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.

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.

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.

Techno-economical evaluation of membrane based biogas upgrading system:A comparison between polymeric membrane and carbon membrane technology

A shift to renewable energy sources will reduce emissions of greenhouse gases and secure future energy supplies. In this context, utilization of biogas will play a prominent role. Focus of this work is upgrading of biogas to fuel quality by membrane separation using a carbon hollow fibre(CHF) membrane and compare with a commercially available polymeric membrane(polyimide) through economical assessment. CHF membrane modules were prepared for pilot plant testing and performance measured using CO_2, O_2, N_2. The CHF membrane was modified through oxidation, chemical vapour deposition(CVD) and reduction process thus tailoring pores for separation and increased performance. The post oxidized and reduced carbon hollow fibres(PORCHFs) significantly exceeded CHF performance showing higher CO_2 permeance(0.021 m^3(STP)/m^2 h bar) and CO_2/CH_4 selectivity of 246(5 bar feed vs 50 mbar permeate pressure). The highest performance recorded through experiments(CHF and PORCHF) was used as simulation basis. A membrane simulation model was used and interfaced to 8.6 V Aspen HYSYS.A 300 Nm^3/h mixture of CO_2/CH_4 containing 30-50% CO_2 at feed pressures 6, 8 and 10 bar, was simulated and process designed to recover99.5% CH_4 with 97.5% purity. Net present value(NPV) was calculated for base case and optimal pressure(50 bar for CHF and PORCHF). The results indicated that recycle ratio(recycle/feed) ranged from 0.2 to 10, specific energy from 0.15 to 0.8(kW/Nm^3 feed) and specific membrane area from 45 to 4700(m^2/Nm^3 feed). The high recycle ratio can create problems during start-up, as it would take long to adjust volumetric flow ratio towards 10. The best membrane separation system employs a three-stage system with polyimide at 10 bar, and a two-stage membrane system with PORCHF membranes at 50 bar with recycle. Considering biomethane price of 0.78 $/Nm^3 and a lifetime of 15 years, the technoeconomic analysis showed that payback time for the best cascade is 1.6 months.

Hierarchically Porous Carbon Membranes Derived from PAN and Their Selective Adsorption of Organic Dyes

Porous carbon membranes were favorably fabricated through the pyrolysis of polyacrylonitrile（PAN） precursors, which were prepared with a template-free technique-thermally induced phase separation. These carbon membranes possess hierarchical pores, including cellular macropores across the whole membranes and much small pores in the matrix as well as on the pore walls. Nitrogen adsorption indicates micropores（1.47 and 1.84 nm） and mesopores（2.21 nm） exist inside the carbon membranes, resulting in their specific surface area as large as 1062 m2/g. The carbon membranes were used to adsorb organic dyes（methyl orange, Congo red, and rhodamine B） from aqueous solutions based on their advantages of hierarchical pore structures and large specific surface area. It is particularly noteworthy that the membranes present a selective adsorption towards methyl orange, whose molecular size（1.2 nm） is smaller than those of Congo red（2.3 nm） and rhodamine B（1.8 nm）. This attractive result can be attributed to the steric structure matching between the molecular size and the pore size, rather than electrostatic attraction. Furthermore, the used carbon membranes can be easily regenerated by hydrochloric acid, and their recovery adsorption ratio maintains above 90% even in the third cycle. This work may provide a new route for carbon-based adsorbents with hierarchical pores via a template-free approach, which could be promisingly applied to selectively remove dye contaminants in aqueous effluents.

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.

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.

STUDY ON THE ELECTROCHEMICAL BEHAVIOR OF ION EXCHANGE MEMBRANE IN PREPARING POTASSIUM CARBONATE

This investigation describes the one step preparation of potassium carbonate by electrolysis of potas-sium chloride solution in electrolyzers with various Nation membranes.Potassium bicarbonate solution wasfed to the cathode compartment,where it was converted into carbonate by reaction with the hydroxideformed at cathode.Because of the low OH^- concentration in the cathode compartment,the back migrationof OH^- through the membrane was almost negligible,resulting in a higher current efficiency,say 90% or more.In this study,electroconductivity,mass transfer,current efficiency and cell voltage were measured.Thefeasibility of the process was discussed and the optimal conditions examined.

