Carbon Molecular Sieve Research Articles

Cellulose-based carbon membranes for gas separations - Unraveling structural parameters and surface chemistry for superior separation performance

Carbon molecular sieve membranes were prepared from the carbonization of a cellulose-based polymeric precursor doped with urea. The addition of urea to the cellulose precursor induces an increase in structural disorder and an increase in pore volume inside the structure of prepared membranes. This unique preparation procedure proved to be an extremely effective method for tuning the pore size of carbon membranes to the desired separations. Urea acts as a pore-forming agent that allows the fabrication of carbon membranes with high porosity. The addition of 2.8 wt% of urea doubled the permeability of the prepared carbon membrane to hydrogen. In addition, a permeability to oxygen of 333 barrer was obtained, without impairing the selectivity. The proposed preparation procedure is compatible with industrial production and scaling, hopefully making carbon membranes a viable solution to produce oxygen-enriched air, recovering of hydrogen from hydrocarbon streams and carbon dioxide removal from natural gas/biogas.

Low-temperature Cu/Zn/SBA-16 integrating carbon membrane reactor for hydrogen production and high CO conversion through water-gas shift reaction

The increasing demand for H2 energy has led to a great amount of research being conducted in a membrane reactor (MR), in which a membrane is applied during the water-gas shift (WGS) reaction. In this study, Cu/Zn/SBA-16 WGS catalysts and carbon molecular sieve (CMS) membranes were integrated into CMS MRs. To improve the CO conversion and H2 yield, C MRs were investigated, and different steam/CO (S/C) ratios were used to evaluate the conversion performance. In this study, a tubular CMS membrane was used as the membrane material for a MR. The as-prepared CMS membrane exhibited excellent selectivity of 185.64 for H2 and CO2 mixed gas, and an ideal H2 permeability of 9.7 × 10−9 mol m−2 s−1 Pa−1 when operated under low temperature/pressure conditions (300 °C/3 bar). The Cu/Zn/SBA-16 catalyst synthesized via coprecipitation was used in the WGS reaction. With a relatively low reaction temperature of 300 °C, 2500 h−1 gas hourly space velocity, and S/C equal to 1.5, the CO conversion efficiency of MR could reach up to 99%, and the recovery of H2 was approximately 76%. However, as the S/C increased to 2, the H2 recovery increased to 99%, whereas the CO conversion decreased to 89% because of the water vapor adsorbed on the active site. The hydrophobic Si/C-modified membrane was further synthesized and showed outstanding performance in CO conversion of over 99% with S/C equal to 2.

Precise Hydrogen Sieving by Carbon Molecular Sieve Membranes Derived from Solution-Processable Aromatic Polyamides

Precise Hydrogen Sieving by Carbon Molecular Sieve Membranes Derived from Solution-Processable Aromatic Polyamides

Preparation and Characterization of Free-Standing Composite Cellulose-Based Carbon Molecular Sieve Membranes

Carbon membranes with excellent strength and mechanical stability were prepared using a cellulose precursor regenerated from an ionic liquid solution with a low loading of boehmite ceramic nanoparticles, ca. 0.1 wt. %. The precursor films show an asymmetrical structure while, after carbonization, the corresponding carbon molecular sieve membranes (c-CMSM) show a dense structure with a uniform thickness of ca. 22 µm. The c-CMSM exhibited excellent separation performance, well above the Robeson Upper Bound. The permeability of the c-CMSM to hydrogen increased from 300 to 530 barrer and the H2/CH4 permselectivity increased to 473, after adding boehmite nanoparticles. Boehmite nanoparticles act as a microporosity-forming agent without compromising the width of the ultramicropores. The prepared c-CMSM is extremely promising for several applications, namely for hydrogen recovery from methane – H2/CH4 (Robeson index:θ=13.5); biogas upgrading – CO2/CH4 (θ=6.5); CO2 removal from combustion flue gas – CO2/N2 (θ=1.7); and hydrogen recovery from ammonia processes – H2/N2 (θ=4.8).

