Polyvinylpyrrolidone-assisted ultrasonic synthesis of SnO nanosheets and their use as conformal templates for tin dioxide nanostructures

Single crystalline SnO nanosheets with exposed {001} facets have been prepared by an ultrasonic aqueous synthesis in the presence of polyvinylpyrrolidone, which hinders the spontaneous formation of the truncated bipyramidal SnO microcrystals and exfoliate them into layer-by-layer hierarchical structures and further into separate SnO nanosheets. The SnO nanosheets have been used as conformal sacrificial templates converted into polycrystalline SnO(2), as well as layered SnO/SnO(2) nanostructures, by calcination in air. The concept of fabrication of two-dimensional tin oxide nanostructures demonstrated here may be relevant for the crystal design of layered materials, in general.     

Preparation of band gap tunable SnO2 nanotubes and their ethanol sensing properties

SnO(2) nanotubes have been prepared via a facile hydrothermal method at low temperatures using polycarbonate (PC) membrane as a hard template. The walls of as-prepared SnO(2) nanotubes are composed of fine nanocrysalline particles and the size of SnO(2) nanocrystals could be modified by changing reaction temperature. Formation mechanism of SnO(2) nanotubes is also discussed according to the experimental results. Cathodoluminescence properties of the SnO(2) product indicated that the band gap of the nanostructures increase from 3.75 eV with a particle size 5.6 nm to 3.99 eV with a particle size 3.3 nm. The as-prepared SnO(2) nanotubes were found to show enhanced gas-sensing activity and may be used as a candidate for the fabrication of gas sensors.     

Fabrication of highly porous and micropatterned SnO2 films by oxygen bubbles generated on the anode electrode

The fabrication process of highly porous SnO(2) thick film by reaction between tin ions and oxygen gas generated by an anodic applied potential on substrates in SnCl(2) aqueous solution is reported; moreover, we succeeded in forming porous SnO(2) micropatterns through site-selective deposition on a Pt-patterned F-doped SnO(2)(FTO) coated substrate .     

Biogenic synthesis of tubular SnO2 with hierarchical intertextures by an aqueous technique involving glycoprotein

Tetragonal SnO2 with hierarchical interwoven structures was prepared by a convenient soaking technique followed by a calcination treatment over 823 K. On the basis of the biomaterial eggshell membrane (ESM) being immersed in aqueous Sn colloid medium and a calcination treatment in succession, SnO2 nanocrystallites with a size of about 5 nm were formed, assembled into tubular fibers, and further intertwisted to construct hollow interconnective fibrous meshworks. With the biomaterial ESM serving as the physical substrate, chemical revulsant, and capping agent, the formation and assembly of hierarchical SnO2 nanomaterials should be under the control of glycoprotein contained in the ESM fiber mantle and directed by the interactions between the glycoprotein macromolecules (containing carboxyl, hydroxyl, and amino groups, etc.) and Sn colloid ingredients of the Sn impregnant. The unique hierarchical SnO2 nanomaterials of structural particularity and complexity are expected to find potential applications in gas sensors, photocatalysts, and dye-sensitized solar cells, etc.     

利用SnO2:Sb干凝胶部分升华产物处理ZnS:Mn荧光粉

以SnCl2•2H2O、SbCl3为原料, 通过溶胶-凝胶法制备SnO2:Sb干凝胶. 利用干凝胶氧化过程中的部分升华产物对新制的ZnS:Mn荧光粉进行了表面处理. 在固定氧气流量和氧化时间的条件下, 考察了SnO2:Sb干凝胶与ZnS:Mn荧光粉的质量比和氧化温度对处理后荧光粉电阻率的影响. 当干凝胶粉与荧光粉的质量比为3.0, 氧化温度为500 ℃处理后荧光粉的电阻率明显下降. 对处理后的荧光粉进行了室温光致荧光(PL)光谱、X射线衍射(XRD)以及透射电镜(TEM)分析. 结果表明对荧光粉进行表面处理没有改变荧光粉的光致发光性质和晶体结构.     

