α-Fe_2O_3空心球的水热法制备及其对苯酚的吸附性能

以铁氰化钾、磷酸二氢铵等为反应物,采用水热法合成了α-Fe2O3空心球,并用XRD,TEM,FESEM(场发射扫描电镜)、UV-Vis和低温氮吸附脱附对其进行了表征。结果表明,α-Fe2O3空心球直径在200～560nm之间,其BET比表面积为80m2·g-1,平均孔径为8.5nm。考察了反应时间、反应物用量和反应温度等对α-Fe2O3空心球形貌和大小的影响,提出了其可能的形成机理。研究了室温下α-Fe2O3空心球吸附苯酚的性能,吸附达平衡时,其吸附苯酚的量达97mg·g-1。     

Adsorption and structure of hydrocarbons in MCM-41: a computational study

The adsorption of linear, branched, and cyclic hydrocarbons in MCM-41 is studied using Configurational Bias Monte Carlo simulations. A new computational model for MCM-41 is proposed which, although simple, is able to predict adsorption isotherms which are in agreement with the scarce experimental data. The structure of the adsorbed phase is analyzed and found to be similar to that of studies using small, hard spheres trapped in pores. The adsorption of mixtures is investigated, and the adsorption hierarchy is discussed. The structure of the adsorbed mixture is revealed and shows that all components of the mixture exhibit structure, even if they are only adsorbed in small quantities. Finally, the model is modified to include surface roughness and the effect on the adsorption isotherms and structure of the adsorbed phase is discussed.     

Fast adsorption and separation of bovine serum albumin and lysozyme using micrometer-sized macromesoporous silica spheres

Micrometer-sized silica spheres with bimodal macromesoporous structures are synthesized continuously by a modified gelation technology, and a novel coaxial microfluidic device is applied to control the size of the silica spheres. These spheres are used as a new protein adsorbent to realize fast adsorption and separation of protein mixture. BSA and lysozyme (LYS) are as model proteins with different sizes and pIs. High protein adsorption capacity and rapid adsorption rate have been achieved. Fast separation of a binary mixture of BSA and LYS through a short packed column (50 mm x 4.6 mm id) has also been successfully realized. LYS was selectively adsorbed while BSA flowed through the column in 12 s at a flow rate of up to 5.0 mL/min. As a result, an ultrafast adsorption and separation of BSA and LYS was obtained, showing great potential for applications in fast, large-scale protein separation processes of these monodispersed silica spheres.     

Facile synthesis of bioglass nanospheres for the adsorption of cationic and anionic dyes from aqueous solution

A novel adsorbent, bioglass nanospheres (BGN), has been prepared by a facile process. The BGN were spheres with an amorphous structure and a relatively high specific surface area, as indicated by SEM, transmission electron microscopy, BET, FTIR, and XRD. This paper was aimed at evaluating the adsorption behavior of this new material for the adsorptive removal of cationic (methylene blue, neutral red) and anionic (congo red) dyes from aqueous solution. The effects of the initial dye concentration, contact time, solution pH, and temperature were investigated. The adsorption kinetics showed that the adsorption behavior followed the pseudo-second-order kinetic model. The adsorption isotherm fit well to the Langmuir model. Thermodynamic analyses showed that the adsorption was physisorption, and it was also a spontaneous and endothermic process. The BGN exhibited a good reusability after five consecutive cycles for cationic dyes. In addition, the possible adsorption mechanism was also proposed based on the above experimental results.     

不同酸对介孔二氧化硅球表面形貌和介相结构的影响

在室温、不同酸性条件下合成出微米级球形介孔二氧化硅材料，通过XRD、SEM以及氮气吸附等手段对介孔二氧化硅材料进行了表征。用TEM跟踪不同反应时间介孔二氧化硅球的形成，对这些球颗粒的合成机理进行了讨论，同时探讨了不同酸性条件下介孔二氧化硅表面形貌和介相结构的变化。     

Density functional theory of adsorption of mixtures of charged chain particles and spherical counterions

We propose a microscopic density functional theory to describe nonuniform ionic fluids composed of chain molecules with charged "heads" and spherical counterions. The chain molecules are modeled as freely jointed chains of hard spheres, the counterions are oppositely charged spheres of the same diameter as all segments of chain molecules. The theory is based on the approach of Yu and Wu [J. Chem. Phys. 117, 2368 (2002)] of adsorption of chain molecules and on theory of adsorption of electrolytes [O. Pizio, A. Patrykiejew, and S. Sokolowski, J. Chem. Phys. 121, 11957 (2004)]. As an application of the proposed formalism we investigate the structure and adsorption of fluids containing segments of different length in a slitlike pore.     

Isolation and pre-concentration of basic proteins in aqueous mixture via solid-phase extraction with multi-walled carbon nanotubes assembled on a silica surface

Multi-walled carbon nanotubes (MWNTs) were assembled on a silica surface using a polyelectrolyte-assisted layer-by-layer (LBL) assembly technique. The surface-assembled silica spheres with MWNTs (MWNTs/SiO(2)), which serve as a novel solid-phase extraction sorbent for separation/pre-concentration of basic proteins, was investigated. The adsorption behavior of cytochrome c (cyto-c) by MWNTs/SiO(2) spheres agrees well with the Langmuir adsorption model. A thorough scrutiny of the experimental parameters affecting the adsorption of cyto-c from aqueous solution onto the MWNTs/SiO(2) spheres and its subsequent desorption was carried out. A maximum adsorption capacity of cyto-c was derived as 112 mg (cyto-c) g(-1) (MWNTs). A distinct feature of the MWNTs/SiO(2)-packed micro-column provides clear advantages of minimized flow impedance when operated in a flow system, in addition to better separation efficiency as well as the favorable enrichment capability of proteins, characterized by an enrichment factor of 30 by using 2.0 mL of aqueous solution. The practical applicability of the MWNTs/SiO(2) spheres as a sorbent for the isolation of basic proteins from acidic protein species was demonstrated by effective separation of cyto-c from bovine serum albumin (BSA).     

Morphological and structural evolution of mesoporous silicas in a mild buffer solution and lysozyme adsorption

Mesoporous silicas with various morphologies and structures were synthesized with the aid of 2,2,4-trimethylpentane (TMP) in the presence of nonionic surfactant P123 [(EO)20(PO)70(EO)20] as a structure-directing agent under mild reaction conditions (HAc-NaAc buffer solution, pH 4.4). The ropelike particles formed by end-to-end interconnected nanorods were obtained at a TMP/P123 weight ratio of 0.5. It is noteworthy to mention that the mesoporous nanorods have channels running parallel to the short axis. The silica hollow spheres can be obtained at a higher TMP/P123 weight ratio because of the fusion of the primary nanorods around the interface of the O/W emulsion. Initial synthesis temperatures of 15, 25, and 40 degrees C can lead to mesoporous silicas with highly ordered 2D hexagonal mesostructure, vesicular mesostructure, and mesostructured cellular foams (MCF), respectively. The mesoporous silicas exhibit high adsorption capacity (up to 536 mg g(-1)) and very rapid (<5 min to reach equilibrium) lysozyme immobilization. More importantly, it is revealed that mesoporous silica hollow spheres with rugged surfaces can greatly accelerate the adsorption rate of the enzyme during the adsorption process.     

用实验和模拟计算确定SiO2空心微球的孔径分布

用巨正则系综蒙特卡罗（GCMC）模拟方法结合统计积分方程（SIE）计算了SiO2空心微球球壳上的孔径分布（PSD）.HRTEM、XRD及氮气吸附等实验测试表明,SiO2空心微球的球壳上有无序的介孔孔道.在模拟中,基于实验数据,将SiO2空心微球模型化为具有一定孔径分布的园柱孔,流体模型化为Lennard-Jones(LJ)球,流体分子和孔壁间的相互作用采用Wang等人[10]最近提出的完全解析的势函数描述.模拟结果显示,用孔径分布拟合的吸附数据和实验吸附等温线吻合良好,说明PSD能够十分有效地表示SiO2空心微球的微孔结构.     

添加聚乙二醇对酚醛树脂基球形活性炭结构和性能的影响

在以线型树脂为原料制备球形活性炭的过程中存在炭难以活化以及所制备活性炭比表积小的问题,本工作对针对此问题,提出了在线型酚醛树脂中添加聚乙二醇作为造孔剂的新方法来制备球形活性炭。结果表明：在线型酚醛树脂中添加17．6％的聚乙二醇中所制备的球形炭具有良好的活性特性;深度活化的球形活性炭球表炭球形完整,结构均匀,与未添加造孔剂的试样相比,该球形活性炭具有比表面积大,中孔率较大以及对肌酐的平衡吸附量大的特点。     

Structure of nonpolarizable water/nitrobenzene interface: potential distribution, ion adsorption, and interfacial tension

Adsorption of hydrophobic and hydrophilic ions at the nonpolarizable interface between two immiscible electrolyte solutions was investigated. The results were analyzed in three different models: (i) Gouy-Chapman model, (ii) ions as hard spheres, and (iii) ion pair formation at the interface. In the Gouy-Chapman model, an analytical expression for the interfacial tension was obtained. It predicts that interfacial tension should be proportional to the square root of the electrolyte concentration, which does not agree with experimental data. Modeling ions as hard spheres only slightly improves the agreement. The third model of interfacial ion pairing as the main origin of adsorption was analyzed using the amphiphilic isotherm (Markin-Volkov isotherm). A good agreement between ion-pairing theory and experimental values was achieved. The MV isotherm takes into account the limited number of adsorption sites, final size of molecules, complex formation at the interface, and interaction between adsorbed particles. The analysis revealed repulsion between adsorbed tetraalkylammonium ions at the nitrobenzene/water interface and demonstrated linear dependence between adsorption site area and the size of a molecule.     

Polyion adsorption onto catanionic surfaces. A Monte Carlo study

The adsorption of a single and negatively charged polyion with varying flexibility onto a surface carrying both negative and positive charges representing a charged membrane surface has been investigated by using a simple model employing Monte Carlo simulations. The polyion was represented by a sequence of negatively charged hard spheres connected with harmonic bonds. The charged surface groups were also represented by charged hard spheres, and they were positioned on a hard surface slightly protruding into the solution. The surface charges were either frozen in a liquidlike structure or laterally mobile. With a large excess of positive surface charges, the classical picture of a strongly adsorbed polyion with an extended and flat configuration emerged. However, adsorption also appeared at a net neutral surface or at a weakly negatively charged surface, and at these conditions the adsorption was stronger with a flexible polyion as compared to a semiflexible one, two features not appearing in simpler models containing homogeneously charged surfaces. The presence of charged surface patches (frozen surface charges) and the ability of polarization of the surface charges (mobile surface charges) are the main reasons for the enhanced adsorption. The stronger adsorption with the flexible chain is caused by its greater ability to spatially correlate with the surface charges.     

Agglomeration of alumina submicronparticles by silica nanoparticles: application to processing spheres by colloidal route

In aqueous media, heterocoagulation between submicronic alumina (400 nm) and nanometric silica (25 nm) leads to the adsorption of silica on the alumina surface. By controlling the coverage rate of alumina particles, this adsorption destabilizes the suspension that leads to a very porous network of agglomerated particles. This work shows that the structure is all the more open as the density of charge carried by the two oxides is high and the ionic strength in the suspension low. From such a flocculated suspension, a new colloidal process to fabricate ceramic spheres is proposed which is based on a size increase of agglomerates. Under a controlled rotation of the vessel, electrostatic attraction between the surface charges of opposite polarity induces a size increase of agglomerates until the formation of spheres occurs. It has been shown that the mechanism of growth is poisoned by species adsorbed such as ions. Nevertheless, this new process proves very promising because it leads to a narrow size distribution of spheres by colloidal way, which can be subsequently consolidated by sintering, with a smooth surface.     