A triple-functional carbon molecular sieve (CMS) that addresses the performance trilemma in practical lithium sulfur batteries

Lithium-sulfur batteries offer an attractive energy storage alternative independent of critical minerals such as cobalt or nickel. However, their inadequate stability under long term cycling, and storage capacity on a volumetric basis hampers their uptake. These limitations can be addressed by seeking to control the formation and crossover of polysulfides, oligomers generated through reaction of solvated sulfur moieties with the lithium anode, and by seeking to restrict the consumption of active materials. Here, we report the development of a triple-functional carbon molecular sieve (CMS) interlayer. The microporous, polar, and conductive structure of the CMS provides physisorption, chemisorption, and reactivation capabilities concurrently. Therefore, the soluble polysulfides can be trapped, suppressed from shuttling, and reutilized to not only improve the kinetics of the redox reaction but also hinder the loss of active materials. As a result, our CMS-based Li–S batteries deliver combined exceptional gravimetric (1282 mAh g−1) and areal (7.05 mAh cm−2) capacities at 0.1 C rate as well as cycling stability up to 1000 cycles at 0.2 C rate over 9 months.

Comprehensive Characterization of Cocos nucifera Palm Residues for Biochar Production

The feasibility of using Cocos nucifera palm residues such as shell, husk, leaflets, fronds, and rachis for biochar production was investigated. Biomass characterization such as proximate, elemental, biochemical, higher heating value, and thermogravimetry were analysed. The results showed that fixed carbon of coconut palm residues was in the range of 10.48% to 17.47%, with the shell being the highest. Carbon, hydrogen, nitrogen, and oxygen content of the residues ranged from 39.46% to 48.60%, 4.23% to 6.00%, 0.42% to 1.66%, and 44.98% to 55.28%, respectively. Among the residues, lignin content was found to be maximum in the shell biomass (29.31%) and minimum in the rachis (21.89%). Thermogravimetric analysis of coconut palm residues revealed the presence of three stages of thermal degradation with overall weight loss ranging between 68.56% and 77.08 per cent. Higher fixed carbon and lignin content unveiled the potential of coconut palm residues for biochar synthesis. Slow pyrolysis of coconut palm residues resulted in biochar generation with fixed carbon content ranging between 65.40% and 78.21%, and proved its suitability for applications such as solid fuel, adsorbent, catalyst, and precursor for biomaterials production such as activated carbon and carbon molecular sieves.

Advanced carbon molecular sieve membranes derived from molecularly engineered cross-linkable copolyimide for gas separations.

Carbon molecular sieve (CMS) membranes with precise molecular discrimination ability and facile scalability are attractive next-generation membranes for large-scale, energy-efficient gas separations. Here, structurally engineered CMS membranes derived from a tailor-made cross-linkable copolyimide with kinked structure are reported. We demonstrate that combining two features, kinked backbones and cross-linkable backbones, to engineer polyimide precursors while controlling pyrolysis conditions allows the creation of CMS membranes with improved gas separation performance. Our results indicate that the CMS membranes provide a versatile platform for a broad spectrum of challenging gas separations. The gas transport properties of the resulting CMS membranes are interpreted in terms of a model reflecting both molecular sieving Langmuir domains and a disordered continuous phase, thereby providing insight into structure evolution from the cross-linkable polyimide precursor to a final CMS membrane. With this understanding of CMS membrane structure and separation performance, these systems are promising for environmentally friendly gas separations.

