOMO for hexagonal pyrrhotite, which contributes to the adsorption of Ca OH+ on the surface of hexagonal pyrrhotite when there is lime. As a result, lime has the inhibitory effect on the floatation of hexagonal pyrrhotite and the coefficient of Fe is very close to that of S for monoclinic pyrrhotite. Therefore, the existence of S prevents the adsorption of Ca OH+on the surface of monoclinic pyrrhotite, which leads to less inhibitory effect on the flotation of monoclinic pyrrhotite.     

Chemial Bond and Stability of Adsorption of [Au（ AsS3 ）]^2- on the Surface of Kaolinite

Density function theory and discrete variation method (DFT-DVM) were used to study the adsorption of [Au( AsS3 )]^2- on the surface of kaolinite. The correlation among structure, chemical bond and stability was discussed. Several models were selected with [ Au( AsS3)]^2- in different directions and sites. The results show that the models with gold on the edge of kaolinite basal layer contain pincerlike bond among gold and several oxygen atoms and form strong Au - 0 covalent bond, so these models are more stable than those with gold above or under the layer. The models with gold near to [ AlO2(OH)4] octahedra are more stable than those with gold near to the vacancy withont aluminium. These two stable tendencies in kaolinite- [ Au( AsS3)]^2- are stronger than that in kaolinite-Au systems. The interaction between [ Au( AsS3 )]^2- and kaolinite is stronger than that between gold and kaolinite, and this interaction is strong enough to form the surface complexes.     

Surface modification of magnesium hydroxide by γ-aminopropyltriethoxysilane

Magnesium hydroxide（MH）,which is commonly used as a halogen-free flame retardant filler in composite materials,was modified by silanization reaction with γ-aminopropyltriethoxysilane （γ-APS） in aqueous solution at different pH values （pH range from 8.0 to 12.0）. The surface properties of grafted γ-APS on MH surface as a function of solution pH value were studied using elemental analysis,Fourier transform infrared spectroscopy and zeta potential measurement. The results show that hydrolysis and condensation of γ-APS are activated in alkaline solution and lead to multilayer adsorption of γ-APS molecules on the surface of MH. The type of adsorption orientation of γ-APS on MH surface is a function of coverage density that is altered by changing solution pH value. At low coverage density （e.g. 55 nm^-2）,γ-APS molecules are preferentially adsorbed to the surface with the silicon moiety towards the surface,and increasing coverage density （e.g. 90 nm^-2） leads to parallel orientation. At an even higher coverage density （e.g. 115 nm^-2）,γ-APS molecules bond to the surface with the amino moiety towards the surface.     

Quantum Chemistry Calculation on Oxygen and Nitrogen Adsorption in Carbon Nanotude

Oxygen and nitrogen adsorption in single-walled carbon nanotube (SWCNT) is studied by density fuaction and discrete variational (DFT- DVM ) method. The models of O2 and N2 adsorption in the SWCNT are optimized based on the energy minimization. The calculated results of density of state, populations and energy gaps of the molecular orbitals show that oxygen adsorption in SWCNT increasea the carbon nanotube‘ s electrical conductivity more notably than nitrogen adsorption, which is consistent with the experiment.     

Oxygen Evolution Efficiency and Chlorine Evolution Efficiency for Electrocatalytic Properties of MnO_2-based Electrodes in Seawater

To improve both oxygen evolution efficiency and stability at high temperatures, Mn, Mn+Mo, Mn+Mo+V, and Mn+Fe+V oxide electrodes were prepared on a Ti substrate, with an intermediate layer of IrO_2, by an anodic deposition method. The crystal structure, surface morphology, pore size distribution, specific surface area, and voltammetric charge were then characterized for each electrode. The results demonstrated that for Mn-O electrodes, the preferential orientation of the(100) crystal plane and the mesopore structure played negative roles in the oxygen evolution reaction. On the basis of the electrocatalytic properties of MnO2-based electrodes in seawater, the outer surface voltammetric charge at a scan rate of 500 mV·s-1 was shown to effectively indicate whether oxygen evolution reactions were preferred over chlorine evolution reactions. The Mn-O electrode exhibited oxygen evolution efficiency of only 47.27%, whereas the Mn+Mo, Mn+Mo+V and Mn+Fe+V oxide electrodes displayed oxygen evolution efficiency of nearly 100%. This means that adding Mo, V, and Fe elements to the electrode can improve its crystal structure and morphology as well as further enhancing its oxygen evolution efficiency.     

