The development of multilayer composite membranes for CO_2 separation has gained increasing attention due to the desire for energy efficient technologies. Multilayer composite membranes have many advantages, including...The development of multilayer composite membranes for CO_2 separation has gained increasing attention due to the desire for energy efficient technologies. Multilayer composite membranes have many advantages, including the possibility to optimize membrane materials independently by layers according to their different functions and to reduce the overall transport resistance by using ultrathin selective layers, and less limitations on the material mechanical properties and processability. A comprehensive review is required to capture details of the progresses that have already been achieved in developing multilayer composite membranes with improved CO_2 separation performance in the past 15-20 years.In this review, various composite membrane preparation methods were compared, advances in composite membranes for CO_2/CH_4 separation,CO_2/N_2 and CO_2/H_2 separation were summarized with detailed data, and challenges facing for the CO_2 separation using composite membranes,such as aging, plasticization and long-term stability, were discussed. Finally the perspectives and future research directions for composite membranes were presented.展开更多
Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane （PDMS） and poly （ethylene glycol） diacrylate ...Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane （PDMS） and poly （ethylene glycol） diacrylate （PEGDA） composite membranes were prepared. The microstructure and physicochemical properties of the compos- ite membranes were characterized. Preparation conditions were systematically optimized. The gas separation performance of the as-prepared membranes was studied by pure gas and binary gas permeation measurement of CO〉 N2 and H〉 Experiments showed that PDMS, as silicone rubber, exhibited larger permeance and lower separation factors. Conversely, PEGDA composite membrane presented smaller gas permeance but higher ideal selectivity for CO2/N2. Compared to the performance of those membranes using polymeric supports or freestanding membranes, the two kinds of ceramic supported composite membranes exhibited higher gas permeance and acceptable selectivity. Therefore, the ceramic supported composite membrane can be expected as a candidate for CO2 separation from light gases.展开更多
In this study, a poly（ether block amide） （Pebax 1657） composite membrane applied for COa capture was prepared by coating Pebax 1657 solution on polyacrylonitrile （PAN） ultrafiltration membrane. Ethanol/water mix...In this study, a poly（ether block amide） （Pebax 1657） composite membrane applied for COa capture was prepared by coating Pebax 1657 solution on polyacrylonitrile （PAN） ultrafiltration membrane. Ethanol/water mixture was used as the solvent of Pebax and the effects of ethanol/water mass ratios and Pebax concentration on the permeation properties of composite membrane were studied. To enhance the com- posite membrane permeance, the gutter layer, made from reactive amino silicone crosslinking with potydimethylsiloxane （PDMS）, was de- signed. The influence of crosslinldng degree of the gutter layer on membrane performance was investigated. As a result, a Pebardamino- PDMS/PAN multilayer membrane with hexane resistance was developed, showing CO2 permeance of 350 GPU and CO2/N2 selectivity over 50. The blend of polyethylene glycol dimethyl ether （PEG-DME） with Pebax as coating material was studied to further improve the membrane performance. After being combined with PEG-DME additive, CO2 permeance of the final Pebax-PEG-DME/amino-PDMS/PAN composite membrane reached 400 GPU above with CO2/Na selectivity over 65.展开更多
A novel hydrophilic nanocomposite additive （TiO2-g-PNIPAAm） was synthesized by the surface modification of titanium dioxide （TiO2） with N-isopropylacrylamide （NIPAAm） via ＂graft-from＂ technique. And the nanoco...A novel hydrophilic nanocomposite additive （TiO2-g-PNIPAAm） was synthesized by the surface modification of titanium dioxide （TiO2） with N-isopropylacrylamide （NIPAAm） via ＂graft-from＂ technique. And the nanocomposite membrane of poly（vinylidene fluoride） （PVDF）/TiO2-g-PNIPAAm was fabricated by wet phase inversion. The graft degree was obtained by thermo-gravimetric analysis （TGA）. Fourier transform infrared attenuated reflection spectroscopy （FTIR-ATR） and X-ray photoelectronic spectroscopy （XPS） characterization results suggested that TiO2-g-PNIPAAm nanoparticles segregated on membrane surface during the phase separation process. Scanning electron microscopy （SEM） was conducted to investigate the surface and cross-section of the modified membranes. The water contact angle measurements confirmed that TiO2-g-PNIPAAm nanoparticles endowed PVDF membranes better hydrophlilicity and thermo-responsive properties compared with those of the pristine PVDF membrane. The water contact angle decreased from 92.8~ of the PVDF membrane to 61.2~ of the nanocompostie membrane. Bovine serum albumin （BSA） static and dynamic adsorption experiments suggested that excellent antifouling properties of membranes was acquired after adding TiO2-g- PNIPAAm. The maximum BSA adsorption at 40℃ was about 3 times than that at 23 ℃. The permeation experiments indicated the water flux recover ratio and BSA rejection ratio were improved at different temperatures.展开更多
The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(d...The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride)(PDDA)polyelectrolyte solution containing positively charged TiO2@PDDA nanoparticles with the assistance of dopamine(DA).Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO2]+PFO-via the counterion exchange between Cl-and PFO-(perfluorooctanoate).The transformation between hydrophilicity and hydrophobicity is reversible.For both hydrophilic and hydrophobic membranes,the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue(MB),Congo red(CR)and Evans blue(EB),and as well metal salt aqueous solution.The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored.The results revealed that both membranes showed high nanofiltration performances for retention of dyes in(non)aqueous solution.For the hydrophilic membrane,the rejection of salts in a sequence is MgSO4>Na2SO4>MgCl2>NaCl.Moreover,both of the hydrophilic and hydrophobic membranes showed high stability and antifouling property.展开更多
Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was deve...Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was developed by interfacial polymerization between 1,3–cyclohexanebis–methylamine(CHMA) and trimesoyl chloride(TMC). ATR-FTIR, SEM and AFM were used to characterize the active thin layer formed inside the PSf hollow fiber. The separation behavior of the CHMA-TMC/PSf membrane was scrutinized by studying various effects like feed gas pressure and temperature. Furthermore, the influence of CHMA concentration and TMC concentration on membrane morphology and performance were investigated. As a result, it was found that mutually the CHMA concentration and TMC concentration play key roles in determining membrane morphology and performance. Moreover, the CHMA-TMC/PSf composite membrane showed good CO_2/CH_4 separation performance. For CO_2/CH_4 mixture gas(30/70 by volume) test, the membrane(PD1 prepared by CHMA 1.0% and TMC 0.5%) showed a CO_2 permeance of 25 GPU and the best CO_2/CH_4 selectivity of 28 at stage cut of 0.1. The high CO_2/CH_4 separation performance of CHMA-TMC/PSf thin film composite membrane was mostly accredited to the thin film thickness and the properties of binary amino groups.展开更多
Membrane fouling is one of the major obstacles for reaching a high flux over a prolonged period of ultrafiltration（UF）process.In this study,a sulfonated-polyethersulfone（SPES）/nano-TiO2 composite UF membrane with ...Membrane fouling is one of the major obstacles for reaching a high flux over a prolonged period of ultrafiltration（UF）process.In this study,a sulfonated-polyethersulfone（SPES）/nano-TiO2 composite UF membrane with good anti-fouling performance was fabricated by phase inversion and self-assembly methods.The TiO2 nanoparticle self-assembly on the SPES membrane surface was confirmed by X-ray photoelectron spectroscopy （XPS）and FT-IR spectrometer.The morphology and hydrophilicity were characterized by scanning electron microscopy（SEM）,atomic force microscopy（AFM）and contact angle goniometer,respectively.The anti-fouling mechanism of composite UF membrane was discussed through the analysis of the micro-structure and component of UF membrane surface.The results showed that the TiO2 content and the micro-structure of the composite UF membrane surface had great influence on the separation and anti-fouling performance.展开更多
This paper reports on a new microporous composite silica membrane prepared via acid-catalyzed polymeric route of sol-gel method with tetraethylorthosilicate(TEOS)and a bridged silsesquioxane[1,2-bis(triethoxysilyl)eth...This paper reports on a new microporous composite silica membrane prepared via acid-catalyzed polymeric route of sol-gel method with tetraethylorthosilicate(TEOS)and a bridged silsesquioxane[1,2-bis(triethoxysilyl)ethane, BTESE]as precursors.A stable nano-sized composite silica sol with a mean volume size of^5 nm was synthesized. A 150 nm-thick defect-free composite silica membrane was deposited on disk support consisting of macroporous α-Al2O3 and mesoporousγ-Al2O3 intermediate layer by using dip-coating approach,followed by calcination under pure nitrogen atmosphere.The composite silica membranes exhibit molecular sieve properties for small gases like H2,CO2,O2,N2,CH4 and SF6 with hydrogen permeances in the range of(1-4)×10 -7mol·m -2·s -1·Pa -1(measured at 200°C,3.0×105 Pa).With respect to the membrane calcined at 500°C,it is found that the permselectivities of H 2 (0.289 nm)with respect to N2(0.365 nm),CH4(0.384 nm)and SF6(0.55 nm)are 22.9,42 and>1000,respectively, which are all much higher than the corresponding Knudsen values(H2/N2=3.7,H2/CH4=2.8,and H2/SF6=8.5).展开更多
For the first time the preparation of the N-doped TiO2-coated NaY zeolite membrane（N-doped TiO2/NaY zeolite membrane） as an electrode material for photoelectrocatalysis has been achieved and reported.The XRD, SEM, U...For the first time the preparation of the N-doped TiO2-coated NaY zeolite membrane（N-doped TiO2/NaY zeolite membrane） as an electrode material for photoelectrocatalysis has been achieved and reported.The XRD, SEM, UV–vis and XPS techniques were used to characterize the structure of the N-doped TiO2/NaY zeolite membrane. The results verified that the surface of the N-doped TiO2/NaY zeolite membrane was coated by TiO2 nanoparticles of ca. 20 nm size and exhibited a distinct red-shift in the UV–vis spectra compared to N-doped TiO2. The photoelectrocatalysis performance of the N-doped TiO2/NaY zeolite membrane electrode was evaluated by phenol degradation. The results revealed it is a promising novel electrode material for application of photoelectrocatalysis in the removal of organic contaminants in waste water.展开更多
Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO...Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO 2(a natase), Al 2SiO 5, and ZrO 2 in these membranes. Changing the molar ratio of Al∶Si∶Ti∶Zr,the kinds and content of crystal phases of composite membranes could be different, which may lead to a variety of microstructure of membranes. The surface nanoscale topography and microstructure of membranes were investiga ted by XRD,SEM,AFM,EPMA. The effects of additives and heat treatments on the sur face nanoscale topography and microstructure of composite ceramic membranes were also analyzed.展开更多
Three phase PebaxMH 1657/PEG-ran-PPG/CuBTC（polymer/liquid/solid） was successfully deposited as a selective layer on a porous Polysulfone（PSF） support. In fact, the beneficial properties of PEG（high selectivity） ...Three phase PebaxMH 1657/PEG-ran-PPG/CuBTC（polymer/liquid/solid） was successfully deposited as a selective layer on a porous Polysulfone（PSF） support. In fact, the beneficial properties of PEG（high selectivity） with those of PPG（high permeability, amorphous） have been combined with superior properties of mixed matrix membrane（MMMs）. The membranes were characterized by DSC, TGA and SEM, while CuBTC was characterized by COand CHadsorption test. Statistically based experimental design（central composite design, CCD） was applied to analyze and optimize the effect of PEG-ran-PPG（10–50 wt%） and CuBTC（0–20 wt%） mass contents on the COpermeance and CO/CHideal selectivity. Based on the regression coefficients of the obtained models, the COpermeance was notably influenced by PEG-ran-PPG,while CuBTC has the most significant effect on the CO/CHideal selectivity. Under the optimum conditions（PEG-ran-PPG: 32.76 wt% and CuBTC: 20 wt%）, nearly 620% increase in the COpermeance and43% enhancement in the CO/CHideal selectivity was observed compared to the neat Pebax. The effect of pressure（3, 9 and 15 bar） on the pure and mixed gas separation performance of the composite membranes was also investigated. The high solubility of COin the membranes resulted in the enhancement of COpermeability with increase in gas pressure.展开更多
