Indispensable gutter layers in thin-film composite membranes for carbon capture

Industrial thin-film composite(TFC)membranes achieve superior gas separation properties from high-performance selective layer materials,while the success of membrane technology relies on high-performance gutter layers to achieve production scalability and low-cost manufacturing.However,the current literature predominantly focuses on the design of polymer architectures to obtain high permeability and selectivity,while the art of fabricating gutter layers is usually safeguarded by industrial manufacturers and appears lackluster to academic researchers.This is the first report aiming to provide a comprehensive and critical review of state-of-the-art gutter layer materials and their design and modification to enable TFC membranes with superior separation performance.We first elucidate the importance of the gutter layer on membrane performance through modeling and experimental results.Then various gutter layer materials used to obtain high-performance composite membranes are critically reviewed,and the strategies to improve their compatibility with the selective layer are highlighted,such as oxygen plasma treatment,polydopamine deposition,and surface grafting.Finally,we present the opportunities of the gutter layer design for practical applications.

Synthesis of a PEBAX-1074/ZnO nanocomposite membrane with improved CO_2 separation performance

In this investigation, polymeric nanocomposite membranes（PNMs） were prepared via incorporating zinc oxide（ZnO） into poly（ether-block-amide）(PEBAX-1074) polymer matrix with different loadings. The neat membrane and nanocomposite membranes were prepared via solution casting and solution blending methods, respectively. The fabricated membranes were characterized by field emission scanning electron microscopy（FESEM） to survey cross-sectional morphologies and thermal gravimetric analysis（TGA）to study thermal stability. Fourier transform infrared（FT-IR） and X-ray diffraction（XRD） analyses were also employed to identify variations of the chemical bonds and crystal structure of the membranes, respectively. Permeation of pure gases, CO, CHand Nthrough the prepared neat and nanocomposite membranes was studied at pressures of 3–18 bar and temperature of 25 °C. The obtained results showed that the fabricated nanocomposite membranes exhibit better separation performance compared to the neat PEBAX membrane in terms of both permeability and selectivity. As an example, at temperature of 25 °C and pressure of 3 bar, COpermeability, ideal CO/CHand CO/Nselectivity values for the neat PEBAX membrane are 110.67 Barrer, 11.09 and 50.08, respectively, while those values are 152.27 Barrer,13.52 and 62.15 for PEBAX/ZnO nanocomposite membrane containing 8 wt% ZnO.

Electrochemical Study of Lincomycin on Au-PtNPs/nanoPAN/ Chitosan Nanocomposite Membrane and Its Determination in Injections

The Au-Pt alloy nanoparticles（Au-PtNPs） were electrochemically deposited on the surface of polyaniline nanotube（nanoPAN） and chitosan（CS） modified glassy carbon electrode（GCE）. The electrochemical behavior of lincomycin at Au-PtNPs/nanoPAN/CS modified GCE was investigated by cyclic voltammetry, linear sweep voltammetry and chronocoulometry. Cyclic voltammetric experiments show that lincomycin at the nanocomposite membrane modified electrode exhibited a pair of quasi-reversible redox peaks in pH=6.0 PBS. The membrane could accelerate the electron transfer of lincomycin on the electrode and significantly enhance the peak current. In a range of 3.0-100.0 mg/L, the reductive peak current of lincomycin at 0.42 V was linearly related to its concentration and the linear regression equation was ip,c=0.2703ρ-0.0042（ip, c： μA; ρ： mg/L; r=0.998, n=7） with a detection limit of 1.0 mg/L（S/N =3）. Compared with other methods, this method exhibited many advantages such as high sensitivity, selectivity, wide linear range and low detection limit. The method was used to determine the content of lincomycin in injections commercially available with satisfactory results. Some electrochemical parameters involved in the redox reaction of lincomycin, such as parameter of kinetic ha, standard rate constant ks and the number of H^＋, were also calculated.