Self‐Assembled Poly(N‐methylaniline)–Lignosulfonate Spheres: From Silver‐Ion Adsorbent to Antimicrobial Material

Self‐assembled poly(N‐methylaniline)–lignosulfonate (PNMA–LS) composite spheres with reactive silver‐ion adsorbability were prepared from N‐methylaniline by using lignosulfonate (LS) as a dispersant. The results show that the PNMA–LS composite consisted of spheres with good size distribution and an average diameter of 1.03–1.27 μm, and the spheres were assembled by their final nanofibers with an average diameter of 19–34 nm. The PNMA–LS composite spheres exhibit excellent silver‐ion adsorption; the maximum adsorption capacity of silver ions is up to 2.16 g g^?1 at an adsorption temperature of 308 K. TEM and wide‐angle X‐ray results of the PNMA–LS composite spheres after absorption of silver ions show that silver ions are reduced to silver nanoparticles with a mean diameter of about 11.2 nm through a redox reaction between the PNMA–LS composite and the silver ions. The main adsorption mechanism between the PNMA–LS composite and the silver ions is chelation and redox adsorption. In particular, a ternary PNMA–LS–Ag composite achieved by using the reducing reaction between PNMA–LS composite spheres and silver ions can be used as an antibacterial material with high bactericidal rate of 99.95 and 99.99 % for Escherichia coli and Staphylococcus aureus cells, respectively.     

Preparation, Properties and Mechanism of Inhomogeneous Calcium Alginate Ion Cross-linking Gel Microspheres

Inhomogeneous calcium alginate ion cross-linking gel microspheres,a novel ion absorbent,were prepared by dropping a sodium alginate solution to a calcium chloride solutioin via an electronic droplet generator.Calcium alginate microspheres have uniform particle sizes.a smooth surface and a microporous structure.The electrode probe reveals the inhomogeneous distribution of calcium ions with the highest concentration on the surface,and the lowest concentration in the cores of the spheres.As a novel ion adsorbent,calcium alginate gel microspheres have a lower limiting adsorption mass concentration,a higher enrichment capacity and a higher adsorption capacity for Pb^2 than usual ion exchange resins.The highest percentage of the adsorption is 99.79%.The limiting adsorption mass concentration is 0.0426mg/L.The adsorption capacity for Pb^2 is 644mg/g,Calcium alginate gel microspheres have a much faster ion exchange velocity than D418 chelating resin and D113 polyacrylate resin.The moving boundary model was employed to interpret the ion exchange kinetics process,which indicates that the ion exchange process is controlled by intraparticle diffusion of adsorbable ions.So the formation of inhomogeneous gel microspheres reduces the diffusion distance of adsorbable ions within the spheres and enhances the ion exchange velocity.Alginate has a higher selectivity for pb^2 than for Ca^2 and the selectivity coefficient KCa^Pb is 316. As an ion cross-linking gel,calcium alginate inhomogeneous microspheres can effectively adsorb heavy metal Pb^2 at a higher selectivity and a higher adsorption velocity.It is a novel and good ion adsorbent.     

Signatures of non locality for short-ranged wetting at curved substrates

The binding potential for wetting near planes, spheres, and cylinders in systems with short-ranged forces is shown to have a universal geometrical structure. This arises from the nonlocal nature of the interfacial interactions and is exactly described by a recently proposed binding potential functional, which provides a systematic framework for studying wetting at arbitrarily shaped substrates. The corrections to the equilibrium wetting layer thickness induced by nonlocality are comparable to those arising from a Tolman length and lead to diverging terms in the total mass adsorption.     

Adsorption of Fluids in Pores Formed between Two Hard Cylinders

We study adsorption in pores with curved hard walls that are made of two uniaxial cylinders by using a density functional approach. Two cases are considered: adsorption of hard spheres and adsorption of a Lennard-Jones fluid. In the case of hard spheres, we perform a comparison with the results of grand canonical ensemble Monte Carlo data. This comparison indicates that the applied approach is capable of reproducing the fluid structure quite satisfactorily. For hard spheres, we also make a comparison of the total adsorption effect (expressed as the average density of a confined fluid) inside pores with curved walls with that evaluated for a slitlike pore. We have found that the differences between adsorption in pores with curved walls and in slits with the same wall-to-wall distance are quite low. The calculations for the Lennard-Jones fluid have been concerned with the investigation of the capillary evaporation and with the evaluation of phase diagrams for different pores, including slitlike pores. We have found that the curvature of the pore walls shifts the transition toward lower values of the chemical potential and increases slightly the value of the critical temperature in comparison with the values obtained for a slitlike pore. Copyright 2000 Academic Press.     

