Applications of metal–organic frameworks for green energy and environment: New advances in adsorptive gas separation, storage and removal

The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH_4 are considered as promising candidates for the replacement of traditional fossil fuels. However, the technologies for the storage of these gases are still immature. In addition, the release of anthropogenic toxic gases into the atmosphere is a worldwide threat of growing concern. Both in academia and industry, considerable research efforts have been devoted to developing advanced porous materials for the effective and energy-efficient separation, storage, or capture of the related gases. In contrast to conventional inorganic porous materials such as zeolites and activated carbons, metal–organic frameworks(MOFs) are considered as a type of promising materials for gas separation and storage. In this contribution, we review the recent research advance of MOFs in some relevant applications, including CO_2 capture, O_2 purification, separation of light hydrocarbons, separation of noble gases, storage of gases(CH_4,H_2, and C_2 H_2) for energy, and removal of some gaseous air pollutants(NH_3, NO_2, and SO_2). Finally, an outlook regarding the challenges of the future research of MOFs in these directions is given.

Enhanced gas separation performance of mixed matrix hollow fiber membranes containing post-functionalized S-MIL-53

Mixed matrix hollow fiber membranes（MMHFMs）filled with metal-organic frameworks（MOFs）have great potential for energy-efficient gas separation processes,but the major hurdle is polymer/MOFs interfacial defects and membrane plasticization.Herein,lab-synthesized MIL-53 was post-functionalized by aminosilane grafting and subsequently incorporated into Ultem-1000 polymer matrix to fabricate high performance MMHFMs.SEM,DLS,XRD and TGA were performed to characterize silane-modified MIL-53（S-MIL-53）and prepared MMHFMs.Moreover,the effect of MOFs loading was systematically investigated first;then gas separation performance of MMHFMs for pure and mixed gas was evaluated under different pressures.MMHFMs containing post-functionalized S-MIL-53 achieved remarkable gas permeation properties which was better than model predictions.Compared to pure HFMs,CO2permeance of MMHFM loaded with 15%S-MIL-53 increased by 157%accompanying with 40%increase for CO2/N2selectivity,which outperformed the MMHFM filled with naked MIL-53.The pure and mixed gas permeation measurements with elevated feed pressure indicated that incorporation of S-MIL-53 also increased the resistance against CO2plasticization.This work reveals that post-modified MOFs embedded in MMHFMs facilitate the improvement of gas separation performance and suppression of membrane plasticization.

Evaluation of a mathematical model using experimental data and artificial neural network for prediction of gas separation

In recent times, membranes have found wide applications in gas separation processes. As most of the industrial membrane separation units use hollow fiber modules, having a proper model for simulating this type of membrane module is very useful in achieving guidelines for design and characterization of membrane separation units. In this study, a model based on Coker, Freeman, and Fleming＇s study was used for estimating the required membrane area. This model could simulate a multicomponent gas mixture separation by solving the governing differential mass balance equations with numerical methods. Results of the model were validated using some binary and multicomponent experimental data from the literature. Also, the artificial neural network （ANN） technique was applied to predict membrane gas separation behavior and the results of the ANN simulation were compared with the simulation results of the model and the experimental data. Good consistency between these results shows that ANN method can be successfully used for prediction of the separation behavior after suitable training of the network

GAS SEPARATION PROPERTIES OF FREESTANDING FILM OF POLYANILINE

The gas separation properties of free- standing film of polyaniline (PANI) for gas pairs of He/N2, H_2/N_2. CO_2/N_2 and CO_2/CH_4 at room temperature were measured as a function of the protonation state. Variation of the gas permeabilities coefficient of PANI with an insulator to metal transition upon the protonation processes was observed, which might be due to a change in both gas solubility coefficient and diffusion coefficient with the protonation state.

A CONDENSED REVIEW ON THE FABRICATION OF HOLLOW FIBER MEMBRANES FOR GAS SEPARATION:HISTORICAL DEVELOPMENT AND TECHNOLOGY CHALLENGES AHEAD

A review on the polymeric hollow fibers membranes for gas separation has been conducted. In order to deyelop high performance membranes for gas separation, there are a few technology challenges awaiting the chemical engineers to overcome. There are four major challenges, namely: 1) material selection and synthesis; 2) fabrication of hollow fiber membranes with an ultra- thin dense selective layer; 3) materials against plasticization; and 4) aging. In each area, we summarize the scientific accomplishments and technical difficulties.