Electrodeposition of SnO2 nanocrystalline thin film using butyl-rhodamine B as a structure-directing agent

<正>Porous SnO_2 nanocrystalline thin films were successfully electrodeposited from an oxygen-saturated acid aqueous solution of SnCl_2 containing different concentrations of butyl-rhodamine B(BRhB) at 70℃.BRhB with substitute of amidocyanogen can be dissolved in the acid deposition solution,where HCl was added to suppress hydrolysis of SnCl_2.So it was used as a structure-directing agent to promote the crystal growth of SnO_2.The formed porous morphology and tetragonal rutile crystalline structure of the electrodeposited thin films were controlled by the addition of BRhB with different amounts.     

Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts

The importance of tin oxide (SnO(x)) to the efficiency of CO(2) reduction on Sn was evaluated by comparing the activity of Sn electrodes that had been subjected to different pre-electrolysis treatments. In aqueous NaHCO(3) solution saturated with CO(2), a Sn electrode with a native SnO(x) layer exhibited potential-dependent CO(2) reduction activity consistent with previously reported activity. In contrast, an electrode etched to expose fresh Sn(0) surface exhibited higher overall current densities but almost exclusive H(2) evolution over the entire 0.5 V range of potentials examined. Subsequently, a thin-film catalyst was prepared by simultaneous electrodeposition of Sn(0) and SnO(x) on a Ti electrode. This catalyst exhibited up to 8-fold higher partial current density and 4-fold higher faradaic efficiency for CO(2) reduction than a Sn electrode with a native SnO(x) layer. Our results implicate the participation of SnO(x) in the CO(2) reduction pathway on Sn electrodes and suggest that metal/metal oxide composite materials are promising catalysts for sustainable fuel synthesis.     

Maleic Anhydride Crosslinked Alginate-Chitosan Blend Membranes for Pervaporation of Ethylene Glycol-Water Mixtures

Calcium alginate-chitosan (CA/CS) blended membranes were prepared and crosslinked with maleic anhydride (MA) for the pervaporation (PV) separation of ethylene glycol (EG)/water mixtures at 30°C. The structure and properties of blend membranes were studied with the aid of FTIR, XRD, TGA, and SEM. The effect of experimental parameters such as feed composition, membrane thickness, and permeate pressure on separation performance of the MA crosslinked membranes were determined in terms of flux, selectivity, and pervaporation separation index. Sorption studies were carried out to evaluate the extent of interaction and degree of swelling of the blend membranes in pure, as well as in binary mixtures. The experimental results suggested that the crosslinked membrane (M-CA/CS) exhibited a good selectivity of 302 at a normalized flux of 0.38 kg.m^{? 2}.h^{? 1}.10 μ m at 30°C for 96.88 wt% EG aqueous solution.     

Transport of99mTc across TBP-kerosene oil supported liquid membranes

Transport of^99mTc across tri-n-butylphosphate (TBP) kerosene oil supported liquid membranes (SLM) has been studied under various conditions. Presence of dichromate ions helps avoid activity scavenging effects. Concentration increase of TBP, the complexing carrier used in the present study has a positive effect on flux (J) and permeability (P) of these ions, as up to 2.87M there is an increase in J and P values. HCl concentration in the feed solution increases J and P with their maximum values at 2.5–3.0M HCl in the feed. Above this concentration there is a decrease in flux and permeability of^99mTc(VII) ions. The given ions are stripped with LiCl or NaCl solutions but more with NaOH. The optimum conditions of transport of the given ions are 2.5M HCl concentration in the feed, 2.87M TBP concentration in the membrane and 1M NaOH concentration in the strip solution. Equations have been developed to indicate the relation between flux, J, viscosity, of TBP in organic membrane phase, temperature, T, [H⁺], in the aqueous feed solutions and Tc ion concentration in the feed solution. Based on P, the values determined from liquid membrane experiments, the quantitative flux values of Tc(VII) ions were also determined as a function of TBP concentration in the membranes, and HCl and Tc concentration in the feed solution using the given equations. This experimental technique provides quantitative results from trace level activity transfer experiments.     

