Selective Separation Of CO2 Research Articles

Porous liquids based on UiO-66@SiO2 through the strategy of growing an ultrathin silica layer for CO2 selective separation

Porous liquids based on UiO-66@SiO2 through the strategy of growing an ultrathin silica layer for CO2 selective separation

Stable hierarchical ionic liquid nanochannels for highly efficient CO2 adsorption, separation and conversion

Constructing stable nanochannels and nanoconfined environments for ionic liquids holds significant application value in gas separation, ion channels, and related fields. The functional polyionic liquid synthesized in this study exhibits a controllable assembly structure and demonstrates liquid crystal properties. Through heating and water treatment, the polyionic liquids crosslink to form multi-hierarchical nanopores, including sub-nanochannels with pore sizes similar to CO2, without the need for a catalyst. The specific surface area and pore size of the polyionic liquid network (PILC) were adjusted by regulating the self-assembly of polyionic liquids in water. The unique PILC, combining ionic liquid nanopores and liquid crystal structure properties, shows high CO2 adsorption performance and excellent CO2/N2 selectivities, surpassing commonly reported ionic liquid porous materials. Furthermore, PILC-2 exhibits good catalytic performance for CO2 cycloaddition, and its catalytic activity and selectivity did not significantly decrease after five cycles. This study successfully introduces hierarchical ionic liquid nanochannels into porous networks without involving any inorganic ordered nanomaterials. This provides a simple and effective approach for the highly selective adsorption and separation of CO2, as well as for the preparation of catalytic materials.

Development of cost-effective cellulose-based bilayer hybrid composite membranes for CO2 separation in biogas purification.

CO2 is the main pollutant in biogas, reducing its calorific value. Among various technological methods to eliminate carbon dioxide from biogas, membrane separation technology stands out for large-scale industrial biogas purification due to its advantages. The selection of membrane material and preparation process are key factors in membrane separation technology. In this study, a premixing process was initially used to blend different masses of packed molecular sieves TS-1 (or ZSM-5) and cellulose derivatives (ethyl cellulose, cellulose acetate) separately. These mixtures were then coated onto porous PVDF substrates using a coating process to create various bilayer hybrid composite membranes. Among these, PVDF/EC-ZSM-5 (containing 15% ZSM-5) bilayer hybrid composite membrane is the most fitting. For CO2/CH4 gas mixtures, the gas selectivity of this membrane surpassed Robeson's 1991 standard line (the CO2 permeability was 597.48 Barrer, and the CO2/CH4 selectivity was 9.14). Overall, this composite membrane, made for the first time from PVDF, ZSM-5, and EC, is expected to be a promising CO2 selective separation membrane material for biogas purification in large-scale industrial processes due to its simple production process.

Facile synthesis of inherently nitrogen-doped PAN-derived microporous carbons activated with NaNH2 for selective CO2 adsorption and separation

N-doped porous carbons (PCs) are extensively researched for CO2 capture and separation under flue gas conditions, but their complex and expensive preparation methods hinder widespread industrial use. Herein, we present a direct approach for synthesizing N-doped PCs by utilizing polyacrylonitrile (PAN) and NaNH2 as precursors, without the need for any solvents. The utilization of NaNH2 as both a porogen and nitrogen supply during carbonization is primarily responsible for the formation of the well-developed pore structure and high specific surface area of N-doped PCs. The optimized sample “PN-3” demonstrated excellent textural features with an excellent specific surface area (SSA) of 2490 m2/g, a pore volume of 2.0559 cm3/g, a well-defined pore size distribution (PSD), and abundant micropores (<1 nm). In addition, PN-3 has the highest pyrrolic nitrogen content (∼40.1 at.%), resulting in a significant capacity for CO2 adsorption (7.15 mmol/g at 273 K/1bar, 4.56 mmol/g at 298 K/1 bar, 26.2 mmol/g at 298 K/ 40 bar). Furthermore, it exhibits an outstanding CO2/N2 selectivity (∼102) based on the ideal adsorbed solution theory (IAST) at 273 K, surpassing the performance of most of previously reported biomass and polymer-derived N-doped carbons in terms of CO2 adsorption and separation. In addition, the adsorption process is characterized by a modest heat of adsorption (39.10 kJ/mol) and a steady cyclic pattern of CO2 adsorption–desorption under flue gas settings (15 % CO2 and 85 % N2). This indicates that the adsorption is mostly governed by physisorption, which allows for an energy-efficient regeneration process. In summary, this study showcases the successful production of highly PCs that can effectively adsorb CO2, enlightening the way toward establishment of a cost-effective and facile synthetic protocol for achieving CO2 capture/separation at the commercial scale.