Highly Durable MIL-96 Membranes via a One-step Active γ-Alumina Conversion Strategy for Gas Separation

Metal-organic frameworks(MOFs)are attractive in membrane separation due to their special pore structure and suitable aperture size.The fabrication of defect-free and robust MOF membranes with excellent durability is highly demanded but remains challenging.In this work,we report a one-step activeγ-alumina conversion strategy for the facile and reliable fabrication of an MIL-96 membrane.In this case,theγ-Al_(2)O_(3) sol was dip-coated and sintered on theα-Al_(2)O_(3) disc as the active aluminum source and substrate for the nucleation and growth of MOF.A continuous and well-intergrown MIL-96 membrane was generated with exceptional stability due to the strong adhesion to the substrate.The resultant MIL-96 membrane yielded a satisfactory H_(2)/CO_(2) permselectivity and high-temperature resistance,delivering a selectivity of 12.35 with H_(2) permeance of 6.20×10^(−7) mol·m^(−2)·s^(−1)·Pa^(−1) at 150℃.Moreover,the probe membrane presented remarkable durability and recyclability under harsh hydrothermal conditions.This method paves the way for constructing highly stable and selective MOF membranes and could accelerate the development of advanced membrane separation technologies for gas purification and recycling in addressing the severe energy and environmental problems.

Ultrapermeable membranes based on connected cluster of hollow polydimethylsiloxane nanoparticles for gas separation

Mixed matrix membranes(MMMs)with the performance between the matrix and the filler is a promising strategy for membranes with excellent gas permeability-selectivity.In this study,the hollow polydimethylsiloxane nanoparticles were synthesized and then incorporated with the poly(oxide ethylene)monomer and tri-functional cross-linker to form mixed matrix membranes by in situ poly-merization.The hollow nanoparticles formed the independent closed nanocavities in membranes,which enhanced the gas permeability contributed by both the improved diffusivity and solubility.At high loading,the hollow polydimethylsiloxane nanoparticle was converted into the continuous phase with the cross-linked poly(oxide ethylene)as the dispersed phase.Gases preferred to permeate through the connected cluster of hollow polydimethylsiloxane nanoparticles,finally leading to ultrahigh gas per-meabilities far going beyond the instinct values of polydimethylsiloxane and the cross-linked poly(oxide ethylene).The optimized membrane with 34 wt%hollow nanoparticles loadings exhibited ultrahigh permeabilities with the values of 44186 Barrer for CO_(2) and 11506 Barrer for O_(2),accompanied with a CO_(2)/N_(2) selectivity of 9.9 and an O_(2)/N_(2) selectivity of 2.6,which exceeded the 2008 Robeson upper bound for O_(2)/N_(2) and located at the 2008 Robeson upper bound for CO_(2)/N_(2).

Remarkably Improved Gas Separation Performance of Polyimides by Forming“Bent and Battered”Main Chain Using Paracyclophane as Building Block

The design and development of highly permeable,selective and stable polymer membranes are great challenges in the gas separation industry.Herein,we constructed two intrinsic microporous polyimides(6FPCA and 6FMCA)derived from two isometric diamines(PCA and MCA),which were synthesized by palladium catalyzed C—N coupling reaction.The PCA and MCA diamines contain a hollow beaded structure of 2,2′-paracyclophane as a building block with a specified window size of 3.09Å.The chemical structures of monomers,polyimides were confirmed by NMR,FTIR,and elementary analysis.6FPCA and 6FMCA exhibit good solubility,excellent thermal stability,and mechanical properties.6FPCA exhibits much larger microporosity(434 versus 120 m2·g−1),FFV(0.22 versus 0.15),d-spacing(6.9 versus 5.9Å),and over 10 times higher permeability with a very little decrease in selectivity than the corresponding polyimide(6FpA)with a plane structure,which remarkably increased their separation performance from far below the 2008 Robeson Upper bounds to reach these limitations for O2/N2 and CO2/CH4.Additionally,the 6FPCA also demonstrates good plasticization resistance,moderate aging properties,and high CO2/CH4 mixed-gas separation performance.These results indicate that paracyclophane subunit can be successfully incorporated into polymers to enhance their ultra-microporosity and separation properties,which open a new avenue for developing high performance gas separation membranes with topological ultra-micropores.