Nanocomposite membranes with high-charge and size-screened phosphorylated nanocellulose fibrils for CO_(2)separation

In this study,cellulose nanofibrils(CNF)of high charge(H-P-CNF)and screened size(H-P-CNF-S)were fabricated by increasing the charge of phosphorylated cellulose nanofibrils(P-CNFs)during the pre-treatment step of CNF production.Results show that the H-P-CNF have a significantly higher charge(3.41 mmol g^(-1))compared with P-CNF(1.86 mmol g^(-1)).Centrifugation of H-P-CNF gave a supernatant with higher charge(5.4 mmol g^(-1))and a reduced size(H-P-CNF-S).These tailored nanocelluloses were added to polyvinyl alcohol(PVA)solutions and the suspensions were successfully coated on porous polysulfone(PSf)supports to produce thin-film nanocomposite membranes.The humid mixed gas permeation tests show that CO_(2)permeability increases for membranes with the addition of H-P-CNF-S by 52%and 160%,compared with the P-CNF/PVA membrane and neat PVA membrane,respectively.

Characterization of Nanocomposite Membrane Based Bacterial Cellulose Made of Pineapple Waste Reinforced by Graphite Nanoplatelets

Waste is the main problem for the environment.Handling waste for various useful applications has a benefit for the future.This work has been studied for handling pineapple peel waste to make composite film bacterial cellulose nanocomposite membrane(BCNM)with addition graphite nanoplatelet(GNP).The concentration of GNP in the membrane influence the membrane properties.The bacterial cellulose(BC)pellicle was synthesized by using media from pineapple peel waste extract.BC pellicle is cleaned with water and NaOH solution to be free from impactors.BCNM is synthesized through the mechanical disintegration stage.The results of disintegration using high pressure homogenizer at 150 bar and five cycles.BCNM/GNP is synthesized with varying addition of GNP of 2.5,5.0,10 and 100 wt%of dry bacterial nanocellulose(BNC).The BC and GNP solution were dried in an oven for 14 h at 80℃.BCNM morphology was observed using SEM.GNP is dispersed and distributed in the BC matrix as reinforcement.FTIR analysis shows many peaks of BNC less pronounced with increasing of GNP.The higher concentration of GNP,the rougher of BCNM.The optimum tensile strength of BCNM was achieved after addition GNP of 2.5 wt%.

Extended adsorption transport models for permeation of copper ions through nanocomposite chitosan/polyvinyl alcohol thin affinity membranes

Transport of copper ions through nanocomposite chitosan/polyvinyl alcohol thin adsorptive membranes has been mathematically investigated in the current study. Unsteady-state diffusive transport model was coupled with the Freundlich isotherm to predict the concentration of the ions in dialysis permeation operation. Pristine model was not successful in predicting the experimental data based upon its low coefficients of determination（0.1

Effects of Functionalized Silica Nanoparticles on Characteristics of Nanocomposites PES Cation Exchange Membranes

Nanocomposite cation exchange membranes（CEMs） were prepared by adding various loadings of functionalized silica nanoparticles to the sulfonated polyethersulfone（s PES） polymeric matrix. The silica nanoparticles were functionalized by mercaptopropyl（F1, IEC=0）, propylsulfonic acid（F2, IEC= 2.71）, and sulfonic acid（F3, IEC=2.84）. The properties of prepared membranes were investigated by varying the loadings of functionalized silica nanoparticles. Applying functionalized nanoparticles provides additional ion exchange groups and enhances water contents as well as conductivities and permselectivities of the membranes. The maximum IEC of 1.9 meq.g^-1 was obtained for the membrane having 3 wt% F3 nanoparticles and the maximum conductivity of 0.237 S·cm^-1 was achieved for the membrane having 2 wt% F3 nanoparticles, which were 19.6% and 64% higher than the corresponding values for s PES membrane, respectively. The excellent properties of the nanocomposite cation-exchange membranes make them appropriate candidates for electrodialysis and desalination processes.

