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.

Enhancing CO_(2) transport with plasma-functionalized ionic liquid membranes

The ionic liquid(IL) 1-butyl-3-methylimidazolium tetrafluoroborate treated with radiofrequency plasma is proposed for functionalization and immobilization on polyethersulfone supports to form supported ionic liquid membranes for CO_(2) separation.The effects of treatment time and transmembrane pressure difference on CO_(2) permeance were evaluated.The best gas permeation performance was obtained with a treatment time of 10 min and the transmembrane pressure difference was 0.25 MPa.Characterization of the materials by Fourier transform infrared spectroscopy,x-ray photoelectron spectroscopy and nuclear magnetic resonance spectroscopy demonstrates that the IL is grafted with carboxyl groups and deprotonated through plasma treatment.A preliminary mechanism for the plasma treatment and facilitated transport of CO_(2)has been proposed on this basis.

Chitosan derived carbon membranes as protective layers on zinc anodes for aqueous zinc batteries

Aqueous zinc batteries with low cost and inherent safety are considered to be the most promising energy storage devices.However,they suffer from poor cycling stability and low coulombic efficiencies caused by the adverse zinc dendrites on the anodes during the discharging/charging processes.Chitosan is a kind of natural amino polysaccharide,which is rich in nitrogen and carbon.When sintered at high temperatures,carbon membranes have been achieved with excellent conductivity and graphitization degree,which could enhance the ability to induce zinc ion uniform deposition to some extent.In this work,a type of carbon membrane using chitosan as raw materials has been fabricated by sintering,and then assembled as the protect layers in aqueous zinc batteries.The results show that the samples could retain smoother surfaces when adopting the sintering temperature of 800℃,and the assembled batteries are able to achieve about 700 h at a current density of 0.25m A·cm^(-2),which is far longer than those of the similar batteries without any carbon membranes.

Carbon Capture from Flue Gas Based on the Combination of Non-Contact Hydrophobic Porous Ceramic Membrane and Bubbling Absorption

A hybrid system combined with a non-contact membrane and bubbling absorption is proposed to capture CO_(2) from flue gas.The non-contact way of membrane and liquid absorbent effectively avoids the reduction of gas diffusion flux through the membrane.High-porosity ceramic membranes in hybrid systems are used for gas-solid separation in fuel gas treatment.Due to the high content of H_(2)O and cement dust in the flue gas of the cement plant,the membrane is hydrophobically modified by polytetrafluoroethylene(PTFE)to improve its anti-water,anti-fouling,and self-cleaning performances.The results show that the diffusion flux of CO_(2) through the membrane is still higher than 7.0×10^(−3) mol/m^(2)s(20%CO_(2) concentration)even under the influence of water and cement dust.In addition,slaked lime selected as the absorbent is cheap and the product after bubbling absorption is nano-scale light calcium carbonate.To sum up,the hybrid system combining non-contact membrane and bubbling absorption is expected to be used to capture carbon dioxide from the flue gas of the cement plant.

Highly Conductive Proton Selectivity Membrane Enabled by Hollow Carbon Sieving Nanospheres for Energy Storage Devices

Ion conductive membranes(ICMs)with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices.However,it is extremely challenging to construct fast proton-selective transport channels in ICMs.Herein,a membrane with highly conductive proton selectivity was fabricated by incorporating porous carbon sieving nanospheres with a hollow structure(HCSNs)in a polymer matrix.Due to the precise ion sieving ability of the microporous carbon shells and the fast proton transport through their accessible internal cavities,this advanced membrane presented a proton conductivity(0.084 S·cm^(-1))superior to those of a commercial Nation 212(N212)membrane(0.033S·cm^(-1))and a pure polymer membrane(0.049 S·cm^(-1)).The corresponding proton selectivity of the membrane(6.68×10^(5) S·min·cm^(-3))was found to be enhanced by about 5.9-fold and 4.3-fold,respectively,compared with those of the N212 membrane(1.13×10^(5) S·min·cm^(-3))and the pure membrane(1.56×10^(5) S·min·cm^(-3)).Low-field nuclear magnetic resonance(LF-NMR)clearly revealed the fast protonselective transport channels enabled by the HCSNs in the polymeric membrane.The proposed membrane exhibited an outstanding energy efficiency(EE)of 84%and long-term stability over 1400 cycles with a0.065%capacity decay per cycle at 120 mA·cm^(-2) in a typical vanadium flow battery(VFB)system.