Joint experimental-computational: Revealing the role of sodium poly(heptazineimide) in the selective separation of CO2 in PEBAX-based mixed matrix membranes

Mixed matrix membranes (MMMs) with the dual properties of porous materials and polymer matrix membranes have become one of the most optimal solutions to the gas separation problem. However, the adapted porous material and the explicit transport mechanism of gases within the mixed matrix membrane hinder its further commercialization. Thanks to their porous nature and tunable gas adsorption properties, heteroatom-doped porous materials, especially nitrogen-doped porous materials, are widely used to design and prepare advanced CO2 separation membranes. Herein, a layered two-dimensional nano-sheet with a nitrogen content of 44.7 % was successfully synthesized via thermal polymerization. And nano-sheets were homogeneously dispersed in a Pebax matrix to make a composite film. Since the CO2 affinity of the nitrogen functional site and the PEO flexible chain, realizing the synergistic improvement of CO2 permeability and selectivity. A comprehensive combined permeation experimental/simulation characterization reveals the CO2 transport pathway within the membrane, indicating the mechanism of action of nitrogen-doped porous packing on CO2 diffusion. Among these, the CO2 permeability of the mixed matrix film containing 5 wt% sodium poly(heptazine imide) (NaPHI) reached 153 Barrer at a feed gas pressure of 9 bar, nearly 149 % compared to the pure Pebax film. The selectivity of CO2/N2 was enhanced to 105, exhibiting a remarkable increase of 159 % and exceeding the 2019 Robeson limit. Importantly, the present work further reveals and demonstrates the gas separation mechanism of nitrogen-doped porous filler/polymer hybrid matrix membranes, which provides new ideas for the design and application of heteroatom-doped porous fillers in the field of gas separation.

Highly Selective CO2 Separation on Na-exchanged DNL-6 Synthesized by Utilization of Spent Industrial Catalyst

Highly Selective CO2 Separation on Na-exchanged DNL-6 Synthesized by Utilization of Spent Industrial Catalyst

A novel PVI-PVA/PS composite membrane modified by metal ions for CO2 separation: Effect and mechanism

The membrane process is potentially more energy-efficient than conventional separation technologies in the separation of carbon dioxide (CO2) /nitrogen (N2) from flue gas. In this work, a series of PVI (Polyvinylimidazole)-PVA (Polyvinyl alcohol) /PS (Polysulfone) membranes were prepared by co-blending two polymers, PVI and PVA, as the separation layer of the fixed carrier composite membrane. The separation performance increased by the dual action of PVA and the imidazole group in the PVI. Furthermore, Mg2+-PVI-PVA/PS and Cu2+-PVI-PVA/PS composite membranes were developed by adding Mg2+ and Cu2+, and the separation performance was considerably improved by complexing metal ions with PVA and PVI. Especially, Mg2+-PVI-PVA/PS demonstrated superior separation performance, with a CO2 permeation rate of 12 GPU and a CO2/N2 separation factor of 183 at a pressure of 1 bar. What’s more, the mechanism study clarified that the prepared composite membrane mainly relies on the facilitated transfer mechanism to achieve the selective separation of CO2. The presence of water molecules significantly improved the CO2 permeability and separation selectivity, indicating that PVI-PVA and Mg2+ could promote the hydration reaction of CO2 and H2O, forming easily mobile HCO3- carriers.