Preparation of ZIF-8@PEBAX/PVDF nanocomposite membrane by the combination of self-assembly and in-situ growth for removing thiophene from the model gasoline

Metal-organic frameworks(MOFs)have gained attention in the development of MOFs/polymer hybrid membranes for pervaporation.However,the agglomeration of MOFs particles and interfacial defects limit its further application.In this study,we present a novel approach to fabricate a ZIF-8@PEBAX/PVDF nanocomposite membrane for removing thiophene from the model gasoline by combination of selfassembly and in-situ growth.Firstly,a PVDF supporting membrane was modified to have a negative charge.Next,positively charged zinc ions were attracted onto the negatively charged PVDF supporting membrane through electrostatic interaction.Afterwards,the Zinc ions deposited PVDF membrane was immersed into dimethylimidazole solution to form a uniform ZIF-8 layer.Finally,the ZIF-8 layer was coated with poly(ether-block-amide)(PEBAX)using the pouring method.Experimental results showed that the separating efficiency of the ZIF-8@PEBAX/PVDF nanocomposite membrane was improved significantly compared to that of pristine PEBAX membrane.The optimal permeation flux and enrichment factor of membrane were 27.80 kg(m^(2)h)^(-1)and 6.9,respectively.

Nanocomposite sodalite/ceramic membrane for pre-combustion CO2 capture： synthesis and morphological characterization

Carbon capture and storage （CCS） is amongst the possible options to reduce CO2 emission. In the application of CCS, CO2 capture techniques such as adsorption and membrane system have been proposed due to less energy requirement and environmental benign than the absorption process. However, membrane system has drawbacks such as poor membrane reproducibility, scale-up difficulty and high cost of the membrane supports. In this study synthesis and characterization of nanocomposite sodalite （HS）/ceramic membrane via ＂pore-plugging＂ hydrothermal synthesis （PPH） protocol for pre- combustion CO2 capture is reported. The morphology and crystallinity of the as-prepared membranes were checked with scanning electron microscopy and X-ray diffraction. Surface chemistry of the membrane was examined with Fourier Transform Infrared spectroscopy. In nanocomposite architecture membranes, zeolite crystals are embedded within the pores of the supports instead of forming thin-film layers of the zeolite crystals on the surface of the supports. Compared to the conventional in situ direct hydrothermal synthesis, membranes obtained from PPH possess higher mechanical strength and thermal stability. In addition, defect control with nanocomposite architecture membranes is possible because the zeolite crystals are embedded within the pores of the support, thereby limiting the maximum defect size to the pore size of the support. Furthermore, the nanocomposite architecture nature of the membranes safeguards the membrane from shocks or abrasion that could promote formation of defects. The aforementioned advantages of the nanocomposite architecture membranes could be beneficial in developing high performance and cost-effective membrane materials for pre-combustion CO2 capture.

Substrate matters:The influences of substrate layers on the performances of thin-film composite reverse osmosis membranes

Thin-film composite(TFC) reverse osmosis(RO) membranes are playing the dominating role in desalination.Tremendous efforts have been put in the studies on the polyamide selective layers. However, the effect of the substrate layers is far less concerned. In this review, we summarize the works that consider the impacts of the substrates, including pore sizes, surface hydrophilicity, on the processes of interfacial polymerization and consequently on the morphologies of the active layers and on final RO performances of the composite membranes. All the works indicate that the pore sizes and surface hydrophilicity of the substrate evidently influence the RO performances of the composite membranes. Unfortunately, we find that the observations and understandings on the substrate effect are frequently varied from case to case because of the lack of substrates with uniform pores and surface chemistries. We suggest using track-etched membranes or anodized alumina membranes having relatively uniform pores and functionalizable pore walls as model substrates to elucidate the substrate effect.Moreover, we argue that homoporous membranes derived from block copolymers have the potential to be used as substrates for the large-scale production of high-performances TFC RO membranes.