Engineering HOF‑Based Mixed‑Matrix Membranes for Efficient CO_(2) Separation

Hydrogen-bonded organic frameworks(HOFs)have emerged as a new class of crystalline porous materials,and their application in membrane technology needs to be explored.Herein,for the first time,we demonstrated the utilization of HOF-based mixed-matrix membrane for CO_(2) separation.HOF-21,a unique metallo-hydrogen-bonded organic framework material,was designed and processed into nanofillers via amine modulator,uniformly dispersing with Pebax polymer.Featured with the mix-bonded framework,HOF-21 possessed moderate pore size of 0.35 nm and displayed excellent stability under humid feed gas.The chemical functions of multiple binding sites and continuous hydrogen-bonded network jointly facilitated the mass transport of CO_(2).The resulting HOF-21 mixed-matrix membrane exhibited a permeability above 750 Barrer,a selectivity of~40 for CO_(2)/CH_(4) and~60 for CO_(2)/N_(2),surpassing the 2008 Robeson upper bound.This work enlarges the family of mixed-matrix membranes and lays the foundation for HOF membrane development.

Effect of powdered activated carbon on Chinese traditional medicine wastewater treatment in submerged membrane bioreactor with electronic control backwashing

Chinese traditional medicine wastewater, rich in macromolecule and easy to foam in aerobic biodegradation such as Glycosides, was treated by two identical bench-scale aerobic submerged membrane bioreactors （SMBRs） operated in parallel under the same feed, equipped with the same electronic control backwashing device. One was used as the control SMBR （CSMBR） while the other was dosed with powdered activated carbon （PAC） （PAC-amended SMBR, PSMBR）. The backwashing interval was 5 min. One suction period was about 90 min by adjusting preestablished backwashing vacuum and pump frequency. The average flux of CSMBR during a steady periodic state of 24 d （576 h） was 5.87 L/h with average hydraulic residence time （HRT） of 5.97 h and that of PSMBR during a steady periodic state of 30 d （720 h） was 5.85 L/h with average HRT of 5.99 h. The average total chemical oxygen demand （COD） removal efficiency of CSMBR was 89.29% with average organic loading rate （OLR） at 4.16 kg COD/（m^3.d） while that of PSMBR was 89.79% with average OLR at 5.50 kg COD/（m^3.d）. COD concentration in the effluent of both SMBRs achieved the second level of the general wastewater effluent standard GB8978-1996 for the raw medicine material industry （300 mg/L）. Hence, SMBR with electronic control backwashing was a viable process for medium-strength Chinese traditional medicine wastewater treatment. Moreover, the increasing rates of preestablished backwashing vacuum, pump frequency, and vacuum and flux loss caused by mixed liquor in PSMBR all lagged compared to those in CSMBR; thus the actual operating time of the PSMBR system without membrane cleaning was extended by up to 1.25 times in contrast with the CSMBR system, and the average total COD removal efficiency of PSMBR was enhanced with higher average OLR.

Coarse grained molecular dynamics and theoretical studies of carbon nanotubes entering cell membrane

Motivated by recent experimental observations that carbon nanotubes （CNT） can enter animal cells, here we conduct coarse grained molecular dynamics and theoretical studies of the intrinsic interaction mechanisms between CNT＇s and lipid bilayer. The results indicate that CNT-cell interaction is dominated by van der Waals and hydrophobic forces, and that CNT＇s with sufficiently small radii can directly pierce through cell membrane while larger tubes tend to enter cell via a wrapping mechanism. Theoretical models are proposed to explain the observed size effect in transition of entry mechanisms.