Halogen-Decorated Metal-Organic Frameworks for Efficient and Selective CO2 Capture, Separation, and Chemical Fixation with Epoxides under Mild Conditions.

In the present work, three novel halogen-appended cadmium(II) metal-organic frameworks [Cd2(L1)2(4,4'-Bipy)2]n·4n(DMF) (1), [Cd2(L2)2(4,4'-Bipy)2]n·3n(DMF) (2), and [Cd(L3)(4,4'-Bipy)]n·2n(DMF) (3) [where L1 = 5-{(4-bromobenzyl)amino}isophthalate; L2 = 5-{(4-chlorobenzyl)amino}isophthalate; L3 = 5-{(4-fluorobenzyl)amino}isophthalate; 4,4'-Bipy = 4,4'-bipyridine; and DMF = N,N'-dimethylformamide] have been synthesized under solvothermal conditions and characterized by various analytical techniques. The single-crystal X-ray diffraction analysis demonstrated that all the MOFs feature a similar type of three-dimensional structure having a binuclear [Cd2(COO)4(N)4] secondary building block unit. Moreover, MOFs 1 and 2 contain one-dimensional channels along the b-axis, whereas MOF 3 possesses a 1D channel along the a-axis. In these MOFs, the pores are decorated with multifunctional groups, i.e., halogen and amine. The gas adsorption analysis of these MOFs demonstrate that they display high uptake of CO2 (up to 5.34 mmol/g) over N2 and CH4. The isosteric heat of adsorption (Qst) value for CO2 at zero loadings is in the range of 18-26 kJ mol-1. In order to understand the mechanism behind the better adsorption of CO2 by our MOFs, we have also performed configurational bias Monte Carlo simulation studies, which confirm that the interaction between our MOFs and CO2 is stronger compared to those with N2 and CH4. Various noncovalent interactions, e.g., halogen (X)···O, Cd···O, and O···O, between CO2 and the halogen atom, the Cd(II) metal center, and the carboxylate group from the MOFs are observed, respectively, which may be a reason for the higher carbon dioxide adsorption. Ideal adsorbed solution theory (IAST) calculations of MOF 1 demonstrate that the obtained selectivity values for CO2/CH4 (50:50) and CO2/N2 (15:85) are ca. 28 and 193 at 273 K, respectively. However, upon increasing the temperature to 298 K, the selectivity value (S = 34) decreases significantly for the CO2/N2 mixture. We have also calculated the breakthrough analysis curves for all the MOFs using mixtures of CO2/CH4 (50:50) and CO2/N2 (50:50 and 15:85) at different entering gas velocities and observed larger retention times for CO2 in comparison with other gases, which also signifies the stronger interaction between our MOFs and CO2. Moreover, due to the presence of Lewis acidic metal centers, these MOFs act as heterogeneous catalysts for the CO2 fixation reactions with different epoxides in the presence of tetrabutyl ammonium bromide (TBAB), for conversion into industrially valuable cyclic carbonates. These MOFs exhibit a high conversion (96-99%) of epichlorohydrin (ECH) to the corresponding cyclic carbonate 4-(chloromethyl)-1,3-dioxolan-2-one after 12 h of reaction time at 1 bar of CO2 pressure, at 65 °C. The MOFs can be reused up to four cycles without compromising their structural integrity as well as without losing their activity significantly.

Graphene Oxide/Melamine/Ionic liquid membranes for selective CO2 separation

Highly permeable and selective membranes with long-term stability are needed to reduce operating and capital costs of industrial gas-separation units. In this study, we fabricate new membranes made of melamine (M)- and imidazolium-based ionic liquid (IL)-modified graphene oxide (GO) deposited on a porous support and buried with a polydimethylsiloxane (PDMS) layer. The CO2/N2 and CO2/CH4 ideal selectivities of the composite membranes are respectively 65 % and 70 % higher than those of the membranes containing only the IL. This significant improvement in ideal selectivity is attributed to synergic effects of nanochannels created by GO, fixed facilitated transport provided by the IL and numerous amine groups in the melamine structure, and the increased polarity of the membrane caused by the presence of the IL. The composite membrane has a pure CO2 permeance of 47 GPU with a high CO2/N2 ideal selectivity of 109 and a satisfactory CO2/CH4 ideal selectivity of 39. The composite membrane maintains stable performance over a 60-hour operation, highlighting its long-term reliability. The outstanding performance, coupled with the ease of fabrication, underscores the potential of these composite membranes for practical and efficient CO2 removal from both natural and flue gas streams in real-world applications.

ZSM-5@MOF-199 core-shell composite adsorbent: Rapid ambient synthesis and CO/CO2 adsorption

Using a hydroxy double salt intermediate, we demonstrated rapid room temperature fabrication of ZSM-5@MOF-199 core–shell sorbents. Copper chloride was compatible with the ZnO-assisted MOF growth scheme. The structural and chemical properties of the composite were fine-tuned through either the core or the shell modification, targeting a superior adsorption capacity for CO and CO2 compared to parent adsorbents. For example, the Na2S2O3-assisted MOF-199 shell reduction enriched surface Cu+ and enhanced CO adsorption capacity. Modulating the zeolite core to protonic hierarchical ZSM-5 (HZSM-5) increased CO and CO2 uptake by 20 % and 28 %, respectively. The isosteric heat of adsorption revealed that the HZSM-5 core altered surface electronic properties and influenced the CO2 adsorption performance. Thermodynamic analysis indicated that the adsorption processes involved a combination of physisorption and electrostatic interactions with an ordered arrangement of adsorbates. The core–shell sorbent can be easily tuned for selective separation of CO and CO2.

Selective CO2 separation through physicochemical absorption by triazole‐functionalized ionic liquid binary absorbents

AbstractThe selective separation of CO2 from CH4‐containing gases is crucial to produce clean energy gases. In this study, triazole anion‐functionalized ionic liquids (TAFILs) were designed by combining low molecular weight cations with triazole anions containing N electronegative site and further mixed with physical solvents to form physicochemical absorbents. The results indicated that [Cho][Triz]/TMS (80 wt%/20 wt%) not only absorbs 0.125 g CO2/g absorbent equal to that of 30 wt% MEA solution at 40°C and 1 bar, but also has low enthalpy of −35.76 kJ/mol less than half of 30 wt% MEA solution. Simultaneously, a super high CO2/CH4 selectivity of 191.0, higher than most of the reported absorbents, is obtained for [Cho][Triz]/TMS solvents. Such great performance of CO2 separation was attributed to relatively weak chemical and physical interaction between CO2 and TAFIL binary absorbents. This study may provide novel promising ionic liquid absorbents for CO2 capture applications from clean energy gases.

Synthesis of amine-pillar[5]arene porous adsorbent for adsorption of CO2 and selectivity over N2 and CH4

A novel amine-modified pillar[5]arene bonded porous silica adsorbent (DETA-P5S) was designed to be applied to dynamic CO2 adsorption and selective separation of CO2 over N2 and CH4 gases mixture. The results demonstrated that reasonable introduction of DETA into the BE-P5 bonded silica support has significantly increased the adsorption capacity of CO2. The DETA-P5S has the optimal adsorption capacity of 9.1 mmol/g with 5 vol% CO2 at 40 °C. The main reason of this increased capacity could be attributed to the enhanced CO2 diffusion into porous adsorbent for its better dispersion in the pores of amine-pillar[5]arene cavity and active site of DETA. Furthermore, the dynamic saturation adsorption capacities of DETA-P5S were 7.11 (0.37) and 6.18 (0.44) mmol/g for CO2/N2 and CO2/CH4, respectively, both the gas mixtures showed high separation selectivity. Simultaneously, the DETA-P5S can maintain outstanding CO2 adsorption capacity after fifteen regeneration cycles. Consequently, the designed DETA-P5S could serve as a promising adsorbent for CO2 capture and storage.

Insight into the selective separation of CO2 from biomass pyrolysis gas over metal-incorporated nitrogen-doped carbon materials: a first-principles study

Insight into the selective separation of CO2 from biomass pyrolysis gas over metal-incorporated nitrogen-doped carbon materials: a first-principles study

Insights into adsorption and diffusion of CO2, CH4 and their mixture in MIL-101(Cr) via molecular simulation

An in-depth comprehension of the adsorption and diffusion properties of CH4, CO2, and their mixture in MIL-101(Cr) is crucial for its application in the highly selective separation of CO2 and CH4 mixtures in biogas. Existing studies often overlook the influence of gas molecular radius and MIL-101 topological structure on adsorption and lack quantitative analysis of the primary and secondary adsorption sites of MIL-101. Additionally, there is a significant gap in research on the adsorption mechanism of gas mixtures. To address these gaps and to provide new knowledge, this study employs Monte Carlo and molecular dynamics simulations to evaluate various factors such as CH4 and CO2 adsorption isotherms, density distribution profiles, self-diffusion coefficients, radial distribution functions (RDF), and CO2/CH4 selectivity within MIL-101 metal-organic framework (MOF). The insightful and comprehensive atomic-level study reveals several unique and new findings, include 1) the RDF analysis shows that the C = C double bond of the benzene ring within MIL-101 primarily governs the adsorption of CH4, while the open metal center (Cr) exhibits significant adsorption effects on CO2; 2) the density distribution profile analysis indicates that CH4 molecules tend to localize in the larger and medium-sized cages, whereas CO2 molecules exhibit relatively uniform distribution. 3) evaluation of self-diffusivity coefficients and diffusion activation energies demonstrated that CH4 diffuses more easily than CO2, and in the CO2 and CH4 two-component gas, the existence of CH4 can further reduce the diffusion coefficient of CO2. This investigation provides a microscopic understanding of adsorption and diffusion phenomena within MIL-101, contributing to the overall comprehension of its behavior in gas separation applications.

Achieving selective CO2 capture and separation in crosslinked porous porphyrin-based polyimide skeletons

The precise control of porous structure has always been a key factor for porous materials. We tuned the porous structures by enhancing alkynyl-groups contents and introducing metal into porphyrin ring. We used simple polymerization and alkynyl crosslinking reactions to construct crosslinked porous porphyrin-based polyimides (CR-PPBPIs) from 2,5-bis(3,4-dicarboxyphenoxy)-4’-phenylethynyl-biphenyl dianhydride (PEPHQDA) and 5,10,15,20-tetra[4-[(3-aminophenyl)ethynyl]phenyl] porphyrin (TAPEPP). CR-PPBPIs revealed BET surface areas (212, 578 and 593 m2 g−1), dominated pore width (1 and 1.9 nm) and abundant CO2-philic substances. Thus, considerable CO2 uptakes (1.92, 2.43 and 2.52 mmol g−1), CO2-adsorption isosteric enthalpies (31.9, 26.0 and 27.9 kJ mol−1) and superior CO2/N2 selectivities (45.77, 38.72 and 46.26) were achieved. This work sheds some light on the precise regulation of porosity parameters in the crosslinked metalloporphyrin-based polyimides for carbon dioxide adsorption and separation.

Mixed matrix membranes with intrinsic microporous/UiO-66 post-synthesis modifications with no defects for efficient CO2/N2 separation

Mixed matrix membranes (MMMs) based on metal–organic frameworks (MOFs) are expected to realize efficient separation of CO2. However, interfacial compatibility issues between MOFs and polymer matrices limit their performance. In this work, a post-synthesis modification (PSM) strategy was adopted to convert UiO-66 into porous liquids (PLs). MMMs were prepared by incorporating PLs into PIM-1 matrix. The PLs have a liquid-like behavior and can be evenly scattered in PIM-1 matrix to form an interface without defect. The SEM morphology analysis further certified that MMMs had no interface defect and PLs had brilliant compatibility with the polymer film. In addition, the CO2-philic ether bonds of the EO fragments enable the MMMs to have superior CO2 selective separation. Compared with pure PIM-1, the highest CO2 permeability was improved by 158.0 % and 62.5 % was the increase in CO2/N2 selectivity, arriving at 7211.7 Barrer and 26.0, respectively. Meanwhile, the overall separation performance of MMMs for CO2/N2 exceeds the 2008 Robson upper limit, showing outstanding gas separation performance.

Multi-Functional Polymer Membranes Enable Integrated CO2 Capture and Conversion in a Single, Continuous-Flow Membrane Reactor under Mild Conditions.

Herein, we present a membrane-based system designed to capture CO2 from dilute mixtures and convert the captured CO2 into value-added products in a single integrated process operated continuously under mild conditions. Specifically, we demonstrate that quaternized poly(4-vinylpyridine) (P4VP) membranes are selective CO2 separation membranes that are also catalytically active for cyclic carbonate synthesis from the cycloaddition of CO2 to epichlorohydrin. We further demonstrate that quaternized P4VP membranes can integrate CO2 capture, including from dilute mixtures down to 0.1 kPa of CO2, with CO2 conversion to cyclic carbonates at 57 °C and atmospheric pressure. The catalytic membrane acts as both the CO2 capture and conversion medium, providing an energy-efficient alternative to sorbent-based capture, compression, transport, and storage. The membrane is also potentially tunable for the conversion of CO2 to a variety of products, including chemicals and fuels not limited to cyclic carbonates, which would be a transformative shift in carbon capture and utilization technology.

Developing High-Capacity Solid "Molecular Basket" Sorbents for Selective CO2 Capture and Separation.

ConspectusSince carbon-based energy continues to dominate (over 80%) the global primary energy supply, carbon dioxide capture, utilization, and sequestration (CCUS) is deemed to be a promising and viable option to mitigate greenhouse gas emissions and climate change, for which CO2 capture is critical to the overall success of CCUS. Although liquid amine scrubbing is a mature technology for carbon capture, it is energy-intensive and costly due to energy consumption in solvent heating and water evaporation apart from the energy needed to break amine-CO2 bonding. To address this challenge, Song's group developed a new design approach for adsorptive CO2 capture and separation, namely, "molecular basket" sorbents (MBS), without the need for dealing with solvent heating and water evaporation. The solid MBS consisting of polymeric amines (such as PEI) immobilized into nanoporous materials (such as SBA-15) possesses a high capacity for CO2 capture with high selectivity, fast kinetics, and good regenerability. Consequently, MBS can greatly reduce energy consumption and carbon capture cost. Conventional adsorbents such as zeolites, activated carbon, alumina, and silica have low adsorption capacities, and their use of CO2 adsorption requires prior removal of moisture and cooling of flue gas (∼35 °C). On the contrast, the CO2 sorption capacity of MBS can even be promoted by the presence of moisture/steam and reaches the best performance closer to flue gas temperature (∼75 °C). This Account presents an overview of our research progress in the material development and fundamental understanding of MBS for CO2 capture and the separation of CO2 from various gas streams. It begins with an illustration of the MBS concept, followed by efforts to improve the performance and pilot-scale demonstration of MBS for CO2 capture. With the systematic characterization of MBS by various ex situ and in situ techniques, a better understanding is developed for the CO2 sorption process mechanistically. Furthermore, this Account demonstrates how the fundamental understanding of the CO2 sorption mechanism promotes the further development of more robust and advanced sorbent materials with improved CO2 sorption capacity, kinetics of sorption and desorption, and cyclic stability. Finally, an outlook is provided for the future design and development of novel sorbent materials and the CO2 sorption process for various gas streams including flue gas, biogas, air, and hydrogen streams.