High CO_(2)permeation using a new Ce_(0.85)Gd_(0.15)O_(2-δ)-LaNiO_(3)composite ceramic–carbonate dual-phase membrane

This work shows the synthesis,characterization and evaluation of dense-ceramic membranes made of Ce_(0.85)Gd_(0.15)O_(2-δ)-LaNiO_(3)(CG-LN)composites,where the fluorite-perovskite ratio(CG:LN)was varied as follows:75:25,80:20 and 85:15 wt.%.Supports were initially characterized by XRD,SEM and electrical conductivity(using vacuum and oxygen atmospheres),to determine the composition,microstructural and ionic-electronic conductivity properties.Later,supports were infiltrated with an eutectic carbonates mixture,producing the corresponding dense dual-phase membranes,in which CO_(2)permeation tests were conducted.Here,CO_(2)permeation experiments were performed from 900 to 700℃,in the presence and absence of oxygen(flowed in the sweep membrane side).Results showed that these composites possess high CO_(2)permeation properties,where the O_(2)addition significantly improves the ionic conduction on the sweep membrane side.Specifically,the GC80-LN20 composition presented the best results due to the following physicochemical characteristics:high electronic and ionic conductivity,appropriate porosity,interconnected porous channels,as well as thermal and chemical stabilities between the composite support and carbonate phases.

Pd micro-nanoparticles electrodeposited on graphene/polyimide membrane for electrocatalytic oxidation of formic acid

A novel Pd electrocatalyst with flowerlike micro-nanostructures was synthesized by electrochemical deposition on a flexible graphene/polyimide（Gr/PI） composite membrane and characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD）.The Pd micro-nanoparticles were prepared on a COOH-CNTs/PI membrane as a comparative sample.The XRD and SEM investigations for Pd electrodeposition demonstrate that the particle size of Gr/PI composite membrane is smaller than that of COOH-CNTs/PI membrane,while the uniform and dense distribution of Pd micro-nanoparticles on the Gr/PI composite membrane is greater than that on the COOH-CNTs/PI membrane.The electrocatalytic properties of Pd/Gr/PI and Pd/COOH-CNTs/PI catalysts for the oxidation of formic acid were investigated by cyclic voltammetry（CV） and chronoamperometry（CA）.It is found that the electrocatalytic activity and stability of Pd/Gr/PI are superior to those of Pd/COOH-CNTs/PI catalyst.This is because smaller metal particles and higher dense distribution desirably provide abundant catalytic sites and mean higher catalytic activity.Therefore,the Pd/Gr/PI catalyst has better catalytic performance for formic acid oxidation than the Pd/COOH-CNTs/PI catalyst.

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.

Conductive and corrosion behaviors of silver-doped carbon-coated stainless steel as PEMFC bipolar plates

Ni–Cr enrichment on stainless steel SS316 L resulting from chemical activation enabled the deposition of carbon by spraying a stable suspension of carbon nanoparticles; trace Ag was deposited in situ to prepare a thin continuous Ag-doped carbon film on a porous carbon-coated SS316 L substrate. The corrosion resistance of this film in 0.5 mol·L^（-1） H_2SO_4 solution containing 5 ppm F- at 80°C was investigated using polarization tests. The results showed that the surface treatment of the SS316 L strongly affected the adhesion of the carbon coating to the stainless steel. Compared to the bare SS316 L, the Ag-doped carbon-coated SS316 L bipolar plate was remarkably more stable in both the anode and cathode environments of proton exchange membrane fuel cell（PEMFC） and the interface contact resistance between the specimen and Toray 060 carbon paper was reduced from 333.0 m？·cm^2 to 21.6 m？·cm^2 at a compaction pressure of 1.2 MPa.

