Effect of solution extrusion rate on morphology and performance of polyvinylidene fluoride hollow fiber membranes using polyvinyl pyrrolidone as an additive

<正>Polyvinylidene fluoride(PVDF) hollow fiber membranes prepared from spinning solutions with different polyvinyl pyrrolidone(PVP) contents(1%and 5%) at different extrusion rates were obtained by wet/dry phase process keeping all other spinning parameters constant.In spinning these PVDF hollow fibers,dimethylacetamide(DMAc) and PVP were used as a solvent and an additive,respectively.Water was used as the inner coagulant.Dimethylformamide(DMF) and water(30/70) were used as the external coagulant.The performances of membranes were characterized in terms of water flux,solute rejection for the wet membranes.The structure and morphology of PVDF hollow fiber were examined by BET adsorption,dry/wet weight method and scanning electron microscopy(SEM).It is found that the increase in PVP content and extrusion rate of spinning solution can result in the increase of water flux and decrease of solute rejection.The improvements of interconnected porous structure and pore size are induced by shear-thinning behavior of spinning solution at high extrusion rates,which could result in the increase of water flux of hollow fiber membranes.The increase of extrusion rate also leads to the increase of membrane thickness due to the recovery effect of elastic property of polymer chains.     

ZIF-67@Cellulose nanofiber hybrid membrane with controlled porosity for use as Li-ion battery separator

Zeolitic imidazolate framework-67(ZIF-67) was synthesized on the surface of cellulose nanofibers(CNFs)in methonal to address the problems of unhomogeneous pore size and pore distribution of pure CNF membrane.A combination of Energy Dispersive X-Ray Spectroscopy(EDS),X-ray photoelectron spectroscopy(XPS) and X-ray powder diffraction(XRD) patterns were used to determine the successful synthesis of ZIF-67@CNFs.The size of the ZIF-67 particles and pore size of the ZIF-67@CNF membrane were50-200 nm and 150-350 nm, respectively.The prepared ZIF-67@CNF membrane exhibited excellent thermal stability,lower thermal shrinkage and high surface wettability.The discharge capacity retention of the Li-ion batteries(LIBs) made with ZIF-67@CNF,glass fiber(GF),CNF and commercial polymer membranes after 100 th cycle at 0.5 C rate were 88.41%,86.22%,83.27%,and 81.03%,respectively.LIBs with ZIF-67@CNF membrane exhibited a better rate capability than these with other membranes.No damage of porous structure or peel-off of ZIF-67 was observed in the SEM images of ZIF-67@CNF membrane after100 th cycle.The improved cycling performance,rate capability,and good electrochemical stability implied that ZIF-67@CNFs membrane can be considered as a good alternative LIB separator.     

Structural Characterization and Property Study on the Activated Alumina-activated Carbon Composite Material

AlCl3,NH3·H2O,HNO3 and activated carbon were used as raw materials to prepare one new type of activated alumina-activated carbon composite material.The influence of heat treatment conditions on the structure and property of this material was discussed;The microstructures of the composite material were characterized by XRD,SEM,BET techniques;and its formaldehyde adsorption characteristic was also tested.The results showed that the optimal heat treatment temperature of the activated alumina-activated carbon composite material was 450 ℃,iodine adsorption value was 441.40 mg/g,compressive strength was 44 N,specific surface area was 360.07 m2/g,average pore size was 2.91 nm,and pore volume was 0.26 m3/g.According to the BET pore size distribution diagram,the composite material has dual-pore size distribution structure,the micro-pore distributes in the range of 0.6-1.7 nm,and the meso-pore in the range of 3.0-8.0 nm.The formaldehyde adsorption effect of the activated alumina-activated carbon composite material was excellent,much better than that of the pure activated carbon or activated alumina,and its saturated adsorption capacity was 284.19 mg/g.     