膜吸收-再生循环技术捕集CO_2操作性能及其参数优化研究

采用N-甲基二乙醇胺(MDEA)+哌嗪(PZ)复合溶液作为捕集CO2吸收剂,研究了膜吸收-再生循环装置的操作性能,考察了气液流量、吸收剂浓度和再生电压等因素对捕集率和传质通量的影响,采用正交实验方法,优化操作条件,确定最佳操作方案。结果表明,气体流量对捕集率的影响明显大于液体流量的影响;气体流量增大对传质通量影响不明显;吸收剂浓度的增大使传质通量迅速增大,但大于一定值时通量不再增大;正交实验得出最佳操作条件为液体流量110 mL/min、气体流量0.65 L/min、吸收剂总浓度2.5 mol/L和再生电压210 V,捕集率大于95%,传质通量维持在5.86×10-4mol/(m2.s)。     

Preparation and characterization of TiO2/Pebax/(PSf‐PES) thin film nanocomposite membrane for humic acid removal from water

New thin film composite (TFC) membrane was prepared via coating of Pebax on PSf‐PES blend membrane as support, and its application in wastewater treatment was investigated. To modify this membrane, hydrophilic TiO₂ nanoparticles were coated on its surface at different loadings via dip coating technique. The as‐prepared membrane was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), field emission SEM, and contact angle analysis. The Fourier transform infrared spectroscopy analysis and surface SEM images indicated that TiO₂ was successfully coated on the membrane surface. In addition, the results stated that the hydrophilicity and roughness of membrane surface increased by addition of TiO₂ nanoparticles. Performance of TFC and modified TFC membranes was evaluated through humic acid removal from aqueous solution. Maximum permeate flux and humic acid rejection were obtained at 0.03 and 0.01 wt% TiO₂ loadings, respectively. Rejection was enhanced from 96.38% to 98.92% by the increase of feed concentration from 10 to 30 ppm. Additionally, membrane antifouling parameters at different pressures and feed concentration were determined. The results indicated that surface modification of membranes could be an effective method for improvement of membrane antifouling property.     

Flux decline in nanofiltration due to adsorption of dissolved organic compounds: model prediction of time dependency

Flux decline during nanofiltration of aqueous solutions containing dissolved organic compounds is mainly caused by adsorption of these compounds in the membrane pores and on the membrane surface. In this paper, flux decline is modeled by incorporating the loss of permeability due to adsorption in the Spiegler-Kedem equation. This results in a logarithmic relation between normalized flux decline and time until the adsorption equilibrium is reached and the flux reaches a constant value. In this way, the expected flux decline due to adsorption of organic compounds can be estimated. Two different parameters were used in the model: the time delay t(0), which corresponds to the time at which the adsorption process in the membrane pores and on the membrane surface sets in, and the corresponding reduction of free (pore) volume (b). Both parameters depend on the hydrophobicity of the compounds and on the feed concentration.     

新型Ti/TiOxHy/Sb-SnO2电极上苯胺电化学氧化反应

苯胺是一种重要的化工原料,广泛应用于印染、制药、造纸、橡胶等领域.随着化工行业的迅速发展,苯胺的需求量越来越大.然而,苯胺毒性高,大量使用势必造成水体中苯胺浓度的升高,给人类健康及生态环境造成危害.因此,急需一种高效、洁净、经济的方法处理含苯胺废水.电化学氧化法比较新颖,相比传统废水处理方法,它具有高效、简单、清洁等优点,因此被应用于很多废水处理当中,但过多的能耗限制了其进一步广泛应用.阳极作为电化学氧化技术的核心部件,直接影响到电化学氧化反应性能.因此开发出一种高效、经济的阳极材料很有必要.此外,对苯胺降解条件的优化也同样重要.关于苯胺电化学氧化,已有的研究包括Pt电极、PbO2电极和石墨电极等阳极材料.比较而言, Ti/Sb-SnO2电极具有制备工艺简单,析氧过电位较高,材料廉价和电催化性能较强等优点.然而,它的稳定性仍有待提高.因此本文制备了一种高稳定性的Ti/TiOxHy/Sb-SnO2电极,并用于处理苯胺废水.较为系统地研究了电流密度、苯胺初始浓度、pH、NaCl投加量及反应器类型对苯胺电催化氧化性能的影响,同时采用扫描电镜(SEM)、X射线衍射(XRD)和电化学测试对该电极进行了表征,并应用紫外-可见光谱、化学需氧量、电流效率及能耗对不同参数进行评定和优化. SEM及XRD结果表明, Ti/TiOxHy/Sb-SnO2电极涂层覆盖比较完全、紧实,未出现裂缝的发生,因而有利于提高电极稳定性.循环伏安测试结果表明,此电极具备较高的析氧过电位(2.0 V vs Ag/AgCl)及电化学孔隙度(76.31%),因此有利于电极催化性能的提高.苯胺电化学氧化实验结果发现,该反应符合准一级动力学模型,且高电流密度、酸性环境、适当NaCl投加量(0.2 wt%)更有利于苯胺的降解.另外, Ti/TiOxHy/Sb-SnO2电极在三维反应器中对苯胺的处理效果要远远好于在二维反应器中.可以看出, Ti/TiOxHy/Sb-SnO2电极具有较好的处理苯胺性能,可为苯胺废水处理的应用提供了一定的理论指导.     

