Pore Engineering Research Articles

A Grafting Hydrogen‐bonded Organic Framework for Benchmark Selectivity of C2H2/CO2 Separation under Ambient Conditions

AbstractReticular chemistry and pore engineering have garnered significant advancements in metal–organic frameworks and covalent organic frameworks, leveraging robust metal‐coordination and covalent bonds. However, these achievements remain elusive in hydrogen‐bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen‐bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF‐FJU‐99 and HOF‐FJU‐100, with distinct pore environments. Remarkably, HOF‐FJU‐100, with its microporous architecture, not only showcases exceptional stability but also achieves unparalleled separation efficiency and ultrahigh selectivity for C2H2/CO2 mixtures (50/50, v/v) under ambient conditions. Its IAST selectivity value of 201 stands as a benchmark, towering over all previously reported HOFs. The pore of HOF‐FJU‐100 boasts an electrostatic potential highly favourable for C2H2 adsorption, as evidenced by single crystal X‐ray diffraction analysis revealing multiple hydrogen bonding interactions between C2H2 molecules and the framework. In situ gas‐carrier powder X‐ray diffraction analysis underscores the adaptability of pore structure, dynamically adjusting its orientation in response to C2H2, thereby enabling a highly efficient and specific separation of C2H2/CO2 mixtures through specific adsorptive interactions.

Water Sorption on Isoreticular CPO-27-Type MOFs: From Discrete Sorption Sites to Water-Bridge-Mediated Pore Condensation

Pore engineering is commonly used to alter the properties of metal–organic frameworks. This is achieved by incorporating different linker molecules (L) into the structure, generating isoreticular frameworks. CPO-27, also named MOF-74, is a prototypical material for this approach, offering the potential to modify the size of its one-dimensional pore channels and the hydrophobicity of pore walls using various linker ligands during synthesis. Thermal activation of these materials yields accessible open metal sites (i.e., under-coordinated metal centers) at the pore walls, thus acting as strong primary binding sites for guest molecules, including water. We study the effect of the pore size and linker hydrophobicity within a series of Ni2+-based isoreticular frameworks (i.e., Ni2L, L = dhtp, dhip, dondc, bpp, bpm, tpp), analyzing their water sorption behavior and the water interactions in the confined pore space. For this purpose, we apply water vapor sorption analysis and Fourier transform infrared spectroscopy. In addition, defect degrees of all compounds are determined by thermogravimetric analysis and solution 1H nuclear magnetic resonance spectroscopy. We find that larger defect degrees affect the preferential sorption sites in Ni2dhtp, while no such indication is found for the other materials in our study. Instead, strong evidence is found for the formation of water bridges/chains between coordinating water molecules, as previously observed for hydrophobic porous carbons and mesoporous silica. This suggests similar sorption energies for additional water molecules in materials with larger pore sizes after saturation of the primary binding sites, resulting in more bulk-like water arrangements. Consequently, the sorption mechanism is driven by classical pore condensation through H-bonding anchor sites instead of sorption at discrete sites.

Enhancing ethanol/water separation in UTSA-280 by a pore engineering strategy

Enhancing ethanol/water separation in UTSA-280 by a pore engineering strategy

Pore Engineering in Biomass-Derived Carbon Materials for Enhanced Energy, Catalysis, and Environmental Applications.

Biomass-derived carbon materials (BDCs) are highly regarded for their renewability, environmental friendliness, and broad potential for application. A significant advantage of these materials lies in the high degree of customization of their physical and chemical properties, especially in terms of pore structure. Pore engineering is a key strategy to enhance the performance of BDCs in critical areas, such as energy storage, catalysis, and environmental remediation. This review focuses on pore engineering, exploring the definition, classification, and adjustment techniques of pore structures, as well as how these factors affect the application performance of BDCs in energy, catalysis, and environmental remediation. Our aim is to provide a solid theoretical foundation and practical guidance for the pore engineering of BDCs to facilitate the rapid transition of these materials from the laboratory to industrial applications.

Rational Synthesis of Spongy Fe3N@N-Doped Carbon Nanorods with Controlled Topography and Porosity for Enhanced Energy Storage Anodes in Lithium-Ion Batteries.