PREPARATION AND CHARACTERIZATION OF PVDF-HFP MICROPOROUS MEMBRANE BY TEMPLATE METHOD

Porous poly（vinylidene fluoride-co-hexafluoropropylene） （PVDF-HFP） membranes were successfully prepared using dibutyl phthalate （DBP）, polyvinylpyrrolidone （PVP-K30）, polyethylene glycol 200 （PEG200） as templates. SEM was used to examine the morphology of the PVDF-HFP porous membranes. It was found that these membranes have an asymmetric structure and the blends of PVDF-HFP/DBP formed nanoporous membranes, whereas the blends of PVDF- HFP/PVP-K30 formed ＂sponge-like＂ and microporous membranes. Moreover, the average pore size and porosity was about 0.3 μm and 48.7%, respectively. The crystallinity, thermal stability and mechanical strength of membranes were characterized by XRD, DSC, TGA and stress-strain tests. The results showed that the membranes are a crystals with excellent thermal stability. It was an effective way to regulate pore size and morphology of the PVDF-HFP membranes.     

Hierarchical Porous Polymer Beads Prepared by Polymerization-induced Phase Separation and Emulsion-template in a Microfluidic Device

Porous polymer beads（PPBs） containing hierarchical bimodal pore structure with gigapores and meso-macropores were prepared by polymerization-induced phase separation（PIPS） and emulsion-template technique in a glass capillary microfluidic device（GCMD）. Fabrication procedure involved the preparation of water-in-oil emulsion by emulsifying aqueous solution into the monomer solution that contains porogen. The emulsion was added into the GCMD to fabricate the（water-in-oil）-in-water double emulsion droplets. The flow rate of the carrier continuous phase strongly influenced the formation mechanism and size of droplets. Formation mechanism transformed from dripping to jetting and size of droplets decreased from 550 μm to 250 μm with the increase in flow rate of the carrier continuous phase. The prepared droplets were initiated for polymerization by on-line UV-irradiation to form PPBs. The meso-macropores in these beads were generated by PIPS because of the presence of porogen and gigapores obtained from the emulsion-template. The pore morphology and pore size distribution of the PPBs were investigated extensively by scanning electron microscopy and mercury intrusion porosimetry（MIP）. New pore morphology was formed at the edge of the beads different from traditional theory because of different osmolarities between the water phase of the emulsion and the carrier continuous phase. The morphology and proportion of bimodal pore structure can be tuned by changing the kind and amount of porogen.     

Preparation of Zeolite X Membranes on Porous Ceramic Substrates with Zeolite Seeds

Zeolite X membranes were investigated by in-situ hydrothermal synthesis on porous ceramic tubes precoated with zeolite X seeds or precursor amorphous aluminosilicate, and porous α-Al2O3 ceramic tubes with a pore size of 50-200 nm were employed as supports. Zeolite X crystals were synthesized by the classic method and mixed into deionized water as a slurry with a concentration of 0.2-0.5wt%, having a range of crystal sizes from 0.2 to 2μm. Crystal seeds were pressed into the pores near the inner surface of the ceramic tubes, and crystallization took place at 95℃ for 24-96 h. It was also investigated that Boehmite sol added with zeolite X seeds was precoated on ceramic supports to form a layer of r-Al2O3 by heating, and hydrothermal crystallization could then take place to prepare the zeolite membranes on the composite ceramic tubes. The crystal species were characterized by XRD, and the morphology of the supports subjected to crystallization was characterized by SEM. The composite zeolite membranes hav     

Polystyrene-based blend nanorods with gradient composition distribution

The polystyrene-based polymer blends, partially miscible poly(bisphenol A carbonate)/polystyrene (PC/PS) and completely miscible poly(2,6-dimethylphenylene oxide)/polystyrene (PPO/PS), in nanorods with gradient composition distribution were discussed. The polymer blend nanorods were prepared by infiltrating the polymer blends into nanopores of anodic aluminum oxide (AAO) templates via capillary action. Their morphology was investigated by micro-Fourier transform infrared spectroscopy (micro-FTIR) and nano-thermal analysis (nano-TA) with spatial resolution. The composition gradient of polymer blends in the nanopores is governed by the difference of viscosity and miscibility between the two polymers in the blends and the pore diameter. The capillary wetting of porous AAO templates by polymer blends offers a unique method to fabricate functional nanostructured materials with gradient composition distribution for the potential application to nanodevices.     