苯酚在热氧化法制备的SnO2/Ti电极上的电氧化研究

以热氧化法制备的ＳｎＯ２／Ｔｉ电极作为阳极用于含苯酚酸性溶液的恒电流电解,测定了苯酚浓度、溶液中化学需氧量（ＣＯＤ）以及瞬时电流效率等随电解时间的变化。结果表明,用ＳｎＯ２／Ｔｉ电极代替铂作为阳极可使相同氧化电量下的ＣＯＤ明显下降,而平均电流效率提高了３倍,讨论了两种电极上苯酚氧化的反应机理。     

Growth and structure evolution of novel tin oxide diskettes

The novel SnO diskettes have been synthesized by evaporating either SnO or SnO(2) powders at elevated temperature. Disregard the source material being SnO or SnO(2), the SnO diskettes are formed at a low-temperature region of 200-400 degrees C. Two types of diskette shapes have been identified: the solid-wheel shape with a drop center rim (type I) and the diskette with cone peak(s) and spiral steps (type II). The diskettes are determined to be tetragonal SnO structure (P4/nmm), with their flat surfaces being (001). The formation of the SnO diskettes is suggested to result from a solidification process. The structural evolution from SnO diskettes to SnO(2) diskettes has been investigated by oxidizing at different temperatures. The result shows that the phase transformation from SnO to SnO(2) occurs in two processes of decomposition and oxidization, and the decomposition process consists of two steps: first from SnO to Sn(3)O(4) and then from Sn(3)O(4) to SnO(2).     

Study on a novel polyester composite nanofiltration membrane by interfacial polymerization of triethanolamine (TEOA) and trimesoyl chloride (TMC): I. Preparation, characterization and nanofiltration properties test of membrane

A novel thin-film composite (TFC) membrane for nanofiltration (NF) was developed by the interfacial polymerization of triethanolamine (TEOA) and trimesoyl chloride (TMC) on the polysulfone (PSf) supporting membrane. The active surface of the membrane was characterized by using FT-IR, XPS and SEM. The performance of TFC membrane was optimized by studying the preparation parameters, such as the reaction time of polymerization, pH of aqueous phase and the concentration of reactive monomers. It is found that the membrane performance is related to the changes of the monomer content in the aqueous phase rather than in the organic phase. Furthermore, the nanofiltration properties of the TFC membrane were tested by examining the separating performance of various salts at 0.6 MPa operating pressure. The rejection to different salt solutions decreased as per the order of Na₂SO₄ (82.2%), MgSO₄ (76.5%), NaCl (42.2%) and MgCl₂ (23%). Also, streaming potential tests indicated that isoelectric point of the TFC membrane is between pH 4 and 5. Moreover, the investigation of the flux for NaCl solution at different pH showed that the polyester NF composite membrane is also particularly suitable for treating acidic feeds: the flux increased from 8.4 to 11.5 L/m² h when pH of the feed decreased from 9 to 3. Additionally, the TFC membrane exhibits good long-term stability.     

Modeling of separation of aqueous solutions of FeCl3 and AlCl3 by zeolite-clay composite membranes using a space-charge model

In our earlier work, we reported the separation of FeCl3 from its aqueous solution and AlCl3 from its aqueous solution by analcime zeolite (Z1) membrane and its nitrated (Z2 membrane) and aminated (Z3 membrane) forms. Experimental data on the separation of aqueous solutions of FeCl3 and AlCl3 by zeolite-clay composite membranes has been simulated using the two-dimensional space-charge model. The computational requirement of the model has been considerably reduced by first obtaining a series solution of the nonlinear Poisson-Boltzmann equation. The effective pore radius of the membrane is taken as the one that gives the best fit to the experimental data, while the pore length is determined from the SEM photograph of the cross-sectional view of the membrane. The effective pore radii of the Z1, Z2, and Z3 membranes for FeCl3 solute are found to be 8.0, 7.0, and 5.0 nm, respectively, while for AlCl3 they are 4.5, 2.5, and 2.5 nm, respectively. These values are much less than the average of the pore size range values determined independently in an earlier work using the bubble point method and indicate partial blocking of the pores by these salts. The effective pore radius is larger for FeCl3 as compared to AlCl3 and decreases on modification. The intrinsic rejection is also found to decrease on modification. The permeate flux calculated from the model matches very well with the experimental values.     

Fish Skin as a Model Membrane to Study Transmembrane Drug Delivery with Cyclodextrins

The possibility of using fish skin as model membrane tostudy drug permeation and penetration enhancement by cyclodextrins was investigated.The permeability of the skin from four species of fish, Anarhichas lupus (catfish),Pleuronectes platessa (Plaice), Hippoglossus hippoglossus (Halibut)and Anarhichas minor (Spotted catfish), was compared in a Franz diffusion cell set-up using 1% hydrocortisone aqueous solution as a donor phase. The drug fluxthrough fish skin was more than 100 times faster than the flux through hairless mouse skin and more than 10 000 times faster than through snake skin. Catfishskin was most easily accessible and was therefore used for further study. The octanol-water partition coefficient did not affect the transmembrane flux of small molecules whereas the aqueous diffusion coefficient could be correlated with the flux.The hydrocortisone flux of from aqueous hydroxypropyl--cyclodextrin solutions, which were saturated with the drug, increased with increasing cyclodextrinconcentration. From these and other observations it was concluded that small moleculesare transported through fish skin in aqueous channels. The properties of thesechannels resemble the properties of the aqueous diffusion layer present in human andanimal skin and other types of biological membranes. Previous studies have shown thatcyclodextrins will enhance drug delivery by increasing aqueous diffusion rate. Catfish skin can therefore be a good model membrane to study penetration enhancementby cyclodextrins.     

On the prediction of permeate flux for nanofiltration of concentrated aqueous solutions with thin-film composite polyamide membranes

The nanofiltration of binary aqueous solutions of glucose, sucrose and sodium sulfate was investigated using thin-film composite polyamide membranes with different molecular weight cut-off's. The NF experiments, in total recycle mode, were performed in a plate-and-frame module Lab 20 (AlfaLaval), at 22 °C and with a flowrate of 8.2 L/min, using the membranes NF90, NF200 and NF270 from FilmTec (Dow Chemical), for transmembrane pressures between 1 and 6 MPa and with aqueous solutions with osmotic pressures of between 0.5 and 3.0 MPa. The permeate flux was predicted by the osmotic pressure model, using the membrane hydraulic resistance and the solution viscosity inside the membrane pores, and computing the concentration polarization with recourse to a mass-transfer correlation specific for the plate-and-frame module used. The flux predictions, using the pure water viscosity, agree reasonably with the experimental data only for low transmembrane pressures and with the most diluted solutions. For higher transmembrane pressures and for higher solute concentration the predicted fluxes can be as far as 2.5, 4.1 and 9.6 times higher than the experimental one, for the aqueous solutions of Na₂SO₄, glucose and sucrose, respectively. These deviations are strongly reduced when the pure water viscosity is replaced by the solution viscosity adjacent to the membrane. In this case, the maximum deviation between predictions and experiments occurs also for higher transmembrane pressures and for higher solute concentration, but the maximum ratio between predicted values and the experiments were reduced now to 1.8, 2.1 and 2.9, for the aqueous solutions of Na₂SO₄, glucose and sucrose, respectively. Even using the solution viscosity adjacent to the membrane, and for the systems investigated, the osmotic pressure model must used with caution for design purposes because it may over predict the permeate flux by a factor of about 2 when the solute concentration is high.     

具有界面交联结构藻酸钠复合膜的制备与性能

报道了一种具有界面交联结构的新型藻酸钠复合膜及其对醇水和其它有机物水体系的渗透汽化分离性能.该膜的活性层为藻酸钠,支撑层为氨化聚丙烯腈(PAN)多孔膜,在这两层之间存在着界面交联结构.研究了PAN多孔膜的水解时间、进行氨基化的二元胺种类及浓度对复合膜分离性能的影响,用己二胺进行氨基化所得到的复合膜的分离性能明显优于用乙二胺的结果.扫描电镜照片显示水解及氨基化改变了PAN超滤膜的孔结构,这也是影响新型复合膜性能的一个重要原因.