Iron nitrides with the merits of high theoretical capacities, cost-effectiveness, and good electronic/ionic conductivity have been recognized as attractive anode candidates for lithium-ion batteries (LIBs). Carbon compositing, pore engineering, and nanostructure construction have proved to be effective strategies to prepare high-performance metal nitride anodes for LIBs. Herein, we synthesized a series of Fe3N-embedded and N-doped carbon nanorods (Fe3N@NCNR) with a hierarchical porous system and controllable topography by metal-catalyzed graphitization-nitridization of the Fe(III)-triazole framework (Fe-MOF) and thermal evaporation of the triblock copolymer F127 template assembled in Fe-MOF via hydrogen bonding interaction, followed by the air oxidation and urea-assisted ammonolysis processes. The Fe3N@NCNR as anodes for LIBs display extraordinary lithium storage capabilities with a high reversible capacity of 830 mA h g-1 at 0.1 C, a good rate performance of 576 mAh g-1 at 5 C, and a long-term cycling stability of 742 mA h g-1 over 600 cycles at 1 C. Such outstanding performance benefits from the spongy carbon nanorods with rich macropores for rapid electronic/ionic transport and effective accommodation of electrode volume expansion, abundant N-doped meso-/microporous carbon for the additional storage of Li+ via capacitive effect, and the efficient utilization of Fe3N nanoparticles uniformly distributed through carbon nanorods. Importantly, this work introduces an effective strategy to construct superior performance nitride anodes from MOF surfactants based on hydrogen bonding-driven interface self-assembly and provides insight into the preparation of highly efficient nanoarchitectures for Li+ storage.

A Grafting Hydrogen-bonded Organic Framework for Benchmark Selectivity of C2H2/CO2 Separation under Ambient Conditions.

Reticular chemistry and pore engineering have garnered significant advancements in metal-organic frameworks and covalent organic frameworks, leveraging robust metal-coordination and covalent bonds. However, these achievements remain elusive in hydrogen-bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen-bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF-FJU-99 and HOF-FJU-100, with distinct pore environments. Remarkably, HOF-FJU-100, with its microporous architecture, not only showcases exceptional stability but also achieves unparalleled separation efficiency and ultrahigh selectivity for C2H2/CO2 mixtures (50/50, v/v) under ambient conditions. Its IAST selectivity value of 201 stands as a benchmark, towering over all previously reported HOFs. The pore of HOF-FJU-100 boasts an electrostatic potential highly favourable for C2H2 adsorption, as evidenced by single crystal X-ray diffraction analysis revealing multiple hydrogen bonding interactions between C2H2 molecules and the framework. In situ gas-carrier powder X-ray diffraction analysis underscores the adaptability of pore structure, dynamically adjusting its orientation in response to C2H2, thereby enabling a highly efficient and specific separation of C2H2/CO2 mixtures through specific adsorptive interactions.

Pore Engineering of MFI Zeolite Membranes: Enhancing Water Flux and Ion Rejection Using Polyacrylamide as a Secondary Template

Pore Engineering of MFI Zeolite Membranes: Enhancing Water Flux and Ion Rejection Using Polyacrylamide as a Secondary Template

Hierarchically Ordered Pore Engineering of Carbon Supports with High-Density Edge-Type Single-Atom Sites to Boost Electrochemical CO2 Reduction.

Metal sites at the edge of the carbon matrix possess unique geometric and electronic structures, exhibiting higher intrinsic activity than in-plane sites. However, creating single-atom catalysts with high-density edge sites remains challenging. Herein, the hierarchically ordered pore engineering of metal-organic framework-based materials to construct high-density edge-type single-atomic Ni sites for electrochemical CO2 reduction reaction (CO2RR) is reported. The created ordered macroporous structure can expose enriched edges, further increased by hollowing the pore walls, which overcomes the low edge percentage in the traditional microporous substrates. The prepared single-atomic Ni sites on the ordered macroporous carbon with ultra-thin hollow walls (Ni/H-OMC) exhibit Faraday efficiencies of CO above 90% in an ultra-wide potential window of 600mV and a turnover frequency of 3.4×104h-1, much superior than that of the microporous material with dominant plane-type sites. Theory calculations reveal that NiN4 sites at the edges have a significantly disrupted charge distribution, forming electron-rich Ni centers with enhanced adsorption ability with *COOH, thereby boosting CO2RR efficiency. Furthermore, a Zn-CO2 battery using the Ni/H-OMC cathode shows an unprecedentedly high power density of 15.9mW cm-2 and maintains an exceptionally stable charge-discharge performance over 100h.