Regenerable Fe3O4-decorated chitosan/carboxymethyl cellulose hollow spheres for adsorption and catalytic degradation of dyes

Biopolymer hollow spheres have shown great promise for wastewater treatment due to their unique structure and properties. However, challenging issues like low efficiency and poor recyclability still exist for most hollow spheres. In this study, the modification of chitosan/carboxymethyl cellulose (CS/CMC) with Fe₃O₄ nanoparticles for the formation of bifunctional CS/CMC-Fe₃O₄ hybrid hollow spheres were prepared using a facile two stage mixing route, which exhibited excellent adsorption and catalytic degradation of dyes. The removal ability of the synthesized hollow spheres towards acid blue-113 (AB) and reactive orange C-3R (RO) using persulfate oxidation system was greatly improved compared with single adsorption or catalysis. The removal ratio of AB and RO could reach up to 96.2 and 97.5%, respectively. The kinetic process conformed to the quasi-second-order kinetics and the adsorption process was the controlling step of dye removal. In addition, the created hollow spheres showed excellent environmental adaptability and regenerative capability. This study provides a convenient and practical method for catalyst loading on biomass hollow spheres, which has perspective applications in wastewater purification.

     

Role of Surface Molecular Architecture and Energetics of Hydrogen Bonding Sites in Adsorption of Polymers and Surfactants

Hydrogen bonding is generally thought to be an ubiquitous adsorption mechanism, which often foils selective adsorption schemes. Through investigation of hydrogen bonding energy and its dependence on surface molecular architecture, it may be possible to develop new methodologies to control the adsorption of surfactants and polymeric flocculants, depressants, and dispersants used in particulate processing industries. A model system using St?ber silica spheres and polyethylene oxide, a polymer known for its ability to form hydrogen bonds, was examined. The effect of two different surface treatments of the silica particles, calcination and rehydroxylation, upon the adsorption of two polymer molecular weights was studied. The adsorption behavior was then linked to the respective surface structures via characterization of the surfaces using FTIR, NMR, and Raman techniques. In this paper role of hydrogen bonding sites and surface architecture on adsorption is discussed. Copyright 2000 Academic Press.     

Synchronous multilayered adsorption of macrocations and macroanions on colloidal spheres. Influence of foreign salt and basicity or acidity of the macroions

The influence of foreign salt, the basicity or the acidity of macroions and the equivalency of the number of ionic groups of macrocations and macroanions upon alternate multiple adsorption on surfaces of colloidal silica (CS91, 110 nm in diameter) and polystyrene spheres (D1A19, 220 nm) have been studied by electrophoretic light scattering measurements. The macrocations used were poly(4-vinyl-N-n-butyl pyridinium bromide (C4PVP, strongly basic), poly(4-vinyl-N-ethyl pyridinium bromide (C2PVP, strongly basic) and poly(allylamine) (PAL, weakly basic). Sodium poly(styrene sulfonate) (NaPSS, strongly acidic) and sodium polyacrylate (NaPAA, weakly acidic) were used as macroanions. The alternate adsorption disappears even in the presence of a small amount of sodium chloride. The alternate multiple adsorption takes place on the addition of C4PVP first and NaPSS next, PAL first and NaPAA next, NaPAA first and C4PVP next, and NaPAA first and PAL next on the CS91 spheres. The influence of the equivalency of the number of ionic groups of C2PVP and NaPAA has been studied for the adsorption on the D1A19 spheres. The synchronous delicate balancing of the electrostatic interactions among the macrocations, the macroanions and the surfaces of the colloidal spheres is important for the alternate multiple adsorption.