制备方法对负载型FeS/Al_2O_3催化剂催化性能的影响

用原位合成法、水热法、共沉淀法和浸渍沉淀法分别制备了负载型纳米Fe2O3/Al2O3催化剂前驱体,并进一步将其还原和硫化制成FeS/Al2O3催化剂用于H2S分解制氢的反应中,同时用BET、XRD、TPR和IR等对催化剂或前驱体的比表面积、晶相结构、孔径分布、还原性和吸附性等进行了表征。结果表明,原位合成法制备的FeS/Al2O3催化剂平均粒径较小,比表面积较大,有利于催化剂的还原和硫化,H2S在该催化剂表面形成的化学吸附态较强,H2S容易发生解离,初活性高于其他方法制备的催化剂,反应60 h后催化剂的活性没有出现明显下降。     

方解石表面结构影响水分子吸附的微观机理

为研究方解石表面结构对水分子吸附的影响规律和机理,首先利用分子动力学模拟研究水分子在不同类型、不同尺寸的表面结构处的吸附特征,分析其对水分子吸附的影响规律. 而后利用分子动力学模拟研究水分子在发育表面缺陷的纳米狭缝中的吸附规律,解释纳米狭缝中的水锁现象. 最终,结合悬键特征和表面能理论定量解释水分子在不同表面结构处差异性吸附的机理. 研究结果表明:表面结构对于水分子吸附具有重要影响,水分子优先在表面结构处聚集吸附,吸附强度与密度远高于理想表面处; 表面结构的尺寸对水分子吸附有较大影响,尺寸越大对水分子吸附越强;纳米狭缝中水分子在表面凸起和空位处快速聚集,形成的吸附凸起结合为水膜阻断流动空间,水锁作用明显;空位表面、凸起表面和理想表面对应的悬键密度和表面能依次为7.275 nm^-2和0.734 J/m²、6.716 m^-2和0.721 J/m²、5.098 nm^-2和0.581 J/m². 空位表面和凸起表面具有更多的反应活性位点、更强的反应活性,因此,水分子优先吸附于空位表面和凸起表面.     

The Theoretical Study of O_2 Adsorption on NiTi (100) and (110) Surfaces

1　IntroductionNiTishapememoryalloyhaswidelybeenusedinmanyfieldsduetoitsexcellentmechanicalproperties ,uniqueshapememoryeffectandsuperelasticity .In 1970’s ,thegoodbiocompatibilityofNiTialloywasdiscoveredanditwasfurtherusedforvariousbiomedicalapplica tions ,suchasorthopaedicsurgery ,cardiovascularandgas trointestinalsurgery[1-4] .Thehighmechanicalpropertiesandbiocompatibilityofthebiomedicalmaterialsarenec essaryfortheirefficientuseinhumanbody .Thecorrosionresistanceofthealloyandthetoxicityo…     

Effect of surface modification of activated carbon on its adsorption capacity for NH3

To investigate the effects of carbon surface characteristics on NH3 adsorption, coal-based and coconut shell activated carbons were modified by treatment with oxidants. The surface properties of the carbons were characterized by low temperature nitrogen sorption, by Boehm's titrations and by XPS techniques. NH3 adsorption isotherms of the original and the modified carbons were determined. The results show that the carbons were oxidized by HNO3 and (NH4)2S2O8, and that there was an increase in oxygen containing functional groups on the surface. However, the pore-size distribution of the coal-based carbons was changed after KMnO4 treatment. It was found that the NH3 adsorption capacity of the modified carbons was enhanced and that the most pronounced enhancement results from (NH4)2S2O8 oxidation. Under our experimental conditions, the capacity is positively corrected to the number of surface functional groups containing oxygen, and to the number of micro-pores. Furthermore, an empirical model of the relationship between NH3 adsorption and multiple factors on the carbon surface was fit using a complex regression method.     