Polyimide/Ionic Liquids Hybrid Membranes with NH3-Philic Channels for Ammonia-Based CO2 Separation Processes.

An efficient separation technology involving ammonia (NH3) and carbon dioxide (CO2) is of great importance for achieving low-carbon economy, environmental protection, and resource utilization. However, directly separating NH3 and CO2 for ammonia-based CO2 capture processes is still a great challenge. Herein, we propose a new strategy for selective separation of NH3 and CO2 by functional hybrid membranes that integrate polyimide (PI) and ionic liquids (ILs). The incorporated protic IL [Bim][NTf2] is confined in the interchain segment of PI, which decreases the fractional free volume and narrows the gas transport channel, benefiting the high separation selectivity of hybrid membranes. At the same time, the confined IL also provides high NH3 affinity for transport channels, promoting NH3 selective and fast transport owing to strong hydrogen bonding interaction between [Bim][NTf2] and NH3 molecules. Thus, the optimal hybrid membrane exhibits an ultrahigh NH3/CO2 ideal selectivity of up to 159 at 30 °C without sacrificing permeability, which is 60 times higher than that of the neat PI membrane and superior to the state-of-the art reported values. Moreover, the introduction of [Bim][NTf2] also reduces the permeation active energy of NH3 and reverses the hybrid membrane toward "NH3 affinity", as understood by studying the effect of temperature. Also, NH3 molecules are much easier to transport at high temperature, showing great application potential in direct NH3/CO2 separation. Overall, this work provides a promising ultraselective membrane material for ammonia-based CO2 capture processes.

Three Robust Isoreticular Metal-Organic Frameworks with High-Performance Selective CO2 Capture and Separation.

Based on the hard-soft acid base (HSAB) theory, three robust isoreticular metal-organic frameworks (MOFs) with nia topology were successfully synthesized by solvothermal reaction {[In3O(BHB)(H2O)3]NO3·3DMA (JLU-MOF110(In)), [Fe3O(BHB)(H2O)3]NO3 (JLU-MOF110(Fe)), and [Fe2NiO(BHB)(H2O)3] (JLU-MOF110(FeNi)) (DMA = N,N-dimethylacetamide, H6BHB = 4,4″-benzene-1,3,5-triyl-hexabenzoic acid)}. Both JLU-MOF110(In) and JLU-MOF110(Fe) are cationic frameworks, and their BET surface areas are 301 and 446 m2/g, respectively. By modification of the components of metal clusters, JLU-MOF110(FeNi) features a neutral framework, and the BET surface area is increased up to 808 m2/g. All three MOF materials exhibit high chemical and thermal stability. JLU-MOF110(In) remains stable for 24 h at pH values ranging from 1 to 11, while JLU-MOF110(Fe) and JLU-MOF110(FeNi) persist to be stable for 24 h at pH from 1 to 12. JLU-MOF110(In) exhibits thermal stability up to 350 °C, whereas JLU-MOF110(Fe) and JLU-MOF(FeNi) can be stable up to 300 °C. Thanks to the microporous cage-based structure and abundant open metal sites, JLU-MOF110(In), JLU-MOF110(Fe), and JLU-MOF110(FeNi) have excellent CO2 capture capacity (28.0, 51.5, and 99.6 cm3/g, respectively, under 298 K and 1 bar). Interestingly, the ideal adsorption solution theory results show that all three MOFs exhibit high separation selectivity toward CO2 over N2 (35.2, 43.2, and 43.2 for CO2/N2 = 0.15/0.85) and CO2 over CH4 (14.4, 11.5, and 10.1 for CO2/CH4 = 0.5/0.5) at 298 K and 1 bar. Thus, all three MOFs are potential candidates for CO2 capture and separation. Among them, JLU-MOF110(FeNi) displays the best separation potential, as revealed by dynamic column breakthrough experiments.