High-permeance crosslinked PTMSP thin-film composite membranes as supports for CO_2 selective layer formation

In the development of the composite gas separation membranes for post-combustion CO_2 capture, little attention is focused on the optimization of the membrane supports, which satisfy the conditions of this technology. The primary requirements to the membrane supports are concerned with their high CO_2 permeance. In this work, the membrane supports with desired characteristics were developed as high-permeance gas separation thin film composite(TFC) membranes with the thin defect-free layer from the crosslinked highly permeable polymer, poly[1-(trimethylsilyl)-1-propyne](PTMSP). This layer is insoluble in chloroform and can be used as a gutter layer for the further deposition of the CO_2-selective materials from the organic solvents. Crosslinking of PTMSP was performed using polyethyleneimine(PEI) and poly(ethyleneglycol) diglycidyl ether(PEGDGE) as crosslinking agents. Optimal concentrations of PEI in PTMSP and PEGDGE in methanol were selected in order to diminish the undesirable effect on the final membrane gas transport characteristics. The conditions of the kiss-coating technique for the deposition of the thin defect-free PTMSP-based layer, namely, composition of the casting solution and the speed of movement of the porous commercial microfiltration-grade support, were optimized. The procedure of post-treatment with alcohols and alcohol solutions was shown to be crucial for the improvement of gas permeance of the membranes with the crosslinked PTMSP layer having thickness ranging within 1-2.5 μm. The claimed membranes showed the following characteristics: CO_2 permeance is equal to 50—54 m^3(STP)/(m^2 h bar)(18,500—20,000 GPU), ideal CO_2/N_2 selectivity is 3.6-3.7, and their selective layers are insoluble in chloroform. Thus, the developed highpermeance TFC membranes are considered as a promising supports for further modification by enhanced CO_2 selective layer formation.

Coordination of thin-film nanofibrous composite dialysis membrane and reduced graphene oxide aerogel adsorbents for elimination of indoxyl sulfate

The protein-bound uremic toxins,represented by indoxyl sulfate(IS),have been associated with the progression of chronic kidney disease and the development of cardiovascular disease in the presence of impaired renal function.Herein,we proposed a novel strategy of thin-film nanofibrous composite(TNFC)dialysis membrane combined with reduced graphene oxide(rGO)aerogel adsorbents for clinical removal of IS as well as high retention of proteins.The TFNC membrane was prepared by electrospinning in conjunction with coating-reaction method and proved to have good selectivity and permeability.To further improve the removal rate of toxins,we used a medium hydrothermal method following by freeze-drying treatment to obtain the r GO aerogel adsorbents.It exhibited excellent adsorption for IS with a maximum adsorption capacity of 69.40 mg·g^(-1)throughπ-πinteraction and hydrogen bonding interaction based on Langmuir isotherm models.Time-dependent absorption experiments showed that it reached adsorption equilibrium within 4 h,which was matched with the hemodialysis time.The coordination was significantly exhibited by introducing r GO aerogel blocks into the dialysate for absorbing the diffused free IS during hemodialysis.Taking the advantages of the TFNC dialysis membrane and the rGO aerogel,the volume of dialysate for hemodialysis was only one-tenth of that without adsorbent blocks but with very comparable dialysis performance(the clearance of IS at 51.8%and the retention of HSA over 98%),which could lighten conventional hemodialysis effectively and be benefit to realize the miniaturization of the hemodialysis equipment.Therefore,the coordination of the TFNC dialysis membrane and rGO aerogel adsorbents would open a new path for the development of portable artificial kidney.

Recent developments in nanofiltration membranes based on nanomaterials

Nanofiltration membranes are the core elements for nanofiltration process. The chemical structures and physical properties of nanofiltration membranes determine water permeability, solute selectivity, mechanical/thermal stability, and antifouling properties, which greatly influence the separation efficiency and operation cost in nanofiltration applications. In recent years, a great progress has been made in the development of high performance nanofiltration membranes based on nanomaterials. Considering the increasing interest in this field, this paper reviews the recent studies on the nanofiltration membranes comprising various nanomaterials, including the metal and metal oxide nanoparticles, carbon-based nanomaterials, metal–organic frameworks(MOFs), water channel proteins, and organic micro/nanoparticles. Finally, a perspective is given on the further exploitation of advanced nanomaterials and novel strategy for fabricating nano-based nanofiltration membranes. Moreover,the development of precision instruments and simulation techniques is necessary for the characterization of membrane microstructure and investigation of the separation and antifouling mechanism of nanofiltration membranes prepared with nanomaterials.

CO2/CH4 separation using inside coated thin film composite hollow fiber membranes prepared by interfacial polymerization

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.

Development of CO2 Selective Poly（Ethylene Oxide）-Based Membranes： From Laboratory to Pilot Plant Scale

Membrane gas separation is one of the most promising technologies for the separation of carbon dioxide （CO2） from various gas streams. One application of this technology is the treatment of flue gases from combustion processes for the purpose of carbon capture and storage. For this application, poly（ethylene oxide）-containing block copolymers such as Pebax or PolyActiveTM polymer are well suited. The thin-film composite membrane that is considered in this overview employs PolyActiveTM polymer as a selective layer material. The membrane shows excellent CO2 permeances of up to 4 m^3（STP）.（m^2·h·bar）^-1 （1 bar = 105 Pa） at a carbon dioxide/nitrogen （CO2/N2） selectivity exceeding 55 at ambient temperature. The membrane can be manufactured reproducibly on a pilot scale and mounted into fiat-sheet membrane modules of different designs. The operating performance of these modules can be accurately predicted by specifically developed simulation tools, which employ single-gas permeation data as the only experimental input. The performance of membranes and modules was investigated in different pilot plant studies, in which flue gas and biogas were used as the feed gas streams. The investigated processes showed a stable separation performance, indicating the applicability of PolyActiveTM polymer as a membrane material for industrialscale gas processing.

In-situ incorporation of halloysite nanotubes with 2D zeolitic imidazolate framework-L based membrane for dye/salt separation

Layered assembled membranes of 2D leaf-like zeolitic imidazolate frameworks(ZIF-L)nanosheets have received great attention in the field of water treatment due to the porous structure and excellent antibacterial ability,but the dense accumulation on the membrane surface and the low permeate flux greatly hinder their application.Herein,we synthesized m HNTs(modified halloysite nanotubes)/ZIF-L nanocomposites on modified m HNTs by in situ growth method.Interestingly,due to the different size of m HNTs and ZIF-L,m HNTs were packed in ZIF-L nanosheets.The hollow m HNTs provided additional transport channels for water molecules,and the accumulation of the ZIF-L nanosheets was decreased after assembling m HNTs/ZIF-L nanocomposites into membrane by filtration.The prepared m HNTs/ZIF-L membrane presented high permeate flux(59.6 L·m^(-2)·h^(-1)),which is 2-4 times of the ZIF-L membranes(14.8 L·m^(-2)·h^(-1)).Moreover,m HNTs/ZIF-L membranes are intrinsically antimicrobial,which exhibit extremely high bacterial resistance.We provide a controllable strategy to improve 2D ZIF-L assembles,and develops novel membranes using 2D package structure as building units.

Effect of silver-nanoparticles generated in poly(vinyl alcohol)membranes on ethanol dehydration via pervaporation

Pervaporation is an important membrane separation method of chemical engineering.In this work,silver-nanoparticles-poly(vinyl alcohol)nanocomposite membranes(AgNPs-PVA)are produced for the sake of improving its potentials for pervaporation of ethanol–water mixture so that the usual opposite trend between membrane selectivity and permeation can be reduced.The nanocomposite membranes are fabricated from an aqueous solution of poly(vinyl alcohol)with silver nanoparticles via the in-situ generation technique in the absence of any reducing agent.Successful generation of the nano size silver is measured by the UV–vis spectrum showing a single peak at 419 nm due to the plasmonic effect of silver nanoparticles.Our nanocomposite AgNPs-PVA membranes are characterized using scanning electron microscope(SEM),Fourier-transform infrared(FT-IR)spectroscopy,X-ray diffraction and thermogravimetric analysis(TGA).The pervaporation tests of our new AgNPs-PVA membranes show good results since at a higher temperature and higher ethanol concentration in the feed,the prepared membranes are highly permeable for the water having stable selectivity values and therefore our membranes show better performance compared to that of the other PVA-based nanocomposite membranes.