Truth and False-carbon Dioxide Mitigation Technologies

Research progress is required to be enhanced for those storage technologies which store CO_(2)fast and permanently.However,temporary storage technologies importance cannot be denied to immediately reduce global warming and reduce higher CO_(2)concentration in the atmosphere.Continuous CO_(2)storage facilities,semi-batch and batch pilot plants deemed necessary to build for future survival of the earth planet.Membranes can be used to separate CO_(2)from common flue gases followed by mineral carbonation to convert CO_(2)into stable carbonates.Modifications in cement industry,coal fired power plants,fertilizer industries and other chemical process industries appears essential.

Superhydrophilic Polydopamine‑Modified Carbon‑Fiber Membrane with Rapid Seawater‑Transferring Ability for Constructing Efficient Hanging‑Model Evaporator

Solar-driven seawater desalination has attracted much attention for alleviating global freshwater shortage,but the practical application is often limited by complicated fabrication processes,unsatisfactory seawater-transferring and severe salt accu-mulation on the photothermal membranes.To solve these problems,hydrophobic industrial-grade carbon fiber membrane(CFM)with good photoabsorption was surface-modified with polydopamine(PDA)to prepare superhydrophilic CFM@PDA for the construction of efficient hanging-model evaporators without salt accumulation.The coating of PDA on CFM is realized by simple self-polymerization of dopamine,and the as-prepared CFM@PDA exhibits high solar absorption effi-ciency of 96.7%,good photothermal effect and superhydrophilicity.Especially,when CFM@PDA is hanging between two water tanks(one contains seawater and the other is empty)in a flat hanging-model evaporator,it can transport seawater at a high rate(26.35 g/h)which is 3.6 times that(7.28 g/h)of commercial cotton fabric.Under simulated sunlight(1.0 kW m^(-2))irradiation,CFM@PDA shows a high evaporation rate of 1.79 kg m^(-2) h^(-1) with a solar evaporation efficiency of 92.6%.Even if NaCl solution with a high concentration(21.0 wt%)is used for the evaporation,the hanging CFM@PDA can retain a high evaporation rate(~1.80 kg m^(-2) h^(-1))without salt accumulation during the long-time test(8 h),which is significantly better than that of the tradition floating model.Therefore,this study not only demonstrates the simple preparation of super-hydrophilic CFM@PDA,but also promotes the further practical applications of hanging-model evaporators for continuous salt-free desalination.

Biomimetic high-flux proton pump constructed with asymmetric polymeric carbon nitride membrane

Biological proton pumps ferry protons in an active manner and have a high flux(a few to 10 protons/(s·nm^(2))).Integrating these features in an artificial membrane may open the way for a wide range of applications but it remains challenging.In this work,we employed a structural engineering strategy to construct an asymmetric photonic polymeric carbon nitride(C3N4)membrane that exhibited photo-driven high flux proton pumping performance.The ion transport path through the membrane is reminiscent of that in the high-flux asymmetric biological ion channel.In addition,it has a photonic structure that mimics the mosquito compound eyes with improved light adsorption.Finally,the asymmetric structure constitutes an isotype(n-n)heterojunction that enhances the separation of the light-induced electron-hole pairs.As a result,the membrane shows a flux of 89μA/cm^(2)under 100 mW/cm^(2)white light illumination(approximately one sun),the highest ever reported.This translates to a pumping rate of~6 proton/(s·nm^(2)),comparable to the biological counterpart.This work highlights the potential of multi-level structural engineering to construct high-performance bionic devices,and may find applications in solar energy harvesting and solar powered membrane process.

Preparation and characterization of novel carbon molecular sieve membrane/PSSF composite by pyrolysis method for toluene adsorption