Simultaneously enhanced gas permeability, selectivity and aging stability of carbon molecular sieve membranes by the molecule doping of silicon

Simultaneously enhancing the gas permeability, selectivity and aging stability of carbon molecular sieve membrane (CMSM) is extremely difficult. Facing such poser, a novel silicon doped CMSM at molecular level was prepared by copolymerizing siloxane with single Si–O–Si unit into the backbone of polyimide (PI). This can effectively avoid prior separated structure or multiple Si–O–Si structures and strongly alter the chains packing and thermostability of PI, finally determine the pore structure and thermodynamic behavior. The simple design adjustment simultaneously exhibits the triple enhanced effects on the gas permeability, selectivity and aging stability. The best molecule doped CMSM exhibits the ultra-high H2 permeability (12482 Barrer, 87% higher), 26% higher H2/CH4 selectivity, and 32% higher H2/N2 selectivity than pure PI based CMSM. Additionally, such CMSM also has a much better aging stability than pure CMSM and most reported CMSMs. After stabilization, it still maintains a high H2 permeability (8000 Barrer). And the hyper-aging CMSM also exhibits a good aging resistance showing a H2 permeability of 5300 Barrer, as well as high selectivity of H2/CH4 (125) and H2/N2 (106) after 35 days. This work opens a new way on designing CMSM with excellent performance through heteroatom doping to need future application.

Hybrid carbon molecular sieve membranes having ordered Fe3O4@ZIF-8-derived microporous structure for gas separation

Carbon molecular sieve (CMS) membranes have great promise in CO2 capture. However, tortuous transport passageways restrict the enhancement in the permeability due to the presence of disordered porous structure and dead-end pore. Herein, the growth of ZIF-8 layer on the surface of Fe3O4 formed magnetic core-shell Fe3O4@ZIF-8 particles, which were fixed into 6FDA/ODA:DABA polyimides under magnetic field-induction to fabricate a precursor membrane with vertically oriented chain-like particles. It was then pyrolyzed to form hybrid carbon molecular sieve (HCMS) membranes with ordered microporous structure under high temperature conditions. The cross-section scanning electron microscopy images and N2 adsorption for resultant HCMS membranes indicate that Fe3O4@ZIF-8-derived carbons frameworks were vertically oriented to form the ordered microporous structure, which also had good compatibility with carbon matrix stemmed from 6FDA/ODA:DABA polyimides. The as-prepared HCMS membranes embedded with 5 wt% Fe3O4@ZIF-8 manifested a highest gas separation performance (permeability of 5130 Barrer; CO2/N2 selectivity of 29; CO2/CH4 selectivity of 48), outperforming the pristine CMS membranes, which were near and beyond 2019 CO2/N2 and CO2/CH4 upper bounds, separately. These good separation performances resulted from vertical chain-like microporous particles, which provided fast transport channels to accelerate CO2 diffusion rate. In addition, we supposed that Fe3O4 prevent ZIF-8 frameworks from destruction during the pyrolysis and promote the size screening capability. More importantly, this membrane exhibited excellent aging resistance over 30 days aging testing compared to pristine CMS membranes. Therefore, it affords a feasible way for carbon capture from flue gas and natural gas.

Selection of gas standards, gas chromatography column and adsorbents for the measurement of very volatile organic compounds (C1–C6) in indoor air

The ISO 16000-6 standard gives directions to adapt the analysis of volatile organic compounds (VOCs) in indoor and test chamber air to very volatile organic compounds (VVOCs). The same techniques with sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (TD-GC/MS) should be used. However, VVOCs require gaseous standards, an adapted GC column and a reliable sampling adsorbent. This work presents experimental results to tackle those three experimental gaps. A stable standard gas mixture containing 47 VVOCs, 13 VOCs and an internal standard was successfully generated. It was employed to study the suitability of seven types of chromatography columns. The use of PLOT (Porous Layer Open Tubular) columns such as PoraBOND Q is well suitable for VVOC analysis. The recoveries of the 60 analytes on a total of 16 adsorbents and their combinations were determined: A combination of the graphitized carbon black Carbograph 5TD 40/60 and the carbon molecular sieve Carbosieve™ SII showed great recoveries for all analytes. Carbon molecular sieves adsorb water which can impair the analysis. A dry purge of the multi-sorbent in the sampling direction led to a complete water removal and promising recoveries of the analytes.