The theoretical study of O<Subscript>2</Subscript> adsorption on NiTi (100) and (110) surfaces

The discrete variational Xa method (DV-Xα) within the framework of density-functional theory was applied to study O₂ molecule adsorption on NiTi (100) and (110) surfaces. The bond order and charge distribution between Ti and O atoms for two possible O₂ molecule adsorption ways on NiTi (100) and (110) surfaces were calculated. It is found that the adsorption way for O−O bond perpendicular to NiTi surface is preferred to that for O−O bond parallel to NiTi surface, and O₂ molecule only interacted with one nearest surface titanium atom during the adsorption process. Mulliken population and the partial density of state analysis show that the interaction between Ti and O atoms is mainly donated by O 2p and Ti 4s electrons on NiTi(110) surface, O 2p and Ti 4s, 4p electrons on NiTi(100) surface, respectively. The total density of state analysis shows that NiTi(100) surface is more favorable for O₂ molecule adsorption. HUA Ying-jie: Born in 1966. Funded by the National Natural Science Foundation of China (No. 50081001)     

硫钝化可提高GaSb表面光学性质

由于锑化镓（GaSb）表面存在着大量的氧化物及悬挂键,使得材料具有较高的表面态密度,这将导致GaSb费米能级钉扎,严重限制了其器件的应用和发展。同时,这些氧化物及悬挂键将构成非辐射复合中心,影响表面发光。本文通过酸性饱和S2Cl2溶液（最优钝化时间为5s）对n型GaSb进行表面钝化后发现：该溶液钝化可有效减少GaSb表面的氧化物及悬挂键,改善光学性质。从理论上分析了S2Cl2溶液的钝化机理,同时利用PL、PL mapping、XPS及AFM等测试手段验证了该分析的准确性。另外,与常规的碱性（NH4）2S溶液（最优钝化时间为180s）对比,发现经S2Cl2钝化后样品的单点发光强度是（NH4）2S溶液处理过的样品1.5倍,是未处理样品的25倍。但S2Cl2溶液中含有较高的硫浓度,操作时不宜控制,极易腐蚀GaSb表面,钝化后样品表面有大量单质S析出,其发光均匀性及表面平整度不如（NH4）2S溶液。     

硫化纳米零价铁去除水中三氯乙烯的研究

通过硫化对纳米零价铁 (nZVI) 进行改性, 制备了硫化纳米零价铁 (S-nZVI), 而后对三氯乙烯 (TCE) 进行降 解实验研究。利用 SEM、XRD 对 S-nZVI 进行材料的结构表征, 进而研究不同材料、不同 S/Fe 摩尔比、不同初始 TCE 浓度、不同初始 pH 条件下, S-nZVI 对 TCE 的降解效果。结果表明, S-nZVI 主要成分为 Fe⁰ 并含有少量的 FeS, 制得的 S-nZVI 为球状结构, 表面有片层状的 FeS 生成；当 S/Fe 摩尔比为 0.6, 初始浓度为 20 mg/L 时, TCE 的降解 率为 87.2%, 远高于 nZVI (降解率为 56.4%)。经动力学分析后, S-nZVI 去除 TCE 符合伪二级动力学过程, 表明其降 解过程以化学还原为主。nZVI 经过硫化后提高了材料的电子选择性, 使其成为修复受污染土壤和地下水的有前途 的功能材料。     

菱锌矿－褐铁矿体系浮选研究

通过Ｈｕｌｌｉｍｏｎｄ管浮选、动电位测定等方法研究了菱锌矿－褐铁矿浮选体系中胺和硫化钠作用机理。结果表明，在较高的ｐＨ下，胺通过络合作用吸附于菱锌矿表面，硫化钠与铁质反应生成ＦｅＳ从而活化褐铁矿的浮选并消耗浮选药剂。     

响应面法优化空气氛围下制备S-nZVI对水中Cr(VI)的去除

在空气氛围下制备硫化纳米零价铁（SnZVI）,通过SEM、XRD等进行表征,并对其去除水中Cr（VI）进行研究。以Cr（VI）去除率为响应值建立了4因素5水平的响应面模型。SEM和XRD结果显示S-nZVI具有片状结构,主要成分为Fe⁰并含有少量的FeS和铁氧化物。响应面法分析结果表明模型可信度高,适用于模拟4种因素对S-nZVI去除Cr（VI）的影响。以伪一级、伪二级动力学模型拟合S-nZVI去除Cr（VI）,结果显示伪二级动力学模型R²为0.999拟合度更好,说明S-nZVI对Cr（VI）的去除主要以化学吸附为主,平衡吸附量达到156.3mg/g.