The low porosity of metal-organic framework glass makes it difficult to prepare membranes with high permeability.To solve this problem,we fabricated a series of self-supported zeolite glass composite membranes with di...The low porosity of metal-organic framework glass makes it difficult to prepare membranes with high permeability.To solve this problem,we fabricated a series of self-supported zeolite glass composite membranes with different 4A zeolite loadings using the abundant pore structure of the zeolite.The 4A zeolite embedded in the zeolite glass composite membrane preserved the ligand bonds and chemical structure.The self-supported zeolite glass composite membranes exhibited good interfacial compatibility.More importantly,the incorporation of the 4A zeolite significantly improved the CO_(2)adsorption capacity of the pure a_(g)ZIF-62 membranes.In addition,gas separation performance measurements showed that the(a_(g)ZIF-62)_(0.7)(4A)_(0.3)membrane had a permeability of 13,329 Barrer for pure CO_(2)and an ideal selectivity of 31.7 for CO_(2)/CH_(4),which exceeded Robeson's upper bound.The(a_(g)ZIF-62)_(0.7)(4A)_(0.3)membrane exhibited good operational stability in the variable pressure test and 48 h long-term continuous test.This study provides a method for preparing zeolite glass composite membranes.展开更多
Poly （N,N-dimethylaminoethyl methacrylate）-poly （ethylene glycol methyl ether methacrylate） （PDMAEMA-PEGMEMA） and cesium fluoride （CsF） were blended and used as the separation material of composite membranes.H...Poly （N,N-dimethylaminoethyl methacrylate）-poly （ethylene glycol methyl ether methacrylate） （PDMAEMA-PEGMEMA） and cesium fluoride （CsF） were blended and used as the separation material of composite membranes.Hollow fiber composite membranes were fabricated by coating the blend on polysulfone （PSf） hollow fiber substrate.Introduction of fluorine ion improved the separation performance of the membrane.The concentration of coating solution was adjusted to obtain a membrane with high permeance.The composite membrane showed good performance with the CO2 permeance of 30.4 GPU （1 GPU=10-6 cm3 （STP）/（cm 2 s cmHg））,and selectivities to CO2/N2,CO2/CH4,CO2/H2 and O2/N2 of 47.2,37.6,1.75 and 4.70,respectively.Potassium fluoride （KF）,due to its low cost,was also used as a substitute of CsF to prepare composite membrane and the permeation data showed that CsF can be replaced by KF.The effect of operating temperature on the permeation properties of the composite membrane was also investigated.展开更多
MoS2/γ－Al2O3 ceramic composite membrane is successfully synthesized by the sol-gel method based on the inorganic salt route. The aluminum hydrate sol derived from the inorganic salt Al(NO3)3, whose transparence and ...MoS2/γ－Al2O3 ceramic composite membrane is successfully synthesized by the sol-gel method based on the inorganic salt route. The aluminum hydrate sol derived from the inorganic salt Al(NO3)3, whose transparence and viscosity are 97% and 1.2 × 10-3 Pa. s, respectively, can be formed through adjusting the ratio of the peptizing agent H+ to Al3+ to 0.3. The aluminum hydrate gel at 110℃ is amorphous in structure and is heat-treated in air at 800℃ to form γ－Al2O3. The precursor derived from the mixture solution of ammonium molybdate, thioacetamide and a reducing agent, can be transformed into crystal MoS2 under reducing condition at 800℃. MoS2/γ－Al2O3 composite membrane is an organic whole and bps no gradation from MoS2 layer to γ－Al2O3 Iayer. The separation factor a H2/H2S through the MoS2/γ－Al2O3 composite membrane increase with rising temperature and a H2/H2S at 600℃ is 4.45 higher than the theoretical separation factor produced by the ideal Knudsen diffusion.展开更多
The perfluorosulfonic acid(PFSA) membrane doped with two-dimensional conductive filler Ti_(3)C_(2)T_(x) is a fuel cell proton exchange membrane with high application potential. Experimental studies showed that the pro...The perfluorosulfonic acid(PFSA) membrane doped with two-dimensional conductive filler Ti_(3)C_(2)T_(x) is a fuel cell proton exchange membrane with high application potential. Experimental studies showed that the proton conductivity of Nafion/Ti_(3)C_(2)T_(x) composite membrane is improved significantly compared with that in pure Nafion. However, the microscopic mechanism of doping on the enhancement of membrane performance is remain unclear now. In this work, molecular dynamics simulation was used to investigate the microscopic morphology and proton transport behaviors of Nafion/Ti_(3)C_(2)T_(x) composite membrane at the molecular level. The results shown that there were significant differences about the diffusion kinetics of water molecules and hydroxium ions in Nafion/Ti_(3)C_(2)T_(x) at low and high hydration levels in the nanoscale region.With the increase of water content, Ti_(3)C_(2)T_(x) in membrane was gradually surrounded by ambient water molecules to form a hydration layer, and forming a relatively continuous proton transport channel between Nafion polymer and Ti_(3)C_(2)T_(x) monomer. The continuous proton transport channel could increase the number of binding sites of proton and thus achieving high proton conductivity and high mobility of water molecules at higher hydration level. The current work can provide a theoretical guidance for designing new type of Nafion composite membranes.展开更多
Al2O3 ceramic powder was applied to modify the large pores defects on the surface of the porous metal Ti support,in situ oxidation method was a convenient method to prepare defect free ceramic/Ti composite membranes o...Al2O3 ceramic powder was applied to modify the large pores defects on the surface of the porous metal Ti support,in situ oxidation method was a convenient method to prepare defect free ceramic/Ti composite membranes on this basis.In situ oxidation conditions experimental results show that the best condition for preparing the TiO2-Al2O3/Ti composite membrane is under 800°C for 2 h,and the microstructure and pore sizes of the TiO2-Al2O3/Ti composite membranes are affected obviously.The thickness and composition of the TiO2/Ti composite membranes are determined by SEM and XRD completely.The pore size distribution of the composite membrane is measured by bubble pressure method,the most probable aperture is about 3.12μm,while the average pore size of defect free TiO2-Al2O3/Ti is about 3.23μm.After ultrasonic treatment,the slight weight change of membranes reveals no observable change,which indicates that TiO2-Al2O3/Ti composite membranes maintain a good stability.展开更多