超细CaCO_3的粒子尺寸对PP结晶行为的影响

The effects of CaCO3 on the crystallization behavior of polypropylene (PP) were studied by means of DSC and WAXD.The average sizes of the CaCO3 powders used were 0.1μm (UC) and 0.5μm (GC),respectively.The PP/CaCO3 composites at compositions of 1phr and 10 phr were investigated.The results showed that the addition of CaCO3 reduced the supercooling,the rate of nucleation and the overall rate of crystallization (except for the 10phr UC/PP sample).The crystallinity of PP was increased and the size distribution of the crystallites of α-PP was broadened.On the other hand,the crystallization rate of 10phr UC/PP is 1.5 times higher than that of neat PP.It has an overall rate of crystallization 2 times as much as that of the neat PP and has the maximum crystallinity.The sizes of crystallites and the unit cell parameters of α-PP were varied by the addition of CaCO3.β-PP was formed by addition of GC and was not detected by addition of UC.The differences of crystallization behaviors of PP might be attributed to the combined effects of the content and size of CaCO3 filled.     

Effects of Co~（2＋）Doping on the Crystal Structure and Electrochemical Performance of LiFePO_4

Co2+-doped LiFePO4/C composite material was prepared by solid-state synthesis method using Fe2O3,Li2CO3 and NH4H2PO4 as the starting materials.The structures and elec-trochemical performance of samples were studied by XRD,SEM and constant current charge-discharge method.The results showed that the Co2+ doping did not change the crystal structure of LiFePO4.The unit cell volume changed with the increase of Co2+,and reached the maximum at x = 0.04.The LiFe0.96Co0.04PO4/C sample proved the best electrochemical properties.Its initial discharge capacity was 138.5 mA·h /g at 1 C rate.After 30 cycles,the capacity remained 127.7 mA·h /g,and the capacity retention rate was 92.2%.     

Ni/Al2O3 catalysts for syngas methanation: Effect of Mn promoter

Ni/Al2O3 catalysts with different amounts of manganese ranging from 1 to 3 wt% as promoter were prepared by co-impregnation method. The catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM. Their catalytic activity towards syngas methanation reaction was also investigated using a fixed-bed integral reactor. It was demonstrated that the addition of manganese to Ni/Al2O3 catalysts can increase the catalyst surface area and average pore volume, but decrease NiO crystallite size, leading to higher activity and stability. The effects of reaction temperature, pressure and weight hourly space velocity (WHSV) on carbon oxides conversion and CH4 formation rate were also studied. High carbon oxides conversion, CH4 selectivity and formation rate were achieved at the reaction temperature range of 280 300℃.     

ZSM-5沸石膜的吸附表征

The framework and thickness of synthesized ZSM-5 membranes were characterized using static and dynamic adsorption methods. It is shown that the adsorptive properties of the membranes are the same as ZSM-5 zeolite, the average thickness of the membranes was 13 μm calculated from the adsorptive ability, which matched very well with the result measured by scanning electron micrograph. The results also shown that zeolite membranes have greated adsorptive ability than zeolite powders. The high Si/Al rate zeolite membranes have selective ability on ethanol/water, and this interpreted the separation of ethanol-water mixtures with the membranes.     

Preparation of multihollow P(St-MAA) particles by sequence soap-free/soap emulsion polymerization and followed by stepwise alkali/acid posttreatment

The effects of ionic emulsifier, sodium dodecylbenzene sulfate (SDBS), on the formation of the multihollow structures in sub-micron sized polymer particles produced by alkali/acid posttreatment were investigated. The original latex particles with narrow size distribution were synthesized by a new sequence emulsifier-free/emulsifier emulsion copolymerization of styrene (St) and methacrylic acid (MAA). Results indicated that the pore size decreased and the pore number increased with the increase of SDBS amount, and the morphology of the posttreated latex particles was also significantly influenced by the introducing time of SDBS in the preparation of the original latex particles, and a suitable introducing time was 3 h of polymerization.     