Tuning the primary selective nanochannels of MOF thin-film nanocomposite nanofiltration membranes for efficient removal of hydrophobic endocrine disrupting compounds

Metal organic framework(MOF)incorporated thin-film nanocomposite(TFN)membranes have the potential to enhance the removal of endocrine disrupting compounds(EDCs).In MOF-TFN membranes,water transport nanochannels include(i)pores of polyamide layer,(ii)pores in MOFs and(iii)channels around MOFs(polyamide-MOF interface).However,information on how to tune the nanochannels to enhance EDCs rejection is scarce,impeding the refinement of TFN membranes toward efficient removal of EDCs.In this study,by changing the polyamide properties,the water transport nanochannels could be confined primarily in pores of MOFs when the polyamide layer became dense.Interestingly,the improved rejection of EDCs was dependent on the water transport channels of the TFN membrane.At low monomer concentration(i.e.,loose polyamide structure),the hydrophilic nanochannels of MIL-101(Cr)in the polyamide layer could not dominate the membrane separation performance,and hence the extent of improvement in EDCs rejection was relatively low.In contrast,at high monomer concentration(i.e.,dense polyamide structure),the hydrophilic nanochannels of MIL-101(Cr)were responsible for the selective removal of hydrophobic EDCs,demonstrating that the manipulation of water transport nanochannels in the TFN membrane could successfully overcome the permeability and EDCs rejection trade-off.Our results highlight the potential of tuning primary selective nanochannels of MOF-TFN membranes for the efficient removal of EDCs.

A Novel Guided Bone Regeneration Membrane Composed of Nano-hydroxyapatite and Aliphatic Polyester-amide

Hydrothermally synthesized nano-hydroxyapatite（n-HA ） varmg m wetght Jrom 10% to 30% was used us filler to make guided bone regeneration （ GBR ） composite membranes with navel aliphatic polyesteramide （ PEA ）. The structare and properties of PEA and its n- HA composites were investigated through TEM, IR, XRD, SEM and EDX. The shape and size of the n- HA crystals are similar to the apatite crystals in nataral bone. Molecule interactions are present between the n- HA and PEA in the compasite, which allows the uniform dispersion of n- HA in PEA matrix. This contributes enhanced mechanical property and bioactivhy to the compasite. The cytacompatibilhy of the composites has been investigated by culturing osteoblasts on the membranes. Good cell attachment and proliferation manner were observed on the membranes after 1 week. These results suggest that the PEA/ n-HA compasite membrane prepared in this study may serve us barrier membranes for guided bone regeneration and potential candidate scaffold for tissue engineering.

Surface modification of mesoporous silica nanoparticle with 4-triethoxysilylaniline to enhance seawater desalination properties of thin-film nanocomposite reverse osmosis membranes

Mesoporous silica nanoparticles(MSN),with higher water permeability than NaA zeolite,were used to fabricate thin-film nanocomposite(TFN)reverse osmosis(RO)membranes.However,only aminoalkyl-modified MSN and low-pressure(less than 2.1 MPa)RO membrane were investigated.In this study,aminophenyl-modified MSN(AMSN)were synthesized and used to fabricate high-pressure(5.52 MPa)RO membranes.With the increasing of AMSN dosage,the crosslinking degree of the aromatic polyamide decreased,while the hydrophilicity of the membranes increased.The membrane morphology was maintained to show a ridge-and-valley structure,with only a slight increase in membrane surface roughness.At the optimum conditions(AMSN dosage of 0.25 g/L),when compared with the pure polyamide RO membrane,the water flux of the TFN RO membrane(55.67 L/m^2/h)was increased by about 21.6%,while NaCl rejection(98.97%)was slightly decreased by only 0.29%.However,the water flux of the membranes was much lower than expected.We considered that the enhancement of RO membrane permeability is attributed to the reduction of the effective thickness of the PA layer.