New Insights into Physical Aging-Induced Structure Evolution in Carbon Molecular Sieve Membranes.

Carbon molecular sieve (CMS) membranes offer the best available combination of scalable economical processability with excellent separation performance. Physical aging of CMS membranes causes pore structure changes over time that affect CMS membrane performance. To provide fundamental insights into the structure evolution in CMS membranes during physical aging, a combined dual-mode sorption and transport model is used in this study to characterize the diffusion coefficients of gas molecules in fresh and 7-day vacuum aged CMS membranes. The results show physical aging of CMS membrane is primarily "diffusion related" and such aging behavior simultaneously causes ultramicropore changes in the continuous phase and Langmuir phase of CMS membrane. The new insights offered in this study suggest strategies to control the physical aging of CMS membranes and even use it as a valuable tool to tune the separation performance of CMS membranes for demanding gas separations.

New Insights into Physical Aging‐Induced Structure Evolution in Carbon Molecular Sieve Membranes

AbstractCarbon molecular sieve (CMS) membranes offer the best available combination of scalable economical processability with excellent separation performance. Physical aging of CMS membranes causes pore structure changes over time that affect CMS membrane performance. To provide fundamental insights into the structure evolution in CMS membranes during physical aging, a combined dual‐mode sorption and transport model is used in this study to characterize the diffusion coefficients of gas molecules in fresh and 7‐day vacuum aged CMS membranes. The results show physical aging of CMS membrane is primarily “diffusion related” and such aging behavior simultaneously causes ultramicropore changes in the continuous phase and Langmuir phase of CMS membrane. The new insights offered in this study suggest strategies to control the physical aging of CMS membranes and even use it as a valuable tool to tune the separation performance of CMS membranes for demanding gas separations.

The concentration dependent permeation properties of binary CO2 gas mixtures through carbon molecular sieve membrane

This paper deals with the permeation properties of binary gas mixtures (CO2/He, CO2/H2) through a carbon molecular sieve membrane (CMSM). The permeation properties of binary gas mixtures were determined via an improved time lag technique, and the permeation flux of an individual component was determined by selectively capturing the CO2 in the permeate stream via a cold trap filled with liquid N2. The ‘true’ permeation properties (i.e., permeability and perm-selectivity) of the CMSM were found to deviate significantly from the ‘ideal’ values based on pure gas permeation, displaying a strong dependency on the composition of the feed gas mixtures. At certain concentration ranges, there was even a ‘reverse’ selectivity observed. This concentration-dependent selectivity was analyzed and modelled via the Maxwell-Stefan Equation, which highlighted the importance of competitive adsorption and competitive diffusion of different permeant components in the porous network of the membrane. Such concentration dependencies of permeabilities may post a challenge for certain gas separations but also represent an opportunity if properly and accurately exploited for certain membrane separation applications.

Research progress on the application of derived porous carbon materials in solid-phase microextraction

固相微萃取是一种集采样、萃取、富集和进样于一体的样品前处理技术,其萃取效果与涂层材料密切相关。多孔碳材料具有比表面积大、多孔结构可控、活性位点多和化学稳定性好等优点,广泛应用于电池、超级电容器、催化、吸附和分离等领域,也是一种热门的用作固相微萃取探针的涂层材料。衍生多孔碳材料因种类丰富、可设计性强被广泛研究,研究主要集中在对衍生多孔碳材料的结构优化方面。但是衍生多孔碳材料在固相微萃取中的应用还存在如下问题:(1)共价有机框架衍生多孔碳材料的制备已取得较大进展,但将其应用于固相微萃取领域的研究仍较少;(2)有待进一步明确制备出的衍生多孔碳材料用作固相微萃取涂层表现出优异提取能力的机理;(3)有待进一步深入研究将衍生多孔碳材料用作固相微萃取涂层以实现对不同物理化学性质污染物的广谱高灵敏度分析。文章综述了近3年衍生多孔碳材料在固相微萃取中的应用研究,并展望了未来衍生多孔碳材料在固相微萃取中的研究前景。引用文献共56篇,主要来源于Elsevier。

Influence of chain length on structural properties of carbon molecular sieving membranes and their effects on CO[formula omitted], CH[formula omitted] and N[formula omitted] adsorption: A molecular simulation study

Carbon molecular sieving membranes (CMSM) derived from 6FDA/BPDA-DAM polymer precursors (6F-CMSM) show excellent adsorption and selectivity towards CO2. Using molecular dynamics (MD) simulations, we investigate how the length of individual carbon chains determines the morphologies emerging from the same monomers. Smaller chains produce densely packed structures, whereas longer chains arrange in layers, creating larger voids comprising both micropores and ultra-micropores. The pure gas adsorption isotherms of CO2, CH4, and N2 inside various 6F-CMSM morphologies, obtained from MD, provide theoretical insights into most feasible structures formed in experiments, thereby providing an estimate of the corresponding 6F-CMSM density. Using grand canonical Monte Carlo simulations, we observe that high isosteric heats of adsorption for CO2 leads to enhanced adsorption capacity and high sorption selectivity from binary mixtures of these gases. Studying the asphericity of carbon chains, we report the existence of an optimum chain length of highest curvature, leading to low density, high porosity, and high CO2 adsorption capacities that compare well with available experimental data, without compromising sorption selectivity of 6F-CMSM. This work provides a theoretical basis of how slight modifications of the physical arrangements of chemical components lead to significant changes in porosity and gas adsorption capacities of molecular sieving membranes.

Environmental remediation through various composite membranes moieties: Performances and thermomechanical properties

Pollution harms ecosystems and poses a serious threat to human health around the world through direct or indirect effects on air, water, and land. The importance of remediating effluents is paramount to reducing environmental concerns. CO2 emissions are removed efficiently and efficaciously with mixed matrix membranes (MMMs), which are viable replacements for less efficient and costly membranes. In the field of membrane technology, MMMs are advancing rapidly due to their good separation properties. The selection of filler to be incorporated in mixed matrix membranes is very considered very important. There has been considerable interest in MOFs, carbon nanotubes (CNTs), ionic liquids (ILs), carbon molecular sieves (CMSs), sulfonated fillers (SFs), and layered silicates (LSs) as inorganic fillers for improving the properties of mixed matrix membranes. These fillers promise superb results and long durability for mixed matrix membranes based on them. The purpose of this review is to review different fillers used in MMMs for improving separation properties, limitations, and thermomechanical properties for environmental control and remediation.

Membrane Separation Processes and Post-Combustion Carbon Capture: State of the Art and Prospects.

Membrane processes have been investigated for carbon capture for more than four decades. Important efforts have been more recently achieved for the development of advanced materials and, to a lesser extent, on process engineering studies. A state-of-the-art analysis is proposed with a critical comparison to gas absorption technology, which is still considered as the best available technology for this application. The possibilities offered by high-performance membrane materials (zeolites, Carbon Molecular Sieves, Metal Oxide Frameworks, graphenes, facilitated transport membranes, etc.) are discussed in combination to process strategies (multistage design, hybrid processes, energy integration). The future challenges and open questions of membranes for carbon capture are finally proposed.

High-performance carbon molecular sieve membrane for C2H4/C2H6 separation: Molecular insight into the structure-property relationships

Carbon molecular sieve (CMS) membranes show attractive potential for energy-efficient separation of C2H4/C2H6 due to their unique slit-like pore structure. In this work, a novel precursor polymer of phenolphthalein-based poly(arylene ether ketone) (PEK-C) was introduced to prepare high-performance CMS membranes for C2H4/C2H6 separation. Molecular insight into the effect of the sp3/sp2 hybridized carbon ratio on the packing morphology of carbon layers, pore size and configuration, and C2H4/C2H6 diffusion and separation properties of CMS membranes was investigated via using in-depth characterization techniques combined with molecular simulations. Results show that the carbon layers with more sp3 hybridized carbons lead to forming a loose and disordered carbon structure and pore structure with large pore volume and micropore size (steric voids), resulting in low C2H4/C2H6 permselectivity of CMS membrane. With the reduction of the sp3/sp2 hybridized carbon ratio, a compact and graphite-like carbon structure with the two-dimensional slit-like ultramicropore structure is formed, and the C2H4/C2H6 permselectivity is obviously enhanced. The CMS membranes derived from the novel precursor of PEK-C exhibit high C2H4 permeability with superior C2H4/C2H6 selectivity, which have surpassed the trade-off bounds of both polymeric membrane and CMS membrane, and reveal a great potential in the industrial applications of C2H4/C2H6 separation.

Polyimide-derived carbon molecular sieve membranes for high-efficient hydrogen purification: The development of a novel phthalide-containing polyimide precursor

Hydrogen-based economy has been considered as a potential solution for energy security and sustainability in the future. And the ever-increasing demand for high-purity hydrogen (H2) provides an urgent force for the H2 purification technologies. Herein, a novel polyimide (BATPPP-6FDA) with rigid and contorted structure was synthesized and used as a precursor to fabricate the carbon molecular sieve membranes (CMSMs) for H2 purification. The structural changes from precursor to CMS were detected and the H2 separation performance of the membranes was optimized by the pyrolysis temperature. The CMSM pyrolyzed at 550 °C exhibited the highest H2 permeability of 10054.1 Barrer and moderate H2 permselectivity due to its highly disordered and turbostratic carbon structure originated from the generally decomposition of thermally labile -CF3 groups and the lactone rings of phthalide structure in the early stages (<550 °C) of pyrolysis. As the pyrolysis temperature raised, the H2 permeability of the derived CMSM decreased, and the H2 permselectivity enhanced greatly. The CMSM pyrolyzed at 800 °C demonstrated a high H2 permeability of 2622.4 Barrer and superior selectivity with H2/N2 of 524.48, H2/CH4 of 1248.76 and H2/CO2 of 7.51, respectively, which was attributed to the low densification of carbon structure resulting from the rigid and contorted structure of the BATPPP-6FDA precursor. The excellent H2 separation performance showed a great potential in hydrogen purification application.

Ultra-Selective CMSMs Derived from Resorcinol-Formaldehyde Resin for CO2 Separation.

A resorcinol-formaldehyde precursor was synthesized to fabricate the CO2 selective Carbon Molecular Sieve Membranes (CMSMs) developed in this study. The degree of polymerization (DP) was analyzed via Gel Permeation Chromatography (GPC) and its effect on the CO2/N2 perm-selectivity and CO2 permeance was investigated. The membrane that was polymerized at 80 °C (named R80) was selected as the best performing CMSM after a preliminary test. The post treatment with oxidative atmosphere was performed to increase the CO2 permeance and CO2/N2 perm-selectivity on membrane R80. The gas permeation results and Pore Size Distribution (PSD) measurements via perm-porometry resulted in selecting the membrane with an 80 °C polymerization temperature, 100 min of post treatment in 6 bar pressure and 120 °C with an oxygen concentration of 10% (named R80T100) as the optimum for enhancing the performance of CMSMs. The 3D laser confocal microscopy results confirmed the reduction in the surface roughness in post treatment on CMSMs and the optimum timing of 100 min in the treatment. CMSM R80T100 exhibiting CO2/N2 ideal selectivity of 194 at 100 °C with a CO2 permeability of 4718 barrier was performed higher than Robeson’s upper bound limit for polymeric membranes and also the other CMSMs fabricated in this work.