To improve operation efficiency,an interlayered thin-film composite forward osmosis(iTFC-FO)membrane was designed by introducing an ultrathin and porous interlayer based on aluminum tetra-(4-carboxyphenyl)porphyrin(a ...To improve operation efficiency,an interlayered thin-film composite forward osmosis(iTFC-FO)membrane was designed by introducing an ultrathin and porous interlayer based on aluminum tetra-(4-carboxyphenyl)porphyrin(a stable metal-organic framework nanosheet,Al-MOF).Surface characterization results revealed that Al-MoF spread evenly in the macro-porous substrate,and provided a flat and smooth reaction interface with moderate hydrophilicity and uniform small aperture.The resultant polyamide(PA)layer had a thin base(without intrusion into substrate)and crumpled surface(with abundant leaves).The leaves size and cross-linking degree of PA layer firstly increased and then decreased with the Al-MOF loading.Compared to the original membrane,the iTFC-FO showed an enhanced water permeability and a reduced reverse sodium flux in both modes of active layer facing feed solution(ALFS)and active layer facing draw solution(AL-DS).To be specific,the specific reverse sodium flux(reverse sodium flux/pure water flux)decreased from 0.27 g/L to 0.04 g/L in the AL-FS mode,while from 1.36 g/L to 0.23 g/L in the AL-DS mode with 2 mol/L NaCl as DS.Moreover,the iTFC-FO maintained high stability and high permeability under high-salinity and contaminated environment.This study offers a new possibility for the rational fabrication of high-performance TFC-FO membranes.展开更多
High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which ...High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which exhibits a superior proton conductivity.PCP-MCN nanoparticles are used as additives to fabricate PCP-MCN/Nafion composite membranes.Microstructures and characteristics of PCP-MCN and these membranes have been extensively investigated.Significant enhancement in proton conduction for PCP-MCN around 55℃ is interestingly found due to the thermal motion of the PCP molecular chains.Robust mechanical properties and higher thermal decomposition temperature of the composite membranes are directly ascribed to strong intermolecular interactions between PCP-MCN and Nafion side chains,i.e.,the formation of substantial acid–base pairs(-SO_(3)^(-)…^(+)H–NH-),which further improves compatibility between additive and Nafion matrix.At the same humidity and temperature condition,the water uptake of composite membranes significantly increases due to the incorporation of porous additives with abundant functional groups and thus less crystallinity degree in comparison to pristine Nafion.Proton conductivity(σ)over wide ranges of humidities(30-100%RH at 25℃)and temperatures(30-98℃ at 100%RH)for prepared membranes is measured.The s in PCPMCN/Nafion composite membranes is remarkably enhanced,i.e.0.245 S/cm for PCP-MCN-3wt.%/Nafion is twice that of Nafion membrane at 98℃ and 100%RH,because of the establishment of well-interconnected proton transport ionic water channels and perhaps faster protonation–deprotonation processes.The composite membranes possess weak humidity-dependence of proton transport and higher water uptake due to excellent water retention ability of PCP-MCN.In particular,when 3 wt.%PCP-MCN was added to Nafion,the power density of a single-cell fabricated with this composite membrane reaches impressively 0.480,1.098 W/cm^(2) under 40%RH,100%RH at 60℃,respectively,guaranteeing it to be a promising proton exchange membrane.展开更多
ZrO2/TiO2 composite photocatalytic film was produced on the pure titanium substrate using in-situ Zr（OH）4 colloidal particle by the micro-arc oxidation technique and characterized by scanning electron microscope （...ZrO2/TiO2 composite photocatalytic film was produced on the pure titanium substrate using in-situ Zr（OH）4 colloidal particle by the micro-arc oxidation technique and characterized by scanning electron microscope （SEM）, energy dispersive X-ray （EDX）, X-ray diffraction （XRD） and ultraviolet-visible （UV-Vis） spectrophotometer. The composite film shows a lamellar and porous structure which consists of anatase, futile and ZrO2 phases. The optical absorption edge of film is shifted to longer wavelength when ZrO2 is introduced to TiO2. Furthermore, the photocatalytic reaction rate constants of degradation of rhodamine B solution with ZrO2/TiO2 composite film and pure TiO2 film under ultraviolet irradiation are measured as 0.0442 and 0.0186 h 1, respectively.展开更多
TiO2-coated activated carbon surface （TAs） composites were prepared by a sol-gel method with supercritical pretreatment. The photocatalytic degradation of acid yellow （AY） was investigated under UV radiation to es...TiO2-coated activated carbon surface （TAs） composites were prepared by a sol-gel method with supercritical pretreatment. The photocatalytic degradation of acid yellow （AY） was investigated under UV radiation to estimate activity of catalysts and determine the kinetics. And the effects of parameters including the initial concentration of AY, light intensity and TiO2 content in catalysts were examined. The results indicate that TAs has a higher efficiency in decomposition of AY than P25, pure TiO2 particles as well as the mixture of TiO2 powder and active carbon. The photocatalytic degradation rate is found to follow the pseudo-first order kinetics with respect to the AY concentration. The new kinetic model fairly resembles the classic Langmuir-Hinshelwood equation, and the rate constant is proportional to the square root of the light intensity in a wide range. However, its absorption performance depends on the surface areas of catalysts. The model fits quite well with the experimental data and elucidates phenomena about the effects of the TiO2 content in TAs on the degradation rate.展开更多
基金supported by the Research Council of Norway through the CLIMIT program(MCIL-CO_2 project,215732)the European Union Seventh Framework Programme(FP7/2007-2013)in HiPerCap project under grant agreement n°608555
文摘The development of multilayer composite membranes for CO_2 separation has gained increasing attention due to the desire for energy efficient technologies. Multilayer composite membranes have many advantages, including the possibility to optimize membrane materials independently by layers according to their different functions and to reduce the overall transport resistance by using ultrathin selective layers, and less limitations on the material mechanical properties and processability. A comprehensive review is required to capture details of the progresses that have already been achieved in developing multilayer composite membranes with improved CO_2 separation performance in the past 15-20 years.In this review, various composite membrane preparation methods were compared, advances in composite membranes for CO_2/CH_4 separation,CO_2/N_2 and CO_2/H_2 separation were summarized with detailed data, and challenges facing for the CO_2 separation using composite membranes,such as aging, plasticization and long-term stability, were discussed. Finally the perspectives and future research directions for composite membranes were presented.