Carbon molecular sieve membrane(CMSM)/paper-like stainless steel fibers(PSSF)has been manufactured by pyrolyzing poly(fiirfuryl alcohol)(PFA)coated on the metal fibers.PFA was synthesized using oxalic acid dihydrate as a catalyst and coated on microfibers by dip coating method.For the purpose of investigating the effects of final carbonization temperature,the composites were carbonized between 400℃ and 800℃ under flowing nitrogen.The morphology and microstructure were examined by X-ray diffraction,Fourier transforms infrared spectroscopy,scanning electron microscopy,thermogravimetric analysis,N2 adsorption and desorption,Raman spectra and X-ray photoelectron spectra.The consequences of characterization showed that the CMSM containing mesopores o f 3.9 nm were manufactured.The specific surface area of the CMSM/PSSF fabricated in different pyrolysis temperature varies from 26.5 to 169.1 m^2·g^-1 and pore volume varies from 0.06 to 0.23 cm^3·g^-1.When pyrolysis temperature exceeds 600℃,the specific surface,pore diameter and pore volume decreased as carbonization temperature increased.Besides,the degree of graphitization in carbon matrix increased with rising pyrolysis temperature.Toluene adsorption experiments on different structured fixed bed that was padded by CMSM/PSSF and granular activated carbon(GAC)were conducted.For the sake of comparison,adsorption test was also performed on fixed bed packed with GAC.The experimental results indicated that the rate constant κ′ was dramatically increased as the proportion of CMCM/PSSF composites increased on the basis of Yoon-Nelson model,which suggested that structured fixed bed padded with CMSM/PSSF composite offered higher adsorption rate and mass transfer efficiency.

Effect of ozone on the performance of a hybrid ceramic membrane-biological activated carbon process

Two hybrid processes including ozonation-ceramic membrane-biological activated carbon （BAC） （Process A） and ceramic membrane-BAC （Process B） were compared to treat polluted raw water. The performance of hybrid processes was evaluated with the removal efficiencies of turbidity, ammonia and organic matter. The results indicated that more than 99% of particle count was removed by both hybrid processes and ozonation had no significant effect on its removal. BAC filtration greatly improved the removal of ammonia. Increasing the dissolved oxygen to 30.0 mg/L could lead to a removal of ammonia with concentrations as high as 7.80 mg/L and 8.69 mg/L for Processes A and B, respectively. The average removal efficiencies of total organic carbon and ultraviolet absorbance at 254 nm （UV254, a parameter indicating organic matter with aromatic structure） were 49% and 52% for Process A, 51% and 48% for Process B, respectively. Some organic matter was oxidized by ozone and this resulted in reduced membrane fouling and increased membrane flux by 25%-30%. However, pre-ozonation altered the components of the raw water and affected the microorganisms in the BAC, which may impact the removals of organic matter and nitrite negatively.

Flexible strain sensors fabricated using aligned carbon nanofiber membranes with cross-stacked structure for extensive applications

Carbon nanofibers(CNFs)with excellent conductivity and stability have become a promising material to design the strain sensing network.To date,however,the effect of the stacked structure of CNF membrane on the sensing performance has rarely been stu-died.In this work,we reported a high-performance sensor based on the cross-stacked aligned CNF membrane.The effects of crossstacked structures on the sensing characteristics were systemati-cally investigated.The flexible strain sensor could capture low detection limit(<0.1%)with a gauge factor(GF)of 4.24 and wide strain range up to 130%.The uniform GF value reached 2050 when the strain was in the range of 100-130%.In addition,the high linearity under 40%strain(>0.998),excellent durability and quick response time(<200 ms)were demonstrated.The excellent com-prehensive performances were simultaneously obtained.The sen-sor could be used in extensive applications,such as monitoring body movements and distinguishing the track of writing.

An oxygen reduction sensor based on a novel type of porous carbon composite membrane electrode

The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using a novel type of porous carbon composite membrane/glassy carbon electrode based on the low-cost common filter paper by a simple method. The resulting device exhibited excellent electrocatalytic activities toward the oxygen reduction reaction. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and electrochemical measurements demonstrated that the porous morphology and uniformly dispersed Fe;C nanoparticles of the PCCM play an important role in the oxygen reduction reaction. A linear response range from 2mmol/L up to 110 mmol/L and a detection limit of 1.4 mmol/L was obtained with this sensor. The repeatability of the proposed sensor,evaluated in terms of relative standard deviation, was 3.0%. The successful fabrication of PCCM/GC electrode may promote the development of new porous carbon oxygen reduction reaction material for the oxygen reduction sensor.