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Purification of C2H4 from the ternary C2 hydrocarbon mixture in one step is of critical significance but still extremely challenging according to its intermediate physical properties between C2H6 and C2H2. Hydrogen-bonded organic frameworks (HOFs) stabilized by supramolecular interactions are emerging as a new kind of adsorbents that facilitate green separation. However, it remains a problem to efficiently realize the one-step C2H4 purification from C2H6/C2H4/C2H2 mixture because of the low C2H2/C2H4 selectivity. We herein report a robust microporous HOF (termed as HOF-TDCPB) with dense O atoms and aromatic rings distributed on the pore surface which provide C2H6 and C2H2 preferred environment simultaneously. Dynamic breakthrough experiments indicate that HOF-TDCPB can not only obtain high-purity C2H4 from binary C2 mixture, but also firstly realize one-step C2H4 purification from ternary C2H6/C2H4/C2H2 mixture, with the C2H4 productivity of 3.2 L/kg (>99.999%) for one breakthrough cycle. Furthermore, HOF-TDCPB displays outstanding stability in air, organic solvents and water, which endow it excellent cycle performance even under high-humidity conditions. Theoretical calculations indicate that multiple O sites on pore channels can create synergistic binding sites for C2H2, thus affording overall stronger multipoint interactions.
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The separation of acetylene (C2H2) from ethylene (C2H4) and ethane (C2H6) is crucial for the production of high-purity C2H2 and the recovery of other gases. Polyhedron-based metal-organic frameworks (PMOFs) are characterized by their spacious cavities, which facilitate gas trapping, and cage windows with varying sizes that enable gas screening. In this study, we carefully selected a class of PMOFs based on V-type tetracarboxylic acid linker (JLU-Liu22 containing benzene ring, JLU-Liu46 containing urea group and recombinant reconstructed In/Cu CBDA on the basis of JLU-Liu46) to study the relationship between pore environment and C2 adsorption and separation performance. Among the three compounds, JLU-Liu46 exhibits superior selectivity toward C2H2/C2H4 (2.06) as well as C2H2/C2H6 (2.43). Comparative structural analysis reveals that the exceptional adsorbed-C2H2 performance of JLU-Liu46 can be attributed to the synergistic effects arising from coordinatively unsaturated Cu sites combined with an optimal pore environment (matched pore size and polarity, urea functional group), resulting in a strong affinity between the framework and C2H2 molecules. Furthermore, transient breakthrough simulations of JLU-Liu46 confirmed its potential for separating C2H2 in ternary C2 gas.
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The adsorptive separation of ternary propyne (C3H4)/propylene (C3H6)/propane (C3H8) mixtures is of significant importance due to its energy efficiency. However, achieving this process using an adsorbent has not yet been accomplished. To tackle such a challenge, herein, we present a novel approach of fine-regulation of the gradient of gate-opening in soft nanoporous crystals. Through node substitution, an exclusive gate-opening to C3H4 (17.1 kPa) in NTU-65-FeZr has been tailored into a sequential response of C3H4 (1.6 kPa), C3H6 (19.4 kPa), and finally C3H8 (57.2 kPa) in NTU-65-CoTi, of which the gradient framework changes have been validated by in situ powder X-ray diffractions and modeling calculations. Such a significant breakthrough enables NTU-65-CoTi to sieve the ternary mixtures of C3H4/C3H6/C3H8 under ambient conditions, particularly, highly pure C3H8 (99.9%) and C3H6 (99.5%) can be obtained from the vacuum PSA scheme. In addition, the fully reversible structural change ensures no loss in performance during the cycling dynamic separations. Moving forward, regulating gradient gate-opening can be conveniently extended to other families of soft nanoporous crystals, making it a powerful tool to optimize these materials for more complex applications.