Ultraselective carbon molecular sieve membrane for hydrogen purification

Hydrogen is a green clean fuel and chemical feedstock. Its separation and purification from hydrogencontaining mixtures is the key step in the production of hydrogen with high purity(>99.99%). In this work, carbon molecular sieve(CMS) membranes with ultrahigh permselectivity for hydrogen purification were fabricated by high-temperature(700–900 ℃) pyrolysis of polymeric precursor of phenolphthaleinbased cardo poly(arylene ether ketone)(PEK-C). The evolution of the microstructural texture and ultramicroporous structure and gas separation performance of the CMS membrane were characterized via TG-MS, FT-IR, XRD, TEM, CO2 sorption analysis and gas permeation measurements. CMS membranes prepared at 700 ℃ exhibited amorphous turbostratic carbon structures and high H2 permeability of 5260 Barrer with H2/CH4, H2/N2 and H2/CO selectivities of 311, 142, 75, respectively. When carbonized at900 ℃, the CMS membrane with ultrahigh H2/CH4 selectivity of 1859 was derived owing to the formation of the dense and ordered carbon structure. CMS membranes with ultrahigh permselectivity exhibit an attractive application prospect in hydrogen purification.

Non-equilibrium Molecular Dynamics Simulation on Pure Gas Permeability Through Carbon Membranes

The permeation of various pure gas （H2, He, Ne, CH4 and At） through carbon membranes is investigated using a dual control volume grand canonical molecular dynamics method. A two-dimensional slit pore is employed instead of the one-dimensional pore. Compared with the experiments, simulation results show that the improvement of pore model is very necessary. The effects of membrane thickness, pore width and temperature on gas permeance and ideal separation factor are also discussed. Results show that gas permeates through membrane according to Knudsen diffusion in large pore, while Knudsen diffusion is accompanied by molecular sieving in small pore. Moreover, methane is easily adsorbed on the membrane surface due to strong attractive interactions of membrane and shows higher permeance than that of Knudsen flow. In addition, it is noted that when membrane thickness is thin enough the permeance of gas does not decrease with the increase of membrane thickness due to the strong adsorption until membrane resistance becomes dominant.

AgBF_4/[emim][BF_4] supported ionic liquid membrane for carbon monoxide/nitrogen separation

In this paper,AgBF_4/[emim][BF_4] supported ionic liquid membranes(SILMs) were prepared successfully for CO/N_2 separation using nitrogen pressure immobilization procedures.The incorporation of AgBF_4 could decrease membrane weight loss,improve the pressure-resistant ability,and keep the critical pressure(0.45 MPa) of the SILMs.The high viscosity and undissolved Ag BF_4 solids in membrane liquid would disturb gas molecular transport through membrane and give rise to the gas transport resistance.Therefore,the gas permeability decreased remarkably with increasing AgBF_4 carrier content in the membrane.When the molar ratio of AgBF_4 to [emim][BF_4] increased from 0:1 to 0.3:1,the CO/N_2 selectivity of the SILMs showed a great increase from ～1 to ～9 at 20 °C and 0.4 MPa,suggesting that AgBF_4 was an effective carrier for CO facilitated transport.The permeabilities of N_2 and CO increased at higher transmembrane pressure,indicating that molecular transport would dominate the transport process at high pressure.The temperature-dependent gas permeability followed the Arrhenius equation.Moreover,the differences between the activation energies of CO and N_2 became larger after introducing AgBF_4,resulting in more obvious decrease in the CO/N_2 selectivity at higher operating temperature.