Novel ZnO-Al2O3 composite particles as sorbent for low temperature H2S removal

ZnO-Al₂O₃ composite particles composed of ZnO nanosheets（thickness of 40-80 nm） on alumina particles were prepared by heterogeneous precipitation method using bayerite seed particles.The asprepared composite particles were characterized in terms of crystal structure,morphology,surface area and pore volume.The composite particles were used as sorbent for H₂S adsorption at low temperature, and were compared with pure ZnO sorbent.The composite sorbent showed a greater sulfur adsorption capacity（0.052 g/g） than pure form of ZnO（0.028 g/g）.This significant improvement was mainly attributed to higher surface area,more pore volume and unique morphology in nanoscale,which were also obtained by low cost presented method in this work for synthesis of ZnO sorbent supported on alumina particles.     

稻壳SiO_2/钒催化剂上苯乙酮液相氧化(英文)

Rice husk silica catalyst loaded with 10 wt% vanadium was synthesized from agricultural biomass via a sol-gel synthetic route at pH = 9. The catalyst was characterized by different physico-chemical methods. The FTIR spectra showed the formation of Si–O–V and V=O stretching bands. The presence of vanadium was confirmed by EDX elemental analysis. RH-10V possessed a high specific surface area of 276 m2/g and pore volume of 0.83 ml/g. The prepared catalyst possessed a narrow pore size distribution centered around 7.9 nm. The catalytic performance of RH-10V was tested in the oxidation of acetophenone at 70 ℃. RH-10V was found to be an active catalyst in the oxidation of acetophenone, producing 36.28% conversion efficiency. The products identified were benzoic acid, 2-hydroxyacetophenone, phenol, acetic acid, and 3-hydroxyacetophenone.     

Shape-controlled synthesis and photocatalytic activity of In2O3 nanostructures derived from coordination polymer precursors

In（BTC）（phen）（H₂O）nanocrystals with controllable morphology and size were successfully obtained by solvothermal method.Hierarchical straw-sheaf-like architectures,nanorods and elongated hexagons have been synthesized by varying the volume ratio of DMF:H₂O:C₂H₅OH.Phase-pure In₂O₃nanocrystals were obtained by the calcination of the precursors without significant alteration of the morphology.The products were characterized by PXRD,SEM,TEM,TGA,IR and gas adsorption measurements.The photocatalytic effect was investigated for the In₂O₃ nanocrystals with different morphology on the degradation of rhodamine B（Rh B）and it was found that the nanorods exhibited the best photocatalytic activity,which shows the degradation efficiency of 94%for 8 h.The results showed that the photocatalytic activity increased with the increase of BET surface area and pore volume.     

Effect of Fumed SiO<Subscript>2</Subscript> on Pore Formation Mechanism and Various Performances of <Emphasis Type="Italic">β</Emphasis>-<Emphasis Type="Italic">i</Emphasis>PP Microporous Membrane Used for Lithium-ion Battery Separator

In this work,four samples containing different contents of fumed SiO2 were prepared to improve the pore size distribution and various properties of βnucleated isotatic polypropylene (β-iPP) biaxial membrane used for lithium-ion battery separator.The wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) results show that the fumed SiO2 promotes the formation of r-crystal slightly and narrows down the thickness distribution of β-lamellae;meanwhile,evenly distributed SiO2 within β-iPP can be inspected by scanning electron microscopy (SEM).Moreover,further detailed characterization of morphological evolutions during biaxial stretching by tensile testing and SEM manifests that SiO2 can strengthen β-iPP and make the samples deform more homogeneously,resulting in a gradually elaborate and finer oriented microfibril structure after longitudinal stretching,in which more uniform defects distribute between fibrils and restrain the formation of coarse fibrils effectively.Therefore,more superior microporous structure emerges with the addition of SiO2,accompanied by narrower pore size distribution and better connectivity between microvoids,which is confirmed by mercury porosimeter and diminished Gurley value.Moreover,the lower thermal shrinkage,decreased shrinkage rate and suppressed porosity reduction indicate that fumed SiO2 improves thermal and dimensional stability of membrane dramatically.Furthermore,due to the excellent wettability of SiO2 with electrolyte,the microporous membranes doped with SiO2 have higher electrolyte uptake,even after heat treatment at elevated temperature.     