Studies on Oxygen Characteristics of YBa_2Cu_3O_(7-x) and Its Applications to Air Separation and Gas Purification

Oxygen diffusion and oxygen selective adsorption properties of rare earths material YBa_2Cu_3O_(7-x) (YBCO) were investigated by thermogravimetric, oxygen static adsorption and selectivity adsorption experiments. The results show that YBCO is a very good deoxidizing material. The oxygen desorption of YBCO begins remarkably at about 400 ℃, mass loss can arrive at 1.2% of its original quantity at 800 ℃. Oxygen can be completely absorbed back into the sample again when temperature descends to 400 ℃. The oxygen adsorption selectivity, reproducibility and oxygen adsorption under very low oxygen partial pressure make the material desirable for air separation and gas purification. High purity nitrogen gas was produced with the YBCO molecular sieves in the air separation and gas purification experiments. 0.017 m^3 of high purity nitrogen (>99.9999%) can be obtained with 1 kg YBCO molecular sieve in one cycle. As a deoxidant, an obvious advantage of YBCO is that no hydrogen is needed in its applications.

Computational design of heterogeneous catalysts and gas separation materials for advanced chemical processing

Functional materials are widely used in chemical industry in order to reduce the process cost while simultaneously increase the product quality.Considering their significant effects,systematic methods for the optimal selection and design of materials are essential.The conventional synthesis-and-test method for materials development is inefficient and costly.Additionally,the performance of the resulting materials is usually limited by the designer’s expertise.During the past few decades,computational methods have been significantly developed and they now become a very important tool for the optimal design of functional materials for various chemical processes.This article selectively focuses on two important process functional materials,namely heterogeneous catalyst and gas separation agent.Theoretical methods and representative works for computational screening and design of these materials are reviewed.

Performance assessment of an inline horizontal swirl tube cyclone for gas-liquid separation at high pressure

The application of swirl tube cyclone for gas-liquid separation is attractive due to its small size and weight. However, very scarce information on the performance of the swirl tube cyclone especially at high operating pressure emulating actual field condition was published in journals. Performance assessment was usually done at a low operating pressure using either air-water, air-fine particle mixtures or dense gas such as SF6 . This paper fills the existing gaps and reports the initial findings on the performance assessment of a horizontal swirl tube cyclone for gas-liquid separation operating at a flow rate of 5 MMSCFD at 40-60 bar operating pressure.

Highly Soluble Polyimides Containing Di-tert-butylbenzene and Dimethyl Groups with Good Gas Separation Properties and Optical Transparency

A rigid aromatic diamine monomer containing di-tert-butylbenzene and dimethyl groups,3,3'-dimethyl-4,4'-diaminophenyl-3",5"-di-tert-butyltoluene,was successfully synthesized by a simple coupling reaction using 3,5-di-tert-butylbenzaldehyde and o-toluidine as starting materials.A series of novel polyimides(PI 3a-3c)with large pendant groups were prepared with the obtained diamine monomer and three different commercial aromatic dianhydrides(3,3',4,4'-biphenyltetracarboxylic dianhydride,4,4'-oxydiphthalic anhydride,and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride)by one-step high temperature polycondensation.The prepared polyimides exhibited high solubility and good membrane forming ability:they could be dissolved not only in some high boiling solvents such as DMF,NMP,DMAc,and m-Cresol at room temperature,but also in some low boiling solvents such as CHCl3,CH2Cl2,and THF.Their solubility in most solvents could exceed 10 wt%,and the flexible membranes could be obtained by casting their solutions.The prepared membranes exhibited good gas separation properties.The permeability coefficients of PI 3c for CO2 and O2 were up to 124.6 and 42.8 barrer,respectively,and the selectivity coefficients for CO2/CH4 and O2/N2 were 14.7 and 3.3,respectively.The membranes had light color and good optical transmission.Their optical transmittance at 450 nm wavelength was in the range of 67%-79%,and the cutoff wavelength was in the range of 310-348 nm.They also had good thermal properties with glass transition temperature(Tg)values in the range of 264-302℃.In addition,these membranes possessed good mechanical properties with tensile strength ranging between 77.8-87.4 MPa,initial modulus ranging between 1.69-1.82 GPa,and elongation at break ranging between 4.8%-6.1%.