Post-crosslinking knitting strategy for triazine-functionalized ionic hypercrosslinked polymers: Enhanced CO2 adsorption and conversion

Pore engineering has gained significant recognition as a pivotal strategy to tailor the structure and functionality of porous materials. In this study, a post-crosslinking knitting strategy was employed to fabricate a series of triazine-functionalized ionic hypercrosslinked polymers (IHCPs) using low specific surface area ionic polymers as precursors and external crosslinkers α,α′-dichloro-p-xylene (DCX) and α,α′-dibromo-p-xylene (DBX) through the Friedel Crafts alkylation reaction. This post-crosslinking knitting methodology increases the specific surface area of the resulting IHCPs, leading to enhanced CO2 adsorption capabilities (reaching 1.92 mmol·g−1 at 1 bar and 273 K), enhanced a remarkable 5.6-fold increase in CO2 uptake compared to the original ionic polymers. Of particular interest, inclusion of –NH– groups in PTA-2-DBX exhibits a synergistic catalytic effect facilitated by hydrogen bonding interactions that enable efficient conversion of CO2 into various cyclic carbonates under solvent- and cocatalyst-free conditions with yields exceeding 99 %. Furthermore, PTA-2-DBX demonstrates excellent recyclability while maintaining its activity even after five consecutive cycles. This study offers an effective approach for modulating pores in ionic polymers while highlighting the promising applications of triazine-functionalized IHCPs as dual-functional materials for both CO2 capture and conversion.

Aromatic pore engineering in microporous metal–organic frameworks for high-production one-step methane purification from ternary alkanes mixtures

The exploitation of competent isolation and purification technology of methane (CH4) is an imperative and challenging task for full utilization of clean natural gas in petrochemical industry. Compared to traditional energy-intensive low-temperature distillation, adsorptive separation using porous metal–organic framework (MOF) materials provides an alternative technique with low energy consumption and high efficiency. In this situation, an aromatic pore engineering strategy in a series of pillar-layered Zn-based MOFs by introducing organic linkers with different degrees of aromatic units was investigated to tune pore size and pore environment for simultaneously removing propane (C3H8) and ethane (C2H6) from C3H8/C2H6/CH4 mixtures. Compared to the other two analogues, i.e. Zn(BDC)(TED)0.5 and Zn(ADC)(TED)0.5, obtained Zn(NDC)(TED)0.5 showed high adsorption capacity for C3H8 (5.18 mmol/g) and C2H6 (5.04 mmol/g) and selectivity for C3H8/CH4 and C2H6/CH4 at 298 K and 1.0 bar. Breakthrough tests proved the three MOFs can effectively separate ternary C3H8/C2H6/CH4 mixtures, and Zn(NDC)(TED)0.5 especially exhibited excellent high-purity CH4 yield of 10.07 mmol/g. Computational simulations showed that suitable pore space and surface aromatic environment in Zn(NDC)(TED)0.5 created beneficial interactions with C3H8 and C2H6 molecules, which ultimately contributed to its favourable adsorption and separation property. This system work provides insights for the development of pore control method in MOF materials for natural gas purification.

Pore Engineering as a General Strategy to Improve Protein-Based Enzyme Nanoreactor Performance.

Enzyme nanoreactors are nanoscale compartments consisting of encapsulated enzymes and a selectively permeable barrier. Sequestration and colocalization of enzymes can increase catalytic activity, stability, and longevity, highly desirable features for many biotechnological and biomedical applications of enzyme catalysts. One promising strategy to construct enzyme nanoreactors is to repurpose protein nanocages found in nature. However, protein-based enzyme nanoreactors often exhibit decreased catalytic activity, partially caused by a mismatch of protein shell selectivity and the substrate requirements of encapsulated enzymes. No broadly applicable and modular protein-based nanoreactor platform is currently available. Here, we introduce a pore-engineered universal enzyme nanoreactor platform based on encapsulins-microbial self-assembling protein nanocompartments with programmable and selective enzyme packaging capabilities. We structurally characterize our protein shell designs via cryo-electron microscopy and highlight their polymorphic nature. Through fluorescence polarization assays, we show their improved molecular flux behavior and highlight their expanded substrate range via a number of proof-of-concept enzyme nanoreactor designs. This work lays the foundation for utilizing our encapsulin-based nanoreactor platform for diverse future biotechnological and biomedical applications.