基金Supported by the National Basic Research Program of China （2009CB623406）, the National Natural Science Foundation of China （20990222） and the Natural Science Foundation of Jiangsu Province （BK2009021, SBK200930313）.
文摘Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane （PDMS） and poly （ethylene glycol） diacrylate （PEGDA） composite membranes were prepared. The microstructure and physicochemical properties of the compos- ite membranes were characterized. Preparation conditions were systematically optimized. The gas separation performance of the as-prepared membranes was studied by pure gas and binary gas permeation measurement of CO〉 N2 and H〉 Experiments showed that PDMS, as silicone rubber, exhibited larger permeance and lower separation factors. Conversely, PEGDA composite membrane presented smaller gas permeance but higher ideal selectivity for CO2/N2. Compared to the performance of those membranes using polymeric supports or freestanding membranes, the two kinds of ceramic supported composite membranes exhibited higher gas permeance and acceptable selectivity. Therefore, the ceramic supported composite membrane can be expected as a candidate for CO2 separation from light gases.
文摘In this study, a poly（ether block amide） （Pebax 1657） composite membrane applied for COa capture was prepared by coating Pebax 1657 solution on polyacrylonitrile （PAN） ultrafiltration membrane. Ethanol/water mixture was used as the solvent of Pebax and the effects of ethanol/water mass ratios and Pebax concentration on the permeation properties of composite membrane were studied. To enhance the com- posite membrane permeance, the gutter layer, made from reactive amino silicone crosslinking with potydimethylsiloxane （PDMS）, was de- signed. The influence of crosslinldng degree of the gutter layer on membrane performance was investigated. As a result, a Pebardamino- PDMS/PAN multilayer membrane with hexane resistance was developed, showing CO2 permeance of 350 GPU and CO2/N2 selectivity over 50. The blend of polyethylene glycol dimethyl ether （PEG-DME） with Pebax as coating material was studied to further improve the membrane performance. After being combined with PEG-DME additive, CO2 permeance of the final Pebax-PEG-DME/amino-PDMS/PAN composite membrane reached 400 GPU above with CO2/Na selectivity over 65.
基金financially supported by the National Natural Science Foundation of China(No.51303028)the Natural Science Foundation of Fujian Province(No.2011J01044)
文摘A novel hydrophilic nanocomposite additive （TiO2-g-PNIPAAm） was synthesized by the surface modification of titanium dioxide （TiO2） with N-isopropylacrylamide （NIPAAm） via ＂graft-from＂ technique. And the nanocomposite membrane of poly（vinylidene fluoride） （PVDF）/TiO2-g-PNIPAAm was fabricated by wet phase inversion. The graft degree was obtained by thermo-gravimetric analysis （TGA）. Fourier transform infrared attenuated reflection spectroscopy （FTIR-ATR） and X-ray photoelectronic spectroscopy （XPS） characterization results suggested that TiO2-g-PNIPAAm nanoparticles segregated on membrane surface during the phase separation process. Scanning electron microscopy （SEM） was conducted to investigate the surface and cross-section of the modified membranes. The water contact angle measurements confirmed that TiO2-g-PNIPAAm nanoparticles endowed PVDF membranes better hydrophlilicity and thermo-responsive properties compared with those of the pristine PVDF membrane. The water contact angle decreased from 92.8~ of the PVDF membrane to 61.2~ of the nanocompostie membrane. Bovine serum albumin （BSA） static and dynamic adsorption experiments suggested that excellent antifouling properties of membranes was acquired after adding TiO2-g- PNIPAAm. The maximum BSA adsorption at 40℃ was about 3 times than that at 23 ℃. The permeation experiments indicated the water flux recover ratio and BSA rejection ratio were improved at different temperatures.
基金financially supported by the National Natural Science Foundation of China(21476005,21878003)the National Natural Science Fund for Innovative Research Groups(51621003)。
文摘The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride)(PDDA)polyelectrolyte solution containing positively charged TiO2@PDDA nanoparticles with the assistance of dopamine(DA).Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO2]+PFO-via the counterion exchange between Cl-and PFO-(perfluorooctanoate).The transformation between hydrophilicity and hydrophobicity is reversible.For both hydrophilic and hydrophobic membranes,the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue(MB),Congo red(CR)and Evans blue(EB),and as well metal salt aqueous solution.The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored.The results revealed that both membranes showed high nanofiltration performances for retention of dyes in(non)aqueous solution.For the hydrophilic membrane,the rejection of salts in a sequence is MgSO4>Na2SO4>MgCl2>NaCl.Moreover,both of the hydrophilic and hydrophobic membranes showed high stability and antifouling property.
基金Supported by the National Research Council of Science&Technology(NST)grant by the Korea government(MSIP)(No.CRC-15-07-KIER)
文摘Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was developed by interfacial polymerization between 1,3–cyclohexanebis–methylamine(CHMA) and trimesoyl chloride(TMC). ATR-FTIR, SEM and AFM were used to characterize the active thin layer formed inside the PSf hollow fiber. The separation behavior of the CHMA-TMC/PSf membrane was scrutinized by studying various effects like feed gas pressure and temperature. Furthermore, the influence of CHMA concentration and TMC concentration on membrane morphology and performance were investigated. As a result, it was found that mutually the CHMA concentration and TMC concentration play key roles in determining membrane morphology and performance. Moreover, the CHMA-TMC/PSf composite membrane showed good CO_2/CH_4 separation performance. For CO_2/CH_4 mixture gas(30/70 by volume) test, the membrane(PD1 prepared by CHMA 1.0% and TMC 0.5%) showed a CO_2 permeance of 25 GPU and the best CO_2/CH_4 selectivity of 28 at stage cut of 0.1. The high CO_2/CH_4 separation performance of CHMA-TMC/PSf thin film composite membrane was mostly accredited to the thin film thickness and the properties of binary amino groups.
基金Supported by the Natural Science Foundation of Shandong Province（Q2007B01）
文摘Membrane fouling is one of the major obstacles for reaching a high flux over a prolonged period of ultrafiltration（UF）process.In this study,a sulfonated-polyethersulfone（SPES）/nano-TiO2 composite UF membrane with good anti-fouling performance was fabricated by phase inversion and self-assembly methods.The TiO2 nanoparticle self-assembly on the SPES membrane surface was confirmed by X-ray photoelectron spectroscopy （XPS）and FT-IR spectrometer.The morphology and hydrophilicity were characterized by scanning electron microscopy（SEM）,atomic force microscopy（AFM）and contact angle goniometer,respectively.The anti-fouling mechanism of composite UF membrane was discussed through the analysis of the micro-structure and component of UF membrane surface.The results showed that the TiO2 content and the micro-structure of the composite UF membrane surface had great influence on the separation and anti-fouling performance.
基金Supported by the National Natural Science Foundation of China(20906047)the State Key Laboratory of Chemical Engineering(SKL-ChE-09A01)the State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201002)
文摘This paper reports on a new microporous composite silica membrane prepared via acid-catalyzed polymeric route of sol-gel method with tetraethylorthosilicate(TEOS)and a bridged silsesquioxane[1,2-bis(triethoxysilyl)ethane, BTESE]as precursors.A stable nano-sized composite silica sol with a mean volume size of^5 nm was synthesized. A 150 nm-thick defect-free composite silica membrane was deposited on disk support consisting of macroporous α-Al2O3 and mesoporousγ-Al2O3 intermediate layer by using dip-coating approach,followed by calcination under pure nitrogen atmosphere.The composite silica membranes exhibit molecular sieve properties for small gases like H2,CO2,O2,N2,CH4 and SF6 with hydrogen permeances in the range of(1-4)×10 -7mol·m -2·s -1·Pa -1(measured at 200°C,3.0×105 Pa).With respect to the membrane calcined at 500°C,it is found that the permselectivities of H 2 (0.289 nm)with respect to N2(0.365 nm),CH4(0.384 nm)and SF6(0.55 nm)are 22.9,42 and>1000,respectively, which are all much higher than the corresponding Knudsen values(H2/N2=3.7,H2/CH4=2.8,and H2/SF6=8.5).
基金supported by the Talent Introduction Fund of Yangzhou University(2012),Jiangsu Province Science and Technology Support Project(No.BE2014613)Six Big Peak Talent in Jiangsu Province(No.2014-XCL-013)the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘For the first time the preparation of the N-doped TiO2-coated NaY zeolite membrane（N-doped TiO2/NaY zeolite membrane） as an electrode material for photoelectrocatalysis has been achieved and reported.The XRD, SEM, UV–vis and XPS techniques were used to characterize the structure of the N-doped TiO2/NaY zeolite membrane. The results verified that the surface of the N-doped TiO2/NaY zeolite membrane was coated by TiO2 nanoparticles of ca. 20 nm size and exhibited a distinct red-shift in the UV–vis spectra compared to N-doped TiO2. The photoelectrocatalysis performance of the N-doped TiO2/NaY zeolite membrane electrode was evaluated by phenol degradation. The results revealed it is a promising novel electrode material for application of photoelectrocatalysis in the removal of organic contaminants in waste water.
文摘Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO 2(a natase), Al 2SiO 5, and ZrO 2 in these membranes. Changing the molar ratio of Al∶Si∶Ti∶Zr,the kinds and content of crystal phases of composite membranes could be different, which may lead to a variety of microstructure of membranes. The surface nanoscale topography and microstructure of membranes were investiga ted by XRD,SEM,AFM,EPMA. The effects of additives and heat treatments on the sur face nanoscale topography and microstructure of composite ceramic membranes were also analyzed.
文摘Three phase PebaxMH 1657/PEG-ran-PPG/CuBTC（polymer/liquid/solid） was successfully deposited as a selective layer on a porous Polysulfone（PSF） support. In fact, the beneficial properties of PEG（high selectivity） with those of PPG（high permeability, amorphous） have been combined with superior properties of mixed matrix membrane（MMMs）. The membranes were characterized by DSC, TGA and SEM, while CuBTC was characterized by COand CHadsorption test. Statistically based experimental design（central composite design, CCD） was applied to analyze and optimize the effect of PEG-ran-PPG（10–50 wt%） and CuBTC（0–20 wt%） mass contents on the COpermeance and CO/CHideal selectivity. Based on the regression coefficients of the obtained models, the COpermeance was notably influenced by PEG-ran-PPG,while CuBTC has the most significant effect on the CO/CHideal selectivity. Under the optimum conditions（PEG-ran-PPG: 32.76 wt% and CuBTC: 20 wt%）, nearly 620% increase in the COpermeance and43% enhancement in the CO/CHideal selectivity was observed compared to the neat Pebax. The effect of pressure（3, 9 and 15 bar） on the pure and mixed gas separation performance of the composite membranes was also investigated. The high solubility of COin the membranes resulted in the enhancement of COpermeability with increase in gas pressure.
基金supported by the S&T Program of Hebei(no.22373709D).
文摘The low porosity of metal-organic framework glass makes it difficult to prepare membranes with high permeability.To solve this problem,we fabricated a series of self-supported zeolite glass composite membranes with different 4A zeolite loadings using the abundant pore structure of the zeolite.The 4A zeolite embedded in the zeolite glass composite membrane preserved the ligand bonds and chemical structure.The self-supported zeolite glass composite membranes exhibited good interfacial compatibility.More importantly,the incorporation of the 4A zeolite significantly improved the CO_(2)adsorption capacity of the pure a_(g)ZIF-62 membranes.In addition,gas separation performance measurements showed that the(a_(g)ZIF-62)_(0.7)(4A)_(0.3)membrane had a permeability of 13,329 Barrer for pure CO_(2)and an ideal selectivity of 31.7 for CO_(2)/CH_(4),which exceeded Robeson's upper bound.The(a_(g)ZIF-62)_(0.7)(4A)_(0.3)membrane exhibited good operational stability in the variable pressure test and 48 h long-term continuous test.This study provides a method for preparing zeolite glass composite membranes.
基金supported by the Chinese Ministry of Science and Technology(973 Program,No. 2009CB623405)the National Natural Science Foundation of China(NSFC program,20706051 and 20836006)
文摘Poly （N,N-dimethylaminoethyl methacrylate）-poly （ethylene glycol methyl ether methacrylate） （PDMAEMA-PEGMEMA） and cesium fluoride （CsF） were blended and used as the separation material of composite membranes.Hollow fiber composite membranes were fabricated by coating the blend on polysulfone （PSf） hollow fiber substrate.Introduction of fluorine ion improved the separation performance of the membrane.The concentration of coating solution was adjusted to obtain a membrane with high permeance.The composite membrane showed good performance with the CO2 permeance of 30.4 GPU （1 GPU=10-6 cm3 （STP）/（cm 2 s cmHg））,and selectivities to CO2/N2,CO2/CH4,CO2/H2 and O2/N2 of 47.2,37.6,1.75 and 4.70,respectively.Potassium fluoride （KF）,due to its low cost,was also used as a substitute of CsF to prepare composite membrane and the permeation data showed that CsF can be replaced by KF.The effect of operating temperature on the permeation properties of the composite membrane was also investigated.
文摘MoS2/γ－Al2O3 ceramic composite membrane is successfully synthesized by the sol-gel method based on the inorganic salt route. The aluminum hydrate sol derived from the inorganic salt Al(NO3)3, whose transparence and viscosity are 97% and 1.2 × 10-3 Pa. s, respectively, can be formed through adjusting the ratio of the peptizing agent H+ to Al3+ to 0.3. The aluminum hydrate gel at 110℃ is amorphous in structure and is heat-treated in air at 800℃ to form γ－Al2O3. The precursor derived from the mixture solution of ammonium molybdate, thioacetamide and a reducing agent, can be transformed into crystal MoS2 under reducing condition at 800℃. MoS2/γ－Al2O3 composite membrane is an organic whole and bps no gradation from MoS2 layer to γ－Al2O3 Iayer. The separation factor a H2/H2S through the MoS2/γ－Al2O3 composite membrane increase with rising temperature and a H2/H2S at 600℃ is 4.45 higher than the theoretical separation factor produced by the ideal Knudsen diffusion.
基金financially supported by the National Key R&D Program of China (Nos.2020YFB1505500 and 2020YFB1505503)。
文摘The perfluorosulfonic acid(PFSA) membrane doped with two-dimensional conductive filler Ti_(3)C_(2)T_(x) is a fuel cell proton exchange membrane with high application potential. Experimental studies showed that the proton conductivity of Nafion/Ti_(3)C_(2)T_(x) composite membrane is improved significantly compared with that in pure Nafion. However, the microscopic mechanism of doping on the enhancement of membrane performance is remain unclear now. In this work, molecular dynamics simulation was used to investigate the microscopic morphology and proton transport behaviors of Nafion/Ti_(3)C_(2)T_(x) composite membrane at the molecular level. The results shown that there were significant differences about the diffusion kinetics of water molecules and hydroxium ions in Nafion/Ti_(3)C_(2)T_(x) at low and high hydration levels in the nanoscale region.With the increase of water content, Ti_(3)C_(2)T_(x) in membrane was gradually surrounded by ambient water molecules to form a hydration layer, and forming a relatively continuous proton transport channel between Nafion polymer and Ti_(3)C_(2)T_(x) monomer. The continuous proton transport channel could increase the number of binding sites of proton and thus achieving high proton conductivity and high mobility of water molecules at higher hydration level. The current work can provide a theoretical guidance for designing new type of Nafion composite membranes.
基金Projects(212006065,21666018)supported by the National Natural Science Foundation of China
文摘Al2O3 ceramic powder was applied to modify the large pores defects on the surface of the porous metal Ti support,in situ oxidation method was a convenient method to prepare defect free ceramic/Ti composite membranes on this basis.In situ oxidation conditions experimental results show that the best condition for preparing the TiO2-Al2O3/Ti composite membrane is under 800°C for 2 h,and the microstructure and pore sizes of the TiO2-Al2O3/Ti composite membranes are affected obviously.The thickness and composition of the TiO2/Ti composite membranes are determined by SEM and XRD completely.The pore size distribution of the composite membrane is measured by bubble pressure method,the most probable aperture is about 3.12μm,while the average pore size of defect free TiO2-Al2O3/Ti is about 3.23μm.After ultrasonic treatment,the slight weight change of membranes reveals no observable change,which indicates that TiO2-Al2O3/Ti composite membranes maintain a good stability.
基金supported by the National Natural Science Foundation of China(Nos.52100089 and 51978312)the Program to Cultivate Middle-aged and Young Science Leaders of Colleges and Universities of Jiangsu Province and Youth Fund of Basic Research Program of Jiangnan University(No.JUSRP121058).
文摘To improve operation efficiency,an interlayered thin-film composite forward osmosis(iTFC-FO)membrane was designed by introducing an ultrathin and porous interlayer based on aluminum tetra-(4-carboxyphenyl)porphyrin(a stable metal-organic framework nanosheet,Al-MOF).Surface characterization results revealed that Al-MoF spread evenly in the macro-porous substrate,and provided a flat and smooth reaction interface with moderate hydrophilicity and uniform small aperture.The resultant polyamide(PA)layer had a thin base(without intrusion into substrate)and crumpled surface(with abundant leaves).The leaves size and cross-linking degree of PA layer firstly increased and then decreased with the Al-MOF loading.Compared to the original membrane,the iTFC-FO showed an enhanced water permeability and a reduced reverse sodium flux in both modes of active layer facing feed solution(ALFS)and active layer facing draw solution(AL-DS).To be specific,the specific reverse sodium flux(reverse sodium flux/pure water flux)decreased from 0.27 g/L to 0.04 g/L in the AL-FS mode,while from 1.36 g/L to 0.23 g/L in the AL-DS mode with 2 mol/L NaCl as DS.Moreover,the iTFC-FO maintained high stability and high permeability under high-salinity and contaminated environment.This study offers a new possibility for the rational fabrication of high-performance TFC-FO membranes.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.12075172,12375288,12205089,and 12105048)National Key R&D Program of China(Grant No.2019YFA0210003)Guangdong Basic and Applied Basic Research Foundation(No.2020A1515110817).
文摘High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which exhibits a superior proton conductivity.PCP-MCN nanoparticles are used as additives to fabricate PCP-MCN/Nafion composite membranes.Microstructures and characteristics of PCP-MCN and these membranes have been extensively investigated.Significant enhancement in proton conduction for PCP-MCN around 55℃ is interestingly found due to the thermal motion of the PCP molecular chains.Robust mechanical properties and higher thermal decomposition temperature of the composite membranes are directly ascribed to strong intermolecular interactions between PCP-MCN and Nafion side chains,i.e.,the formation of substantial acid–base pairs(-SO_(3)^(-)…^(+)H–NH-),which further improves compatibility between additive and Nafion matrix.At the same humidity and temperature condition,the water uptake of composite membranes significantly increases due to the incorporation of porous additives with abundant functional groups and thus less crystallinity degree in comparison to pristine Nafion.Proton conductivity(σ)over wide ranges of humidities(30-100%RH at 25℃)and temperatures(30-98℃ at 100%RH)for prepared membranes is measured.The s in PCPMCN/Nafion composite membranes is remarkably enhanced,i.e.0.245 S/cm for PCP-MCN-3wt.%/Nafion is twice that of Nafion membrane at 98℃ and 100%RH,because of the establishment of well-interconnected proton transport ionic water channels and perhaps faster protonation–deprotonation processes.The composite membranes possess weak humidity-dependence of proton transport and higher water uptake due to excellent water retention ability of PCP-MCN.In particular,when 3 wt.%PCP-MCN was added to Nafion,the power density of a single-cell fabricated with this composite membrane reaches impressively 0.480,1.098 W/cm^(2) under 40%RH,100%RH at 60℃,respectively,guaranteeing it to be a promising proton exchange membrane.
基金Project(gf200901002)supported by the Open Research Fund of National Defense Key Disciplines Laboratory of Light Alloy Processing Science and Technology of Nanchang Hangkong University,China
文摘ZrO2/TiO2 composite photocatalytic film was produced on the pure titanium substrate using in-situ Zr（OH）4 colloidal particle by the micro-arc oxidation technique and characterized by scanning electron microscope （SEM）, energy dispersive X-ray （EDX）, X-ray diffraction （XRD） and ultraviolet-visible （UV-Vis） spectrophotometer. The composite film shows a lamellar and porous structure which consists of anatase, futile and ZrO2 phases. The optical absorption edge of film is shifted to longer wavelength when ZrO2 is introduced to TiO2. Furthermore, the photocatalytic reaction rate constants of degradation of rhodamine B solution with ZrO2/TiO2 composite film and pure TiO2 film under ultraviolet irradiation are measured as 0.0442 and 0.0186 h 1, respectively.
基金Project(50802034) supported by the National Natural Science Foundation of ChinaProject(11A093) supported by the Key Project Foundation by the Education Department of Hunan Province,China
文摘TiO2-coated activated carbon surface （TAs） composites were prepared by a sol-gel method with supercritical pretreatment. The photocatalytic degradation of acid yellow （AY） was investigated under UV radiation to estimate activity of catalysts and determine the kinetics. And the effects of parameters including the initial concentration of AY, light intensity and TiO2 content in catalysts were examined. The results indicate that TAs has a higher efficiency in decomposition of AY than P25, pure TiO2 particles as well as the mixture of TiO2 powder and active carbon. The photocatalytic degradation rate is found to follow the pseudo-first order kinetics with respect to the AY concentration. The new kinetic model fairly resembles the classic Langmuir-Hinshelwood equation, and the rate constant is proportional to the square root of the light intensity in a wide range. However, its absorption performance depends on the surface areas of catalysts. The model fits quite well with the experimental data and elucidates phenomena about the effects of the TiO2 content in TAs on the degradation rate.