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Ethylene (C2H4) purification and propylene (C3H6) recovery are highly relevant in polymer synthesis, yet developing physisorbents for these industrial separation faces the challenges of merging easy scalability, economic feasibility, high moisture stability with great separation efficiency. Herein, we reported a robust and scalable MOF (MAC-4) for simultaneous recovery of C3H6 and C2H4. Through creating nonpolar pores decorated by accessible N/O sites, MAC-4 displays top-tier uptakes and selectivities for C2H6 and C3H6 over C2H4 at ambient conditions. Molecular modelling combined with infrared spectroscopy revealed that C2H6 and C3H6 molecules were trapped in the framework with stronger contacts relative to C2H4. Breakthrough experiments demonstrated exceptional separation performance for binary C2H6/C2H4 and C3H6/C2H4 as well as ternary C3H6/C2H6/C2H4 mixtures, simultaneously affording record productivities of 27.4 and 36.2â L kg-1 for high-purity C2H4 (≥99.9 %) and C3H6 (≥99.5 %). MAC-4 was facilely prepared at deckgram-scale under reflux condition within 3â hours, making it as a smart MOF to address challenging gas separations.
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The separation challenge posed by propylene/propane mixtures arises from their nearly identical molecular sizes and physicochemical properties. Metal-organic frameworks (MOFs) have demonstrated potential in addressing this challenge through the precision tailoring of pore sizes and surface chemistry. However, introducing modifications at the molecular level remains a considerable hurdle. This work presents an approach to reversibly tune the propylene/propane adsorption preference in zeolitic imidazolate framework-8 (ZIF-8) by manipulating the particle size and gas flow rate. Systematically increasing the ZIF-8 crystals from 9 to 224 µm restricts propane diffusion, thereby reversing its preferential adsorption over propylene. Furthermore, raising the gas flow rate of mixed propylene/propane shifts the rate-determining breakthrough step from thermodynamic equilibrium to kinetics, again reversing the adsorption preference in a particular ZIF-8 sample. We propose "dynamic selectivity (Sd(t))" as a concept that incorporates both thermodynamic and kinetic factors to elucidate these unexpected findings. Moreover, the driving force equation, grounded on the concept of Sd(t), has improved the precision and stability of the computational simulation for fixed-bed adsorption processes. This work underscores the potential of diffusion-based modulation, implemented through manageable external changes, as a viable strategy to optimize separation performance in porous adsorbent materials.
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Purification of ethylene (C2H4) as the most extensive and output chemical, from complex multi-components is of great significance but highly challenging. Herein we demonstrate that precise pore structure tuning by controlling the network hydrogen bonds in two highly-related porous coordination networks can shift the efficient C2H4 separation function from C2H2/C2H4/C2H6 ternary mixture to CO2/C2H2/C2H4/C2H6 quaternary mixture system. Single-crystal X-ray diffraction revealed that the different amino groups on the triazolate ligands resulted in the change of the hydrogen bonding in the host network, which led to changes in the pore shape and pore chemistry. Gas adsorption isotherms, adsorption kinetics and gas-loaded crystal structure analysis indicated that the coordination network Zn-fa-atz (2) weakened the affinity for three C2 hydrocarbons synchronously including C2H4 but enhanced the CO2 adsorption due to the optimized CO2-host interaction and the faster CO2 diffusion, leading to effective C2H4 production from the CO2/C2H2/C2H4/C2H6 mixture in one step based on the experimental and simulated breakthrough data. Moreover, it can be shaped into spherical pellets with maintained porosity and separation performance.
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Separating propyne/propadiene to produce pure propadiene is extremely challenging in industry due to their similar properties. Herein, a novel ZrF6 2- anion pillared cage-like metal-organic framework (termed as CuZrF6 -TPA) for highly efficient propyne/propadiene separation is reported. It exhibits high propyne capacity (177.4/188.6 cm3 /cm3 at 0.5/1.0 bar and 298 K), benchmark separation selectivity (6.0), and remarkable separation potential (5.7 mol L-1 ) simultaneously. Record propadiene productivity (≈4.7 mol L-1 ) is achieved through a single adsorption process in breakthrough experiments with excellent recycle stability even under humid conditions. Based on the structure of propyne-loaded single crystals, two binding sites are identified, including a major propyne trapping site at the windows and a minor binding site located in the large cages. Modelling studies further confirm that the contracted cage windows surrounded with rotating Lewis basic F atoms and aromatic rings are the optimal bonding sites to capture propyne with multiple hydrogen bonding and π···π interactions.