Separation of methane from different gas mixtures using modified silicon carbide nanosheet: Micro and macro scale numerical studies

This research discusses the separation of methane gas from three different gas mixtures,CH4/H2 S,CH4/N2 and CH4/CO2,using a modified silicon carbide nanosheet(Si CNS)membrane using both molecular dynamics(MD)and computational fluid dynamics(CFD)methods.The research examines the effects of different structures of the Si CNSs on the separation of these gas mixtures.Various parameters including the potential of the mean force,separation factor,permeation rate,selectivity and diffusivity are discussed in detail.Our MD simulations showed that the separation of CH4/H2 S,and CH4/CO2 mixtures was successful,while simulation demonstrated a poor result for the CH4/N2 mixture.The effect of temperature on the diffusivity of gas is also discussed,and a correlation is introduced for diffusivity as a function of temperature.The evaluated value for diffusivity is then used in the CFD method to investigate the permeation rate of gas mixtures.

Gas separation using porous cement membrane

Gas separation is a key issue in various industrial fields. Hydrogen has the potential for application in clean fuel technologies. Therefore, the separation and purification of hydrogen is an important research subject. CO2 capture and storage have important roles in ＂green chemistry＂. As an effective clean technology, gas separation using inorganic membranes has attracted much attention in the last several decades. Membrane processes have many applications in the field of gas separation. Cement is one type of inorganic material, with the advantages of a lower cost and a longer lifespan. An experimental setup has been created and improved to measure twenty different cement membranes. The purpose of this work was to investigate the influence of gas molecule properties on the material transport and to explore the influence of operating conditions and membrane composition on separation efficiency. The influences of the above parameters are determined, the best conditions and membrane type are found, it is shown that cementitious material has the ability to separate gas mixtures, and the gas transport mechanism is studied.

Design of metal-organic framework membranes towards ultimate gas separation

Metal-organic framework(MOF)membranes have shown unprecedented opportunities for energy efficient separation of diverse industrially important gas pairs(e.g.H_(2)/CO_(2),CO_(2)/N_(2),CO_(2)/CH_(4),and C3H6/C3H8).Among the various factors,microstructure manipulation(including thickness,orientation,and grain boundary structure)and framework tuning(including pore size,framework rigidity/flexibility,and stimuli responsiveness)of MOF membranes have been found playing dominant roles in their separation performances.In this perspective,we highlighted some recent progress in polycrystalline MOF membranes with emphasis on the elucidation of the structure-performance relationship at different scales.

Smart light-responsive hierarchical metal organic frameworks constructed mixed matrix membranes for efficient gas separation

One type of new light-responsive hierarchical metal organic framework(MOF) has been successfully prepared using Co(NO_(3))_(3)·6H_(2)O as the metal salt and 4,4’-azobenzenedicarboxylic acid as the ligand by microwave method for the first time. It is found that MOF [Co(Az DC)] exhibits a light-responsive characteristic to SO_(2)adsorption due to the presence of azo group from the ligand. The light-responsive hierarchical MOFs are incorporated into Matrimid■ 5218(PI) matrix to prepare mixed matrix membranes(MMMs) for gas separation application. The morphology, crystallinity, chain mobility and thermal stability of MMMs are explored. Results show that Co(Az DC) may elevate both the CO_(2)(SO_(2)) permeability and CO_(2)(SO_(2))/N_(2)selectivity of the MMMs. In particular,the Co(Az DC) doped MMMs exhibit the significantly improved CO_(2)(SO_(2))/N_(2)selectivity from 33(123) for PI control membrane to 78(420) for MMMs, overcoming the 2008 Robeson upper bound for CO_(2)/N_(2)system. Sizesieving effect of Co(Az DC) with pore size 0.35 nm enhances the selectivity, while the –N=N– group from Co(Az DC) shows affinity to CO_(2)molecular rather than N_(2), also elevating selectivity of MMMs. In brief, enhanced selectivity of high-performance membrane is attributed to incorporation of Co(Az DC) particles, which displays synergistic effects both in size-sieving and CO_(2)-philic interaction for CO_(2)/N_(2)separation. Smart highly selective interface is constructed in MMMs by switching the configuration of MOFs from cis to trans. The SO_(2)permeability and SO_(2)/N_(2)selectivity of MMMs are investigated under both visible light and ultraviolet light states, and the SO_(2)/N_(2)separation performance under visible light is notably improved in comparison with that under ultraviolet light state.

A mixed-ligand approach for a gigantic and hollow heterometallic cage {Ni_(64)Gd_(96)} for gas separation and magnetic cooling applications

Subject Code:E01With the support of the National Natural Science Foundation of China,the research team led by Prof.Zheng Yanzhan(郑彦臻)at the Frontier Institute of Science and Technology,Xi'an Jiaotong University,recently reported a gigantic rare-earth transition metal cuboidal hollow cluster {Ni_(64)Gd_(96)}that exhibits high selectivity for absorbing CO_2over CH_4or N_2at room temperature and large magnetocaloric effects at

Unique Ligand Exchange Dynamics of Metal-Organic Polyhedra for Vitrimer-like Gas Separation Membranes

Metal-organic polyhedra(MOPs)possess a microporous framework and impose hierarchical constraints on their surface ligands,leading to the long-ignored,logarithmic ligand exchange dynamics.Herein,polymer networks with MOP as nanoscale cross-linkers(MOP-CNs)can integrate unique ligand exchange dynamics and microporosity,affording vitrimer-like gas separation membranes with promising mechanical performance and(re)processability.All the ligands on the MOP surfaces are confined and correlated via a 3D coordination framework and their neighboring spaces,giving rise to a high energy barrier for ligand exchange.Therefore,MOP-CNs demonstrate high mechanical strengths at room temperature due to their negligible ligand dynamics.The thermo-activated ligand exchange process with integrated network topology enables facile(re)processing and high solvo-resistance at high temperatures.This facilitates Arrhenius type temperature dependence of flowability and stress relaxation,giving rise to the simultaneous achievement of promising mechanical strengths and(re)processability.Finally,the cage topologies of MOPs endow the materials with a bonus microporous feature and spur their applications as gas separation membranes.

Modification strategies for metal-organic frameworks targeting at mem brane-based gas separations

Metal-organic frameworks(MOFs)hold great promises as membrane candidates for highly efficient separation applications,benefiting from the diversified structures,high surface areas and adjustable chemical functionalities.However,non-selective defects and framework flexibility are two main concerns which would attenuate the ultimate separation performance and stability.Modification helps to orientationally optimize the gas adsorption and diffusion behaviors via manipulation towards framework chemical components,aperture sizes,nanocages,and intercrystalline/intracrystalline defects,consequently promoting membrane separation performance and membrane stability.In view of recent progresses of modification on MOF-based membranes,two categories of modification strategies were summarized,namely post-synthetic modification and in situ modification.And the merits and demerits are elucidated.Furthermore,challenges and opportunities for the current modification strategies were discussed from our perspectives,with an expectation to provide guidelines to the future development of MOF-based membranes which were aspired to reach the commercially attractive performance region.

MULTIDIMENSIONAL GAS CHROMATOGRAPHY FOR THE SEPARATION OF TCDD ISOMERS

A multidimensional gas chromatographic technique with heartcutting was used for the determination of complex isomeric mixtures of tetra- chlorodibenzo-p-dioxins(TCDDs)which could not be completely separated on a single capillary column.When using so-called heartcutting technique ,only the interested single peak or section of the fraction eluting from the first column was transferred onto the second column with different stationary phase.Flame ionization detection was used as the monitor detector and electron capture detection as the main detector.This arrangement offers complete separation and avoids interference of the possible remained chlorinated solvents.The separation power of multi- dimensional GC was demonstrated by the determination of TCDD isomers.