In situ grown nanoscale platinum on carbon powder as catalyst layer in proton exchange membrane fuel cells(PEMFCs)

An extensive study has been conducted on the proton exchange membrane fuel cells （PEMFCs） with reducing Pt loading. This is commonly achieved by developing methods to increase the utilization of the platinum in the catalyst layer of the electrodes. In this paper, a novel process of the catalyst layers was introduced and investigated. A mixture of carbon powder and Nafion solution was sprayed on the glassy carbon electrode （GCE） to form a thin carbon layer. Then Pt particles were deposited on the surface by reducing hexachloroplatinic （IV） acid hexahydrate with methanoic acid. SEM images showed a continuous Pt gradient profile among the thickness direction of the catalytic layer by the novel method. The Pt nanowires grown are in the size of 3 nm （diameter） x l0 nm （length） by high solution TEM image. The novel catalyst layer was characterized by cyclic voltammetry （CV） and scanning electron microscope （SEM） as compared with commercial Pt/C black and Pt catalyst layer obtained from sputtering. The results showed that the platinum nanoparticles deposited on the carbon powder were highly utilized as they directly faced the gas diffusion layer and offered easy access to reactants （oxygen or hydrogen）.

Impregnation of carbonaceous nanofibers into glassy polymer-based composite membrane for CO_2 separation

The development of defect-free composite membrane(CM) is often challenging due to poor dispersion and distribution of filler particles in the polymer matrix. Despite the attractive physicochemical properties and gas separation performance of carbon nanotube(CNT) based CM, CNT displayed poor dispersion characteristics in most polymer matrix domain. Instead of incorporating CNT, a viable alternative, carbon nanofiber(CNF) which exhibits similar properties as CNT, but improved dispersion quality in the polymer matrix is found. In this work,CNF particles were incorporated in poly(2,6-dimethyl-1,4-phenylene oxide)(PPOdm) polymer continuous phase for CM development. The optimum gas separation performance of the PPOdm-CNF CM(11.25 at 197.02 barrer of CO_2 permeability) was obtained at 3 wt% of CNF loading. Compared to pristine PPOdmmembrane,CO_2 permeability and CO_2/CH_4 selectivity of PPOdm-3 wt% CNF CM were enhanced by 180% and 55%, respectively.At 3 wt% CNF loading, the filler particles were dispersed and distributed more homogenously, in which no obvious CNF agglomeration was observed. In addition, the incorporation of CNF particles also enhanced the mechanical and thermal properties of the resultant CM.

High-performance proton exchange membrane fuel cell with ultra-low loading Pt on vertically aligned carbon nanotubes as integrated catalyst layer

Reducing a Pt loading with improved power output and durability is essential to promote the large-scale application of proton exchange membrane fuel cells(PEMFCs).To achieve this goal,constructing optimized structure of catalyst layers with efficient mass transportation channels plays a vital role.Herein,PEMFCs with order-structured cathodic electrodes were fabricated by depositing Pt nanoparticles by Ebeam onto vertically aligned carbon nanotubes(VACNTs)growth on Al foil via plasma-enhanced chemical vapor deposition.Results demonstrate that the proportion of hydrophilic Pt-deposited region along VACNTs and residual hydrophobic region of VANCTs without Pt strongly influences the cell performance,in particular at high current densities.When Pt nanoparticles deposit on the top depth of around 600 nm on VACNTs with a length of 4.6μm,the cell shows the highest performance,compared with others with various lengths of VACNTs.It delivers a maximum power output of 1.61 W cm^(-2)(H_(2)/O_(2),150 k Pa)and 0.79 W cm^(-2)(H_(2)/Air,150 k Pa)at Pt loading of 50μg cm^(-2),exceeding most of previously reported PEMFCs with Pt loading of<100μg cm^(-2).Even though the Pt loading is down to 30μg cm^(-2)(1.36 W cm^(-2)),the performance is also better than 100μg cm^(-2)(1.24 W cm^(-2))of commercial Pt/C,and presents better stability.This excellent performance is critical attributed to the ordered hydrophobic region providing sufficient mass passages to facilitate the fast water drainage at high current densities.This work gives a new understanding for oxygen reduction reaction occurred in VACNTs-based ordered electrodes,demonstrating the most possibility to achieve a substantial reduction in Pt loading<100μg cm^(-2) without sacrificing in performance.

High-performance SSZ-13 membranes prepared using ball-milled nanosized seeds for carbon dioxide and nitrogen separations from methane

SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis.Separation performances of SSZ-13 membranes in CO2/CH4 and N2/CH4 mixtures were enhanced after synthesis modification.Single-gas permeances of CO2,N2 and CH4 and ideal selectivities were recorded through SSZ-13 membranes.The effects of temperature,pressure,feed flow rate and humidity on separation performance of the membranes were discussed.Three membranes prepared after synthesis modifications had an average CO2 permeance of 1.16×10-6 mol·(m2·s·Pa)-1(equal to 3554 GPU)with an average CO2/CH4 selectivity of 213 in a 50 vol%/50 vol%CO2/CH4 mixture.It suggests that membrane synthesis has a good reproducible.The membrane also displayed a N2 permeance of 1.07×10-7 mol·(m2·s·Pa)-1(equal to 320 GPU)with a N2/CH4 selectivity of 13 for a 50 vol%/50 vol%N2/CH4 mixture.SSZ-13 membrane displayed stable and good separation performance in the wet CO2/CH4 mixture for a long test period over 100 h at 348 K.The current SSZ-13 membranes show great potentials for the simultaneous removals of CO2 and N2 in natural gas purification as a facile process suitable for industrial application.

Polyvinyl acetate/poly(amide-12-b-ethylene oxide) blend membranes for carbon dioxide separation

In this paper,blend membranes from polyvinyl acetate(PVAc)and block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074)are prepared by solution casting and solvent evaporation method.Although they are homogeneous on a macro-scale,the observations from DSC and SEM indicate micro-phase separation for PVAc/Pebax1074 blend membranes.With the increase of Pebax1074 content,gas permeabilities of CO2,H2,N2and CH4all increase greatly.PVAc/Pebax1074 blend membranes with high PVAc content are appropriate for CO2/CH4separation.The temperature dependence of gas permeability is divided into rubbery region and glassy region.The activation energies of permeation in rubbery region are smaller than those in glassy region,and they all decrease with increasing Pebax1074 content.For N2,H2and CH4,their gas permeation properties are mainly influenced by the dual-mode sorption and hydrostatic pressure effect.But for CO2,its permeability increases with the increase of pressure due to CO2-induced plasticization effect,which is more obvious for PVAc/Pebax1074 blend membranes with high PVAc content.

Poly(amide-6-b-ethylene oxide)/[Bmim][Tf2N] blend membranes for carbon dioxide separation

Poly（amide-6-b-ethylene oxide）（Pebax1657）/1-butyl-3-methylimidazo-lium bis[trifluoromethyl）sulfonyl]-imide（[Bmim][Tf2N]） blend membranes with different [Bmim][Tf2N] contents were prepared via solution casting and solvent evaporation method. The permeation properties of the blend membranes for CO2, N2,CH4 and H2 were studied, and the physical properties were characterized by differential scanning calorimeter（DSC） and X-ray diffraction（XRD）. Results showed that [Bmim][Tf2N] was dispersed as amorphous phase in the blend membranes, which caused the decrease of Tg（PE） and crystallinity（PA）. With the addition of [Bmim][Tf2N], the CO2 permeability increased and reached up to approximately 286 Barrer at 40 wt%[Bmim][Tf2N], which was nearly double that of pristine Pebax1657 membrane. The increase of CO2 permeability may be attributed to high intrinsic permeability of [Bmim][Tf2N], the increase of fractional free of volume（FFV） and plasticization effect. However, the CO2 permeability reduced firstly when the [Bmim][Tf2N]content was below 10 wt%, which may be due to that the small ions of [Bmim][Tf2N] in the gap of polymer chain inhibited the flexibility of polymer chain; the interaction between Pebax1657 and [Bmim][Tf2N]decreased the content of EO units available for CO2 transport and led to a more compact structure. For Pebax1657/[Bmim][Tf2N] blend membranes, the permeabilities of N2, H2 and CH4decreased with the increase of feed pressure due to the hydrostatic pressure effect, while CO2 permeability increased with the increase of feed pressure for that the CO2-induced plasticization effect was stronger than hydrostatic pressure effect.

Study on durability of Pt supported on graphitized carbon under simulated start-up/shut-down conditions for polymer electrolyte membrane fuel cells

The primary issue for the commercialization of proton exchange membrane fuel cell（PEMFC） is the carbon corrosion of support under start-up/shut-down conditions. In this study, we employ the nanostructured graphitized carbon induced by heat-treatment. The degree of graphitization starts to increase between 900 and 1300 ℃ as evidenced by the change of specific surface area, interlayer spacing, and ID/IG value. Pt nanoparticles are deposited on fresh carbon black（Pt/CB） and carbon heat-treated at 1700 ℃（Pt/HCB17） with similar particle size and distribution. Electrochemical characterization demonstrates that the Pt/HCB17 shows higher activity than the Pt/CB due to the inefficient microporous structure of amorphous carbon for the oxygen reduction reaction. An accelerating potential cycle between 1.0 and 1.5 V for the carbon corrosion is applied to examine durability at a single cell under the practical start-up/shutdown conditions. The Pt/HCB17 catalyst shows remarkable durability after 3000 potential cycles. The Pt/HCB17 catalyst exhibits a peak power density gain of 3%, while the Pt/CB catalyst shows 65% loss of the initial peak power density. As well, electrochemical surface area and mass activity of Pt/HCB17 catalyst are even more stable than those of the Pt/CB catalyst. Consequently, the high degree of graphitization is essential for the durability of fuel cells in practical start-up/shut-down conditions due to enhancing the strong interaction of Pt and π-bonds in graphitized carbon.

Diffusion of H2, CO, N2,O2 and CH4 Through Nanoporous Carbon Membranes

Diffusion of pure H2, CO, N2,O2 and CH4 gases through nanoporous carbon membrane is investigated by carrying out non-equilibrium molecular dynamics （NEMD） simulations. The flux, transport diffusivity and activation energy for the pure gases diffusing through carbon membranes with various pore widths were investigated. The simulation results reveal that transport diffusivity increases with temperature and pore width, and its values have a magnitude of 10^-7 m^2·s^-1 for pore widths of about 0.80 to 1.21 nm at 273 to 300 K. The activation energies for the gases diffusion through the membrane with various pore widths are about 1-5 kJ·mol^-1, The results of transport diffusivities are comparable with that of Rao and Sircar （J. Membr. Sci., 1996）, indicating the NEMD simulation method is a good tool for predicting the transport diffusivities for gases in porous materials, which is always difficult to be accurately measured by experiments.

Removal of Pesticides from Water Using Granular Activated Carbon and Ultrafiltration Membrane—A Pilot Plant Study

The use of powdered activated carbon for fouling control in the membrane processes is limited by some secondary problems associated with its use, like cake formation, long backwash times and blackening of pipes. Granular activated carbon (GAC) was used as an alternative of powdered activated carbon due to its large particle size which was kept from being entering into the membrane system. The secondary problems associated with the use of powdered activated carbon as foul control were not observed for granular activated carbon. Langmuir and Freundlich adsorption were used to describe the adsorption of 2,4-D and paraquat on GAC. Adsorption capacity of adsorbent was high for 2,4-D as compared to paraquat. Also, the R2 value was high for Langmuir model as compared to Freundlich model. Retention percentage of 2,4-D by membrane was high and thus the decline in permeate flux was high as compared to paraquat in ultrafiltration (UF) membrane process. 100% retention of 2,4-D was achieved in GAC/UF hybrid system. Improved permeate fluxes were observed for both contaminants in the hybrid system.