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Recently, examples of metal-organic frameworks (MOFs) have been identified displaying ethane (C2H6) over ethylene (C2H4) adsorption selectivity. However, it remains a challenge to construct MOFs with both large C2H6 adsorption capacity and high C2H6/C2H4 adsorption selectivity, especially under humid conditions. Herein, we reported two isoreticular MOF-5 analogues (JNU-6 and JNU-6-CH3) and their potential applications in one-step separation of C2H4 from C2H6/C2H4 mixtures. The introduction of CH3 groups not only reduces the pore size from 5.4 Å in JNU-6 to 4.1 Å in JNU-6-CH3 but also renders an increased electron density on the pyrazolate N atoms of the organic linker. JNU-6-CH3 retains its framework integrity even after being immersed in water for six months. More importantly, it exhibits large C2H6 adsorption capacity (4.63 mmol g-1) and high C2H6/C2H4 adsorption selectivity (1.67) due to the optimized pore size and surface function. Breakthrough experiments on JNU-6-CH3 demonstrate that C2H4 can be directly separated from C2H6/C2H4 (50/50, v/v) mixtures, affording benchmark productivity of 22.06 and 18.71 L kg-1 of high-purity C2H4 (≥99.95%) under dry and humid conditions, respectively.
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Soft porous coordination polymers (PCPs) have the remarkable ability to recognize similar molecules as a result of their structural dynamics. However, their guest-induced gate-opening behaviors often lead to issues with selectivity and separation efficiency, as co-adsorption is nearly unavoidable. Herein, we report a strategy of a confined-rotational shutter, in which the rotation of pyridyl rings within the confined nanospace of a halogen-bonded coordination framework (NTU-88) creates a maximum aperture of 4.4â Å, which is very close to the molecular size of propyne (C3 H4 : 4.4â Å), but smaller than that of propylene (C3 H6 : 5.4â Å). This has been evidenced by crystallographic analyses and modelling calculations. The NTU-88o (open phase of activated NTU-88) demonstrates dedicated C3 H4 adsorption, and thereby leads to a sieving separation of C3 H4 /C3 H6 under ambient conditions. The integrated nature of high uptake ratio, considerable capacity, scalable synthesis, and good stability make NTU-88 a promising candidate for the feasible removal of C3 H4 from C3 H4 /C3 H6 mixtures. In principle, this strategy holds high potential for extension to soft families, making it a powerful tool for optimizing materials that can tackle challenging separations with no co-adsorption, while retaining the crucial aspect of high capacity.
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An ethynyl-modified interpenetrated MOF material with lvt topology, [Cu2(BTEB)(NMF)2]·NMF·8H2O (compound 1, H4BTEB = 4,4',4'',4'''-(benzene-1,2,4,5-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid, NMF = N-Methylformamide), was successfully synthesized by using an alkynyl-functionalized H4BTEB organic ligand under solvothermal conditions. Structural analysis shows that compound 1, consisting of a tetradentate carboxylic acid ligand and classical [Cu2(CO2)4] paddle-wheel structure building units, has a rare 4-connected lvt topology with dual interpenetrating structure, which can improve the framework stability, as well as the gas adsorption capacity and selectivity due to the restricted pore channel. According to the study of gas adsorption performance, compound 1 with a larger surface area, boasts a superior adsorption capacity for small gas molecules. Also, ideal adsorption solution theory (IAST) computational simulation shows that compound 1 has good gas adsorption selectivity for C3H8/CH4, indicating its potential application in gas separation.
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Precise ion recognition plays a key role in the anionic decontamination in water. However, the established anionic recognition based on neutral or cationic anion receptor is still restricted by the inherent limitation, such as narrow application scope in organic solvent rather than water for neutral anion receptor and poor selectivity due to non-directional electrostatic interaction for cationic anion receptor. Herein, for the first time, a neutral metal-organic framework (MOF) anion receptor is shown, enabling precise anion recognition, for example, the presence of a variety of 1000-fold competitive anions does not affect the selective adsorption of the target anion at all. A radical-dominating anion-recognition mechanism is proposed for rationalizing the efficacy of the neutral MOF.
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Removing CO2 from crude syngas via physical adsorption is an effective method to yield eligible syngas. However, the bottleneck in trapping ppm-level CO2 and improving CO purity at higher working temperatures are major challenges. Here we report a thermoresponsive metal-organic framework (1 a-apz), assembled by rigid Mg2 (dobdc) (1 a) and aminopyrazine (apz), which not only affords an ultra-high CO2 capacity (145.0/197.6â cm3 g-1 (0.01/0.1â bar) at 298â K) but also produces ultra-pure CO (purity ≥99.99 %) at a practical ambient temperature (TA ). Several characterization results, including variable-temperature tests, in situ high-resolution synchrotron X-ray diffraction (HR-SXRD), and simulations, explicitly unravel that the excellent property is attributed to the induced-fit-identification in 1 a-apz that comprises self-adaption of apz, multiple binding sites, and complementary electrostatic potential (ESP). Breakthrough tests suggest that 1 a-apz can remove CO2 from 1/99 CO2 /CO mixtures at practical 348â K, yielding 70.5â L kg-1 of CO with ultra-high purity of ≥99.99 %. The excellent separation performance is also revealed by separating crude syngas that contains quinary mixtures of H2 /N2 /CH4 /CO/CO2 (46/18.3/2.4/32.3/1, v/v/v/v/v).
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One-step harvest of high-purity light hydrocarbons without the desorption process represents an advanced and highly efficient strategy for the purification of target substances. The separation and purification of acetylene (C2H2) from carbon dioxide (CO2) by CO2-selective adsorbents are urgently demanded yet are very challenging owing to their similar physicochemical properties. Here, we employ the pore chemistry strategy to adjust the pore environment by immobilizing polar groups into an ultramicroporous metal-organic framework (MOF), achieving one-step manufacture of high-purity C2H2 from CO2/C2H2 mixtures. Embedding methyl groups into prototype stable MOF (Zn-ox-trz) not only changes the pore environment but also improves the discrimination of guest molecules. The methyl-functionalized Zn-ox-mtz thus exhibits the benchmark reverse CO2/C2H2 uptake ratio of 12.6 (123.32/9.79 cm3 cm-3) and an exceptionally high equimolar CO2/C2H2 selectivity of 1064.9 at ambient conditions. Molecular simulations reveal that the synergetic effect of pore confinement and surfaces decorated with methyl groups provides high recognition of CO2 molecules through multiple van der Waals interactions. The column breakthrough experiments suggest that Zn-ox-mtz dramatically achieved the one-step purification capacity of C2H2 from the CO2/C2H2 mixture with a record C2H2 productivity of 2091 mmol kg-1, surpassing all of the CO2-selective adsorbents reported so far. In addition, Zn-ox-mtz exhibits excellent chemical stability under different pH values of aqueous solutions (pH = 1-12). Moreover, the highly stable framework and excellent inverse selective CO2/C2H2 separation performance showcase its promising application as a C2H2 splitter for industrial manufacture. This work paves the way to developing reverse-selective adsorbents for the challenging gas separation process.
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Ultramicroporous materials can be highly effective at trace gas separations when they offer a high density of selective binding sites. Herein, we report that sql-NbOFFIVE-bpe-Cu, a new variant of a previously reported ultramicroporous square lattice, sql, topology material, sql-SIFSIX-bpe-Zn, can exist in two polymorphs. These polymorphs, sql-NbOFFIVE-bpe-Cu-AA (AA) and sql-NbOFFIVE-bpe-Cu-AB (AB), exhibit AAAA and ABAB packing of the sql layers, respectively. Whereas NbOFFIVE-bpe-Cu-AA (AA) is isostructural with sql-SIFSIX-bpe-Zn, each exhibiting intrinsic 1D channels, sql-NbOFFIVE-bpe-Cu-AB (AB) has two types of channels, the intrinsic channels and extrinsic channels between the sql networks. Gas and temperature induced transformations of the two polymorphs of sql-NbOFFIVE-bpe-Cu were investigated by pure gas sorption, single-crystal X-ray diffraction (SCXRD), variable temperature powder X-ray diffraction (VT-PXRD), and synchrotron PXRD. We observed that the extrinsic pore structure of AB resulted in properties with potential for selective C3H4/C3H6 separation. Subsequent dynamic gas breakthrough measurements revealed exceptional experimental C3H4/C3H6 selectivity (270) and a new benchmark for productivity (118 mmol g-1) of polymer grade C3H6 (purity >99.99%) from a 1:99 C3H4/C3H6 mixture. Structural analysis, gas sorption studies, and gas adsorption kinetics enabled us to determine that a binding "sweet spot" for C3H4 in the extrinsic pores is behind the benchmark separation performance. Density-functional theory (DFT) calculations and Canonical Monte Carlo (CMC) simulations provided further insight into the binding sites of C3H4 and C3H6 molecules within these two hybrid ultramicroporous materials, HUMs. These results highlight, to our knowledge for the first time, how pore engineering through the study of packing polymorphism in layered materials can dramatically change the separation performance of a physisorbent.
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The achievement of direct C2H4 separation from C2 hydrocarbons is very challenging in the petrochemical industry due to their similar molecular sizes, boiling points, and physicochemical properties. In this work, a nonpolar/inert ultramicroporous metal-organic framework (MOF), [Co3(µ3-OH)(tipa)(bpy)1.5]·3DMF·6H2O (1), with stand-alone one-dimensional square tubular channels was successfully constructed, its pore enriched with plenty of aromatic rings causing nonpolar/inert pore surfaces. The MOF shows preferential adsorption of C2H6 compared to C2H4 and C2H2 in the low-pressure region, which is further verified by adsorption heats and selectivities. The C2H4 separation potential in one step for binary C2H6/C2H4 (50/50 and 10/90) and ternary C2H4/C2H6/C2H2 (89/10/1) is also examined by transient breakthrough simulations. Moreover, grand canonical Monte Carlo simulations demonstrate that the unique reversed adsorption mechanism is due to the shortest and most number of C-H···π interactions between C2H6 and the framework.
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Hydrogen-bonded organic frameworks (HOFs) show great potential in energy-saving C2 H6 /C2 H4 separation, but there are few examples of one-step acquisition of C2 H4 from C2 H6 /C2 H4 because it is still difficult to achieve the reverse-order adsorption of C2 H6 and C2 H4 . In this work, we boost the C2 H6 /C2 H4 separation performance in two graphene-sheet-like HOFs by tuning pore polarization. Upon heating, an in situ solid phase transformation can be observed from HOF-NBDA(DMA) (DMA=dimethylamine cation) to HOF-NBDA, accompanied with transformation of the electronegative skeleton into neutral one. As a result, the pore surface of HOF-NBDA has become nonpolar, which is beneficial to selectively adsorbing C2 H6 . The difference in the capacities for C2 H6 and C2 H4 is 23.4â cm3 g-1 for HOF-NBDA, and the C2 H6 /C2 H4 uptake ratio is 136 %, which are much higher than those for HOF-NBDA(DMA) (5.0â cm3 g-1 and 108 % respectively). Practical breakthrough experiments demonstrate HOF-NBDA could produce polymer-grade C2 H4 from C2 H6 /C2 H4 (1/99, v/v) mixture with a high productivity of 29.2â L kg-1 at 298â K, which is about five times as high as HOF-NBDA(DMA) (5.4â L kg-1 ). In addition, in situ breakthrough experiments and theoretical calculations indicate the pore surface of HOF-NBDA is beneficial to preferentially capture C2 H6 and thus boosts selective separation of C2 H6 /C2 H4 .
Asunto(s)
Etano , Etilenos , Adsorción , HidrógenoRESUMEN
Engineering pore environments exhibit great potential in improving gas adsorption and separation performances but require specific means for acetylene/carbon dioxide (C2 H2 /CO2 ) separation due to their identical dynamic diameters and similar properties. Herein, a novel sulfate-pillared MOF adsorbent (SOFOUR-TEPE-Zn) using 1,1,2,2-tetra(pyridin-4-yl) ethene (TEPE) ligand with dense electronegative pore surfaces is reported. Compared to the prototype SOFOUR-1-Zn, SOFOUR-TEPE-Zn exhibits a higher C2 H2 uptake (89.1 cm3 g-1 ), meanwhile the CO2 uptake reduces to 14.1 cm3 g-1 , only 17.4% of that on SOFOUR-1-Zn (81.0 cm3 g-1 ). The high affinity toward C2 H2 than CO2 is demonstrated by the benchmark C2 H2 /CO2 selectivity (16 833). Furthermore, dynamic breakthrough experiments confirm its application feasibility and good cyclability at various flow rates. During the desorption cycle, 60.1 cm3 g-1 C2 H2 of 99.5% purity or 33.2 cm3 g-1 C2 H2 of 99.99% purity can be recovered by stepped purging and mild heating. The simulated pressure swing adsorption processes reveal that 75.5 cm3 g-1 C2 H2 of 99.5+% purity with a high gas recovery of 99.82% can be produced in a counter-current blowdown process. Modeling studies disclose four favorable adsorption sites and dense packing for C2 H2 .
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Propyne/propylene (C3H4/C3H6) separation is an important industrial process yet challenged by the trade-off of selectivity and capacity due to the molecular similarity. Herein, record C3H4/C3H6 separation performance is achieved by fine tuning the pore structure in anion pillared MOFs. SIFSIX-Cu-TPA (ZNU-2-Si) displays a benchmark C3H4 capacity (106/188 cm3 g-1 at 0.01/1 bar and 298 K), excellent C3H4/C3H6 IAST selectivity (14.6-19.3) and kinetic selectivity, and record high C3H4/C3H6 (10/90) separation potential (36.2 mol kg-1). The practical C3H4/C3H6 separation performance is fully demonstrated by breakthroughs under various conditions. 37.8 and 52.9 mol kg-1 of polymer grade C3H6 can be produced from 10/90 and 1/99 C3H4/C3H6 mixtures. 4.7 mol kg-1 of >99% purity C3H4 can be recovered by a stepped desorption process. Based on the in situ single crystal analysis and DFT calculation, an unprecedented entropy-enthalpy balanced adsorption pathway is discovered. MD simulation further confirmed the thermodynamic-kinetic synergistic separation of C3H4/C3H6 in ZNU-2-Si.
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Ethylene (C2H4) purification from multi-component mixtures by physical adsorption is a great challenge in the chemical industry. Herein, we report a GeF62- anion embedded MOF (ZNU-6) with customized pore structure and pore chemistry for benchmark one-step C2H4 recovery from C2H2 and CO2. ZNU-6 exhibits significantly high C2H2 (1.53 mmol/g) and CO2 (1.46 mmol/g) capacity at 0.01 bar. Record high C2H4 productivity is achieved from C2H2/CO2/C2H4 mixtures in a single adsorption process under various conditions. The separation performance is retained over multiple cycles and under humid conditions. The potential gas binding sites are investigated by density functional theory (DFT) calculations, which suggest that C2H2 and CO2 are preferably adsorbed in the interlaced narrow channel with high aff0inity. In-situ single crystal structures with the dose of C2H2, CO2 or C2H4 further reveal the realistic host-guest interactions. Notably, rare C2H2 clusters are formed in the narrow channel while two distinct CO2 adsorption locations are observed in the narrow channel and the large cavity with a ratio of 1:2, which accurately account for the distinct adsorption heat curves.
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Herein, we represent a bimetallic approach to enhance the defect number, leading to eight defect sites per node in a metal-organic framework, showing both a higher SO2 adsorption capacity and higher SO2/CO2 selectivity. The results can be further strongly supported by density functional theory calculations.