Research on KOH/La-Ba-Al2O3 catalysts for biodiesel production via transesterification from microalgae oil

Alumina supports modified by lanthanum(La)and barium(Ba)were prepared by peptization.Catalysts with different KOH contents supported on modified alumina were prepared by impregnation method.Various techniques,including N2 adsorption-desorption(Brunauer-Emmet-Teller method,BET),X-ray diffraction(XRD),scanning electron microscopy(SEM),and fourier transform infrared absorption spectroscopy(FT-IR). Catalytic activity for microalgae oil conversion to methyl ester via transesterification was evaluated and analyzed by GC-MS and GC.BET results showed that the support possessed high specific surface area,suitable pore volume and pore size distribution.Activity results indicated that the catalyst with 25 wt%KOH showed the best activity for microalgae oil conversion.XRD and SEM results revealed that Al-O-K compound was the active phase for microalgae oil conversion.The agglomeration and changing of pore structure should be the main reasons for the catalyst deactivation when KOH content was higher than 30 wt%.     

稻壳SiO2/钒催化剂上苯乙酮液相氧化（英文）

Rice husk silica catalyst loaded with 10 wt% vanadium was synthesized from agricultural biomass via a sol-gel synthetic route at pH = 9. The catalyst was characterized by different physico-chemical methods. The FTIR spectra showed the formation of Si–O–V and V=O stretching bands. The presence of vanadium was confirmed by EDX elemental analysis. RH-10V possessed a high specific surface area of 276 m2/g and pore volume of 0.83 ml/g. The prepared catalyst possessed a narrow pore size distribution centered around 7.9 nm. The catalytic performance of RH-10V was tested in the oxidation of acetophenone at 70 ℃. RH-10V was found to be an active catalyst in the oxidation of acetophenone, producing 36.28% conversion efficiency. The products identified were benzoic acid, 2-hydroxyacetophenone, phenol, acetic acid, and 3-hydroxyacetophenone.     

二氧化钛膜参数对离子液体基染料敏化纳米薄膜太阳电池性能的影响

Photo correlation spectroscopy was used to measure the particle size distribution of TiO2 films. Other parameters, such as porosity, BET surface area, average pore size, crystallite size D101, distribution of pore size etc. were also measured. The effects of these parameters on the ionic liquid based dye-sensitized solar cells （DSC） were studied. It was concluded that the particle size distribution of nanocrystalline TiO2 played an important role on the performance of DSC. The narrow particle size distribution of nanocrystalline TiO2 increased the efficiency of DSC, while the wide distribution decreased the efficiency of DSC. From the result above, it was also concluded that the photo correlation spectroscopy was a good method to identify the performance of TiO2 films. Based on electrochemical impedance spectroscopy, we found that the particle size distribution could affect the electronic contact between the TiO2 layers as well. The narrow particle size distribution made the electronic contact between TiO2 layers better than the wide particle size distribution of the TiO2 films, and then better the electronic contact, higher the efficiency of the DSC.     

Theoretical and Experimental Study on the Adsorption and Desorption of Methane by Granular Activated Carbon at 25 ℃

A theoretical and experimental study was conducted to accurately determine the amount of adsorption and desorption of methane by various Granular Activated Carbon(GAC)under different physical conditions.To carry out the experiments,the volumetric method was used up to 500 psia at constant temperature of 25℃.In these experiments,adsorption as well as desorption capacities of four different GAC in the adsorption of methane,the major constituent of natural gas,at various equilibrium pressures and a constant temperature were studied.Also,various adsorption isotherm models were used to model the experimental data collected from the experiments.The accuracy of the results obtained from the adsorption isotherm models was compared and the values for the regressed parameters were reported.The results shows that the physical characteristics of activated carbons such as BET surface area,micropore volume,packing density,and pore size distribution play an important role in the amount of methane to be adsorbed and desorbed.