Construction of negative electrostatic sugared gourd pore within nickel-based metal-organic framework for one-step purification acetylene from ethylene and carbon dioxide mixture

The development of highly efficient adsorbents for purifying acetylene from multi-component mixtures is crucial in the chemical industry, yet the tradeoff between renewability and selectivity severely constrains practical industrial applications. This study introduces sugar gourd pore framework (SGPF-1), an innovative ultra-microporous framework synthesized using 1,2-di(4-pyridyl)ethylene (BPE), 4,4′,4′’-nitrilotribenzoic acid (NTA), and hexanitronickel under solvothermal conditions. The X-ray diffraction analysis has been used to prove the detailed structure and phase purity of SGPF-1. The structure of SGPF-1 was tailored for selectively adsorbing and separating the target compound, C2H2. The negative electrostatic effect, inspired by the natural sugared gourd structure, enhances the selectivity and adsorption capacity for C2H2, while minimizing the interaction with impurities like C2H4 and CO2. Experimental data show that SGPF-1 exhibits significantly higher adsorption of C2H2 compared to C2H4 and CO2 at 298 K and 100 kPa, demonstrating exceptional selectivity towards 50/50 C2H2/CO2 and 1/99 C2H2/C2H4 to be 7.33 and 15.46. Breakthrough experiments confirm its effectiveness in separating C2H2 from C2H4/CO2 mixtures, with C2H4 saturation reached within 5 to 15 min, while C2H2 retention time at 298 K was as long as 26 min. Theoretical calculations have revealed that SGPF-1 exhibits electrostatic compatibility with C2H2 while repelling C2H4 and CO2 through an electrostatic exclusion mechanism. This highlights the importance of rational pore engineering in optimizing the electrostatic properties of adsorbents for high-efficiency multi-component separations. The research aims to advance gas separation technologies and improve the purity of acetylene, a valuable industrial raw material.

Pore engineering of Porous Materials: Effects and Applications.

Porous materials, characterized by their controllable pore size, high specific surface area, and controlled space functionality, have become cross-scale structures with microenvironment effects and multiple functions and have gained tremendous attention in the fields of catalysis, energy storage, and biomedicine. They have evolved from initial nanopores to multiscale pore-cavity designs with yolk-shell, multishells, or asymmetric structures, such as bottle-shaped, multichambered, and branching architectures. Various synthesis strategies have been developed for the interfacial engineering of porous structures, including bottom-up approaches by using liquid-liquid or liquid-solid interfaces "templating" and top-down approaches toward chemical tailoring of polymers with different cross-linking degrees, as well as interface transformation using the Oswald ripening, Kirkendall effect, or atomic diffusion and rearrangement methods. These techniques permit the design of functional porous materials with diverse microenvironment effects, such as the pore size effect, pore enrichment effect, pore isolation and synergistic effect, and pore local field enhancement effect, for enhanced applications. In this review, we delve into the bottom-up and top-down interfacial-oriented synthesis approaches of porous structures with advanced structures and microenvironment effects. We also discuss the recent progress in the applications of these collaborative effects and structure-activity relationships in the areas of catalysis, energy storage, electrochemical conversion, and biomedicine. Finally, we outline the persisting obstacles and prospective avenues in terms of controlled synthesis and functionalization of porous engineering. The perspectives proposed in this paper may contribute to promote wider applications in various interdisciplinary fields within the confined dimensions of porous structures.

Pore engineering in highly stable hydrogen-bonded organic frameworks for efficient CH4 purification

The unsatisfactory stability of hydrogen-bonded organic frameworks (HOFs) arising from the weakness and flexibility of hydrogen-bonding (H-bonding) has generally hindered their practical applications. By synergistically employing three key strategies: (Ⅰ) introducing charge-assisted H-bonding to increase the polarity of the framework, (Ⅱ) optimizing the length of the building unit by extending the core structure of the linker molecule, and (III) incorporating functional sites containing methoxy and trifluoromethyl, to increase the stability of HOFs and the adsorption affinity for gas molecules, we successfully synthesized three charge-assisted hydrogen-bonded HOFs (NKM-HOF-3, NKM-HOF-4, and NKM-HOF-5; NKM = Nankai Materials). These HOFs exhibit distinct space configurations of nonporous packing, discrete cavities or continuous one-dimensional channels. Notably, NKM-HOF-5 exhibits commendable thermal and chemical stability and can be readily regenerated by re-solvothermal reaction. The activated NKM-HOF-5a exhibits a low affinity for CH4 but captures C2H6 and C3H8 with a relatively high affinity. According to theoretical calculations, the suitable pore size, together with functionalized and polarized surface environments in NKM-HOF-5a contribute to the excellent selective gas adsorption performance of NKM-HOF-5a. Furthermore, the dynamic breakthrough experiments demonstrate the highly efficient separation performance of NKM-HOF-5a for C2H6/CH4, C3H8/CH4, and C3H8/C2H6/CH4.

Precise Pore Engineering of Zirconium Metal‐Organic Cages for One‐Step Ethylene Purification from Ternary Mixtures

AbstractOne‐step purification of ethylene from ternary mixtures (C2H2, C2H4, and C2H6) can greatly reduce the energy consumption of the separation process, but it is extremely challenging. Herein, we use crystal engineering and reticular chemistry to introduce unsaturated bonds (ethynyl and alkyne) into ligands, and successfully design and synthesized two novel Zr‐MOCs (ZrT‐1‐ethenyl and ZrT‐1‐alkyne). The introduction of carbon‐carbon unsaturated bonds provides abundant adsorption sites within the framework while modulating the pore window size. Comprehensive characterization techniques including single crystal and powder X‐ray diffraction, as well as electrospray ionization time‐of‐flight mass spectrometry (ESI‐TOF‐MS) confirm that ZrT‐1‐ethenyl and ZrT‐1‐alkyne possess an isostructural framework with ZrT‐1 and ZrT‐1‐Me, respectively. Adsorption isotherms and breakthrough experiments combined with theoretical calculations demonstrate that ZrT‐1‐ethenyl can effectively remove trace C2H2 and C2H6 in C2H4 and achieve separation of C2H2 from C2H4 and CO2. ZrT‐1‐ethenyl can also directly purify C2H4 in liquid solutions. This work provides a benchmark for MOCs that one‐step purification of ethylene from ternary mixtures.

Precise Pore Engineering of Zirconium Metal-Organic Cages for One-Step Ethylene Purification from Ternary Mixtures.

One-step purification of ethylene from ternary mixtures (C2H2, C2H4, and C2H6) can greatly reduce the energy consumption of the separation process, but it is extremely challenging. Herein, we use crystal engineering and reticular chemistry to introduce unsaturated bonds (ethynyl and alkyne) into ligands, and successfully design and synthesized two novel Zr-MOCs (ZrT-1-ethenyl and ZrT-1-alkyne). The introduction of carbon-carbon unsaturated bonds provides abundant adsorption sites within the framework while modulating the pore window size. Comprehensive characterization techniques including single crystal and powder X-ray diffraction, as well as electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) confirm that ZrT-1-ethenyl and ZrT-1-alkyne possess an isostructural framework with ZrT-1 and ZrT-1-Me, respectively. Adsorption isotherms and breakthrough experiments combined with theoretical calculations demonstrate that ZrT-1-ethenyl can effectively remove trace C2H2 and C2H6 in C2H4 and achieve separation of C2H2 from C2H4 and CO2. ZrT-1-ethenyl can also directly purify C2H4 in liquid solutions. This work provides a benchmark for MOCs that one-step purification of ethylene from ternary mixtures.

Pore Environmental Modification by Amino Groups in Robust Microporous MOFs for SF6 Capturing and SF6/N2 Separation.

Capturing and separating the greenhouse gas SF6 from nitrogen N2 have significant greenhouse mitigation potential and economic benefits. We used a pore engineering strategy to manipulate the pore environment of the metal-organic framework (MOF) by incorporating organic functional groups (-NH2). This resulted in an enhanced adsorption of SF6 and separation of the SF6/N2 mixture in the MOF. The introduction of amino (-NH2) groups into YTU-29 resulted in a reduction of the Brunauer-Emmett-Teller surface but an increase in interactions with SF6 within the confined pores. Water-stable YTU-29-NH2 showed a significantly higher SF6 uptake (95.5 cm3/g) than YTU-29 (77.4 cm3/g). The results of the breakthrough experiments show that YTU-29-NH2 has a significantly improved separation performance for SF6/N2 mixtures, with a high SF6 capture of 0.88 mmol/g compared to 0.56 mmol/g by YTU-29. This improvement is due to the suitable pore confinement and accessible -NH2 groups on pore surfaces. Considering its excellent regeneration ability and cycling performance, ultrastable YTU-29-NH2 demonstrates great potential for SF6 capturing and SF6/N2 separation.

Chitosan-based high-performance flexible supercapacitor via “in-situ co-doping/self-regulation-activation” strategy

The construction of N, P co-doped hierarchically porous carbons (NPHPC) by a facile and green approach is crucial for high-performance energy storage but still an enormous challenge. Herein, an environment-friendly “in-situ co-doping, self-regulation-activation” strategy is presented to one-pot synthesize NPHPC using a phytic acid-induced polyethyleneimine/chitosan gel (PEI-PA-CS) as single precursor. NPHPC displayed a specific surface area of up to 1494 m2 g−1, high specific capacitance of 449 F g−1 at 1 A g−1, outstanding rate capability and cycling durability in a wide temperature range (−20 to 60 °C). NPHPC and PEI-PA-CS electrolyte assembled symmetric quasi-solid-state flexible supercapacitor presents superb energy outputs of 27.06 Wh kg−1 at power density of 225 W kg−1. For capacitive deionization (CDI), NPHPC also exhibit an excellent salt adsorption capacity of 16.54 mg g−1 in 500 mg L−1 NaCl solution at a voltage of 1.4 V, and regeneration performance. This study provides a valuable reference for the rational design and synthesis of novel biomass-derived energy-storage materials by integrating phytic acid induced heteroatom doping and pore engineering.

Modulation of Water Vapor Sorption by Pore Engineering in Isostructural Square Lattice Topology Coordination Networks.

We report a crystal-engineering study conducted upon a platform of three mixed-linker square lattice (sql) coordination networks of general formula [Zn(Ria)(bphy)] [bphy = 1,2-bis(pyridin-4-yl)hydrazine, H2Ria = 5-position-substituted isophthalic acid, and R = -Br, -NO2, and -OH; compounds 1-3]. Analysis of single-crystal X-ray diffraction data of 1-2 and the simulated crystal structure of 3 revealed that 1-3 are isomorphous and sustained by bilayers of sql networks linked by hydrogen bonds. Although similar pore shapes and sizes exist in 1-3, distinct isotherm shapes (linear and S shape) and uptakes (2.4, 11.6, and 13.3 wt %, respectively) were observed. Ab initio calculations indicated that the distinct water sorption properties can be attributed to the R groups, which offer a range of hydrophilicity. Calculations indicated that the significantly lower experimental uptake in compound 1 can be attributed to a constricted channel. The calculated water-binding sites provide insights into how adsorbed water molecules bond to the pore walls, with the strongest interactions, water-hydroxyl hydrogen bonding, observed for 3. Overall, this study reveals how pore engineering can result in large variations in water sorption properties in an isomorphous family of rigid porous coordination networks.

Immobilization of Lewis Basic Sites into a Quasi‐Molecular‐Sieving Metal–Organic Framework for Enhanced C3H6/C3H8 Separation

AbstractControlling gas sorption through pore engineering is indispensable in molecular recognition and separation processes. The challenge lies in developing high‐efficiency adsorbents for C3H6/C3H8 separation, specifically enhancing the affinity toward C3H6 for high selectivity while maintaining a large gas uptake to obