Carbon monoxide separation: past, present and future.

Large amounts of carbon monoxide are produced by industrial processes such as biomass gasification and steel manufacturing. The CO present in vent streams is often burnt, this produces a large amount of CO2, e.g., oxidation of CO from metallurgic flue gasses is solely responsible for 2.7% of manmade CO2 emissions. The separation of N2 from CO due to their very similar physical properties is very challenging, meaning that numerous energy-intensive steps are required for CO separation, making the CO separation from many process streams uneconomical in spite of CO being a valuable building block in the production of major chemicals through C1 chemistry and the production of linear hydrocarbons by the Fischer-Tropsch process. The development of suitable processes for the separation of carbon monoxide has both industrial and environmental significance. Especially since CO is a main product of electrocatalytic CO2 reduction, an emerging sustainable technology to enable carbon neutrality. This technology also requires an energy-efficient separation process. Therefore, there is a great need to develop energy efficient CO separation processes adequate for these different process streams. As such the urgency of separating carbon monoxide is gaining greater recognition, with research in the field becoming more and more crucial. This review details the principles on which CO separation is based and provides an overview of currently commercialised CO separation processes and their limitations. Adsorption is identified as a technology with the potential for CO separation with high selectivity and energy efficiency. We review the research efforts, mainly seen in the last decades, in developing new materials for CO separation via ad/bsorption and membrane technology. We have geared our review to both traditional CO sources and emerging CO sources, including CO production from CO2 conversion. To that end, a variety of emerging processes as potential CO2-to-CO technologies are discussed and, specifically, the need for CO capture after electrochemical CO2 reduction is highlighted, which is still underexposed in the available literature. Altogether, we aim to highlight the knowledge gaps that could guide future research to improve CO separation performance for industrial implementation.

Improved Synthesis of Hollow Fiber SSZ-13 Zeolite Membranes for High-Pressure CO2/CH4 Separation.

High-silica CHA zeolite membranes are highly desired for natural gas upgrading because of their separation performance in combination with superior mechanical and chemical stability. However, the narrow synthesis condition range significantly constrains scale-up preparation. Herein, we propose a facile interzeolite conversion approach using the FAU zeolite to prepare SSZ-13 zeolite seeds, featuring a shorter induction and a longer crystallization period of the membrane synthesis on hollow fiber substrates. The membrane thickness was constant at ~3 µm over a wide span of synthesis time (24-96 h), while the selectivity (separation efficiency) was easily improved by extending the synthesis time without compromising permeance (throughput). At 0.2 MPa feed pressure and 303 K, the membranes showed an average CO2 permeance of (5.2±0.5)×10-7 mol m-2 s-1 Pa-1 (1530 GPU), with an average CO2/CH4 mixture selectivity of 143±7. Minimal defects ensure a high selectivity of 126 with a CO2 permeation flux of 0.4 mol m-2 s-1 at 6.1 MPa feed pressure, far surpassing requirements for industrial applications. The feasibility for successful scale-up of our approach was further demonstrated by the batch synthesis of 40 cm-long hollow fiber SSZ-13 zeolite membranes exhibiting CO2/CH4 mixture selectivity up to 400 (0.2 MPa feed pressure and 303 K) without using sweep gas.

Water and Metal-Organic Frameworks: From Interaction toward Utilization.

The steep stepwise uptake of water vapor and easy release at low relative pressures and moderate temperatures together with high working capacities make metal-organic frameworks (MOFs) attractive, promising materials for energy efficient applications in adsorption devices for humidity control (evaporation and condensation processes) and heat reallocation (heating and cooling) by utilizing water as benign sorptive and low-grade renewable or waste heat. Emerging MOF-based process applications covered are desiccation, heat pumps/chillers, water harvesting, air conditioning, and desalination. Governing parameters of the intrinsic sorption properties and stability under humid conditions and cyclic operation are identified. Transport of mass and heat in MOF structures, at least as important, is still an underexposed topic. Essential engineering elements of operation and implementation are presented. An update on stability of MOFs in water vapor and liquid systems is provided, and a suite of 18 MOFs are identified for selective use in heat pumps and chillers, while several can be used for air conditioning, water harvesting, and desalination. Most applications with MOFs are still in an exploratory state. An outlook is given for further R&D to realize these applications, providing essential kinetic parameters, performing smart engineering in the design of systems, and conceptual process designs to benchmark them against existing technologies. A concerted effort bridging chemistry, materials science, and engineering is required.

Highly Water-Permeable Metal-Organic Framework MOF-303 Membranes for Desalination.

New membrane materials with excellent water permeability and high ion rejection are needed. Metal-organic frameworks (MOFs) are promising candidates by virtue of their diversity in chemistry and topology. In this work, continuous aluminum MOF-303 membranes were prepared on α-Al2O3 substrates via an in situ hydrothermal synthesis method. The membranes exhibit satisfying rejection of divalent ions (e.g., 93.5% for MgCl2 and 96.0% for Na2SO4) on the basis of a size-sieving and electrostatic-repulsion mechanism and unprecedented permeability (3.0 L·m-2·h-1·bar-1·µm). The water permeability outperforms typical zirconium MOF, zeolite, and commercial polymeric reverse osmosis and nanofiltration membranes. Additionally, the membrane material exhibits good stability and low production costs. These merits recommend MOF-303 as a next-generation membrane material for water softening.

High-Silica CHA Zeolite Membrane with Ultra-High Selectivity and Irradiation Stability for Krypton/Xenon Separation.

Capture and storage of the long-lived 85 Kr is an efficient approach to mitigate the emission of volatile radionuclides from the spent nuclear fuel reprocessing facilities. However, it is challenging to separate krypton (Kr) from xenon (Xe) because of the chemical inertness and similar physical properties. Herein we prepared high-silica CHA zeolite membranes with ultra-high selectivity and irradiation stability for Kr/Xe separation. The suitable aperture size and rigid framework endures the membrane a strong size-exclusion effect. The ultrahigh selectivity of 51-152 together with the Kr permeance of 0.7-1.3×10-8  mol m-2 s-1 Pa-1 of high-silica CHA zeolite membranes far surpass the state-of-the-art polymeric membranes. The membrane is among the most stable polycrystalline membranes for separation of humid Kr/Xe mixtures. Together with the excellent irradiation stability, high-silica CHA zeolite membranes pave the way to separate radioactive Kr from Xe for a notable reduction of the volatile nuclear waste storage volume.

Activity Descriptors Derived from Comparison of Mo and Fe as Active Metal for Methane Conversion to Aromatics.

Producing aromatics directly from the smallest hydrocarbon building block, methane, is attractive because it could help satisfy increasing demand for aromatics while filling the gap created by decreased production from naphtha crackers. The system that catalyzes the direct methane dehydroaromatization (MDA) best so far is Mo supported on zeolite. Mo has shown to outperform other transition metals (TMs). Here we attempt to explain the superiority of Mo by directly comparing Fe and Mo supported on HZSM-5 zeolite. To determine the most important parameters responsible for the superior performance of Mo, detailed characterization using X-ray absorption spectroscopy (XAS) techniques combined with catalytic testing and theoretical calculations are performed. The higher abundance of mono- and dimeric sites for the Mo system, their ease of carburization in methane, as well as intrinsically lower activation energy barriers of breaking the methane C-H bond over Mo explain the better catalytic performance. In addition, a pretreatment in CO is presented to more easily carburize Fe and thereby improve its catalytic performance.

Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes.

The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.

Xenon Recovery by DD3R Zeolite Membranes: Application in Anaesthetics.

Xe is only produced by cryogenic distillation of air, and its availability is limited by the extremely low abundance. Therefore, Xe recovery after usage is the only way to guarantee sufficient supply and broad application. Herein we demonstrate DD3R zeolite as a benchmark membrane material for CO2 /Xe separation. The CO2 permeance after an optimized membrane synthesis is one order magnitude higher than for conventional membranes and is less susceptible to water vapour. The overall membrane performance is dominated by diffusivity selectivity of CO2 over Xe in DD3R zeolite membranes, whereby rigidity of the zeolite structure plays a key role. For relevant anaesthetic composition (<5 % CO2 ) and condition (humid), CO2 permeance and CO2 /Xe selectivity stabilized at 2.0×10-8  mol m-2 s-1 Pa-1 and 67, respectively, during long-term operation (>320 h). This endows DD3R zeolite membranes great potential for on-stream CO2 removal from the Xe-based closed-circuit anesthesia system. The large cost reduction of up to 4 orders of magnitude by membrane Xe-recycling (>99+%) allows the use of the precious Xe as anaesthetics gas a viable general option in surgery.

Influence of Filler Pore Structure and Polymer on the Performance of MOF-Based Mixed-Matrix Membranes for CO2 Capture.

To gain insight into the influence of metal-organic framework (MOF) fillers and polymers on membrane performance, eight different composites were studied by combining four MOFs and two polymers. MOF materials (NH2 -MIL-53(Al), MIL-69(Al), MIL-96(Al) and ZIF-94) with various chemical functionalities, topologies, and dimensionalities of porosity were employed as fillers, and two typical polymers with different permeability-selectivity properties (6FDA-DAM and Pebax) were selected as matrices. The best-performing MOF-polymer composites were prepared by loading 25 wt % of MIL-96(Al) as filler, which improved the permeability and selectivity of 6FDA-DAM to 32 and 10 %, while for Pebax they were enhanced to 25 and 18 %, respectively. The observed differences in membrane performance in the separation of CO2 from N2 are explained on the basis of gas solubility, diffusivity properties, and compatibility between the filler and polymer phases.

Towards High Performance Metal-Organic Framework-Microporous Polymer Mixed Matrix Membranes: Addressing Compatibility and Limiting Aging by Polymer Doping.

Membrane separation for gas purification is an energy-efficient and environment-friendly technology. However, the development of high performance membranes is still a great challenge. In principle, mixed matrix membranes (MMMs) have the potential to overcome current materials limitations, but in practice there is no straightforward method to match the properties of fillers and polymers (the main components of MMMs) in such a way that the final membrane performance reflects the high performance of the microporous filler and the processability of the continuous polymer phase. This issue is especially important when high flux polymers are utilized. In this work, we demonstrate that the use of small amounts of a glassy polymer in combination with high performance PIM-1 allow for the preparation of metal-organic framework (MOF)-based MMMs with superior separation properties and low aging rates under humid conditions, meeting the commercial target for post-combustion CO2 capture.

Revealing the Transient Concentration of CO2 in a Mixed-Matrix Membrane by IR Microimaging and Molecular Modeling.

Through IR microimaging the spatially and temporally resolved development of the CO2 concentration in a ZIF-8@6FDA-DAM mixed matrix membrane (MMM) was visualized during transient adsorption. By recording the evolution of the CO2 concentration, it is observed that the CO2 molecules propagate from the ZIF-8 filler, which acts as a transport "highway", towards the surrounding polymer. A high-CO2 -concentration layer is formed at the MOF/polymer interface, which becomes more pronounced at higher CO2 gas pressures. A microscopic explanation of the origins of this phenomenon is suggested by means of molecular modeling. By applying a computational methodology combining quantum and force-field based calculations, the formation of microvoids at the MOF/polymer interface is predicted. Grand canonical Monte Carlo simulations further demonstrate that CO2 tends to preferentially reside in these microvoids, which is expected to facilitate CO2 accumulation at the interface.

Sensitive and Reversible Detection of Methanol and Water Vapor by In Situ Electrochemically Grown CuBTC MOFs on Interdigitated Electrodes.

The in situ electrochemical growth of Cu benzene-1,3,5-tricarboxylate (CuBTC) metal-organic frameworks, as an affinity layer, directly on custom-fabricated Cu interdigitated electrodes (IDEs) is described, acting as a transducer. Crystalline 5-7 µm thick CuBTC layers are grown on IDEs consisting of 100 electrodes with a width and a gap of both 50 µm and a height of 6-8 µm. These capacitive sensors are exposed to methanol and water vapor at 30 °C. The affinities show to be completely reversible with higher affinity toward water compared to methanol. For exposure to 1000 ppm methanol, a fast response is observed with a capacitance change of 5.57 pF at equilibrium. The capacitance increases in time followed diffusion-controlled kinetics (k = 2.9 mmol s-0.5 g-1CuBTC ). The observed capacitance change with methanol concentration follows a Langmuir adsorption isotherm, with a value for the equilibrium affinity Ke = 174.8 bar-1 . A volume fraction fMeOH = 0.038 is occupied upon exposure to 1000 ppm of methanol. The thin CuBTC affinity layer on the Cu-IDEs shows fast, reversible, and sensitive responses to methanol and water vapor, enabling quantitative detection in the range of 100-8000 ppm.

Structural and elemental influence from various MOFs on the performance of Fe@C catalysts for Fischer-Tropsch synthesis.

The structure and elementary composition of various commercial Fe-based MOFs used as precursors for Fischer-Tropsch synthesis (FTS) catalysts have a large influence on the high-temperature FTS activity and selectivity of the resulting Fe on carbon composites. The selected Fe-MOF topologies (MIL-68, MIL-88A, MIL-100, MIL-101, MIL-127, and Fe-BTC) differ from each other in terms of porosity, surface area, Fe and heteroatom content, crystal density and thermal stability. They are re-engineered towards FTS catalysts by means of simple pyrolysis at 500 °C under a N2 atmosphere and afterwards characterized in terms of porosity, crystallite phase, bulk and surface Fe content, Fe nanoparticle size and oxidation state. We discovered that the Fe loading (36-46 wt%) and nanoparticle size (3.6-6.8 nm) of the obtained catalysts are directly related to the elementary composition and porosity of the initial MOFs. Furthermore, the carbonization leads to similar surface areas for the C matrix (SBET between 570 and 670 m2 g-1), whereas the pore width distribution is completely different for the various MOFs. The high catalytic performance (FTY in the range of 1.9-4.6 × 10-4 molCO gFe-1 s-1) of the resulting materials could be correlated to the Fe particle size and corresponding surface area, and only minor deactivation was found for the N-containing catalysts. Elemental analysis of the catalysts containing deliberately added promoters and inherent impurities from the commercial MOFs revealed the subtle interplay between Fe particle size and complex catalyst composition in order to obtain high activity and stability next to a low CH4 selectivity.

Metal Organic Framework Crystals in Mixed-Matrix Membranes: Impact of the Filler Morphology on the Gas Separation Performance.

Mixed-matrix membranes (MMMs) comprising NH2-MIL-53(Al) and Matrimid® or 6FDA-DAM have been investigated. The MOF loading has been varied between 5 and 20 wt%, while NH2-MIL-53(Al) with three different morphologies: nanoparticles, nanorods and microneedles have been dispersed in Matrimid®. The synthesized membranes have been tested in the separation of CO2 from CH4 in an equimolar mixture. At 3 bar and 298 K for 8 wt% MOF loading, incorporation of NH2-MIL-53(Al) nanoparticles leads to the largest improvement compared to nanorods and microneedles. The incorporation of the best performing filler, i.e. NH2-MIL-53(Al) nanoparticles, to the highly permeable 6FDA-DAM has a larger effect, and the CO2 permeability increased up to 85 % with slightly lower selectivities for 20 wt% MOF loading. Specifically, these membranes have a permeability of 660 Barrer with CO2/CH4 separation factor of 28, leading to a performance very close to the Robeson limit of 2008. Furthermore, a new non-destructive technique based on Raman spectroscopy mapping is introduced to assess the homogeneity of the filler dispersion in the polymer matrix. The MOF contribution can be calculated by modelling the spectra. The determined homogeneity of the MOF filler distribution in the polymer is confirmed by FIB-SEM analysis.

Metal-organic framework nanosheets in polymer composite materials for gas separation.

Composites incorporating two-dimensional nanostructures within polymeric matrices have potential as functional components for several technologies, including gas separation. Prospectively, employing metal-organic frameworks (MOFs) as versatile nanofillers would notably broaden the scope of functionalities. However, synthesizing MOFs in the form of freestanding nanosheets has proved challenging. We present a bottom-up synthesis strategy for dispersible copper 1,4-benzenedicarboxylate MOF lamellae of micrometre lateral dimensions and nanometre thickness. Incorporating MOF nanosheets into polymer matrices endows the resultant composites with outstanding CO2 separation performance from CO2/CH4 gas mixtures, together with an unusual and highly desired increase in the separation selectivity with pressure. As revealed by tomographic focused ion beam scanning electron microscopy, the unique separation behaviour stems from a superior occupation of the membrane cross-section by the MOF nanosheets as compared with isotropic crystals, which improves the efficiency of molecular discrimination and eliminates unselective permeation pathways. This approach opens the door to ultrathin MOF-polymer composites for various applications.

Azine-Linked Covalent Organic Framework (COF)-Based Mixed-Matrix Membranes for CO2 /CH4 Separation.

Mixed-matrix membranes (MMMs) comprising Matrimid and a microporous azine-linked covalent organic frameworks (ACOF-1) were prepared and tested in the separation of CO2 from an equimolar CO2 /CH4 mixture. The COF-based MMMs show a more than doubling of the CO2 permeability upon 16 wt % ACOF-1 loading together with a slight increase in selectivity compared to the bare polymer. These results show the potential of COFs in the preparation of MMMs.

Structural Effects in Visible-Light-Responsive Metal-Organic Frameworks Incorporating ortho-Fluoroazobenzenes.

The ability to control the interplay of materials with low-energy photons is important as visible light offers several appealing features compared to ultraviolet radiation (less damaging, more selective, predominant in the solar spectrum, possibility to increase the penetration depth). Two different metal-organic frameworks (MOFs) were synthesized from the same linker bearing all-visible ortho-fluoroazobenzene photoswitches as pendant groups. The MOFs exhibit different architectures that strongly influence the ability of the azobenzenes to isomerize inside the voids. The framework built with Al-based nodes has congested 1D channels that preclude efficient isomerization. As a result, local light-heat conversion can be used to alter the CO2 adsorption capacity of the material on exposure to green light. The second framework, built with Zr nodes, provides enough room for the photoswitches to isomerize, which leads to a unique bistable photochromic MOF that readily responds to blue and green light. The superiority of green over UV irradiation was additionally demonstrated by reflectance spectroscopy and analysis of digested samples. This material offers promising perspectives for liquid-phase applications such as light-controlled catalysis and adsorptive separation.

Assessing the Surface Area of Porous Solids: Limitations, Probe Molecules, and Methods.

In this modeling study, the uses of nitrogen (77.3 K), probe molecule of choice for decades, and argon, opted as alternative in the 2015 IUPAC report on adsorptive characterization, as probe molecules for geometric surface area determination are compared. Graphene sheets possessing slit-shaped pores with varying size (width) are chosen as model porous solids, and different methods for the determination of specific surface areas are investigated. The BET method, which is the most commonly applied analysis, is compared to the Langmuir and relatively recently proposed ESW (excess sorption work) method. We show that either using argon or nitrogen as adsorptive, the physical meaningfulness of adsorption-derived surface areas highly depends on the pore size. When less than two full layers of adsorbate molecules can be formed within slitlike pores of a graphitic material (Dpore < 5.8 Å for Ar/N2), adsorption-derived surface areas are about half that of the geometric surface area. Between two and four layers (6.8 < Dpore < 12.8 Å), adsorption surface areas can be significantly larger (up to 75%) than the geometric surface area because monolayer-multilayer formation and pore filling cannot be distinguished. For four or more layers of adsorbate molecules (Dpore > 12.8 Å), adsorption-derived surface areas are comparable to their geometrically accessible counterparts. Note that for the Langmuir method this only holds if pore-filling effects are excluded during determination. This occurs in activated carbon materials as well. In the literature, this indistinguishability issue has been largely overlooked, and erroneous claims of materials with extremely large surface areas have been made. Both the BET and Langmuir areas, for Dpore > 12.8 Å, correspond to geometric surface areas, whereas the ESW method yields significantly lower values. For the 6.8 Å < Dpore < 12.8 Å range, all methods erroneously overestimate the specific surface area. For the energetically homogeneous graphene sheets, differences between argon and nitrogen for the assessment of surface areas are minor.

Investigating the Case of Titanium(IV) Carboxyphenolate Photoactive Coordination Polymers.

The reactivity of 2,5-dihydroxyterephthalic acid (H4DOBDC) with titanium(IV) precursors was thoroughly investigated for the synthesis of metal-organic frameworks under solvothermal conditions. Four crystalline phases were isolated whose structures were studied by a combination of single-crystal or powder X-ray diffraction and solid-state NMR. The strong coordination ability of the phenolate moieties was found to favor the formation of isolated TiO6 octahedra bearing solely organic ligands in the resulting structures, unless hydrothermal conditions and precondensed inorganic precursors are used. It is worth noting that these solids strongly absorb visible light, as a consequence of the ligand-to-metal charge transfer (LMCT) arising from Ti-phenolate bonds. Preliminary photocatalytic tests suggest that one compound, namely, MIL-167, presents a higher activity for hydrogen evolution than the titanium carboxylate MIL-125-NH2 but that such an effect cannot be directly correlated with its improved light absorption feature.

Metal-organic framework based mixed matrix membranes: a solution for highly efficient CO2 capture?

The field of metal-organic framework based mixed matrix membranes (M(4)s) is critically reviewed, with special emphasis on their application in CO2 capture during energy generation. After introducing the most relevant parameters affecting membrane performance, we define targets in terms of selectivity and productivity based on existing literature on process design for pre- and post-combustion CO2 capture. Subsequently, the state of the art in M(4)s is reviewed against these targets. Because final application of these membranes will only be possible if thin separation layers can be produced, the latest advances in the manufacture of M(4) hollow fibers are discussed. Finally, the recent efforts in understanding the separation performance of these complex composite materials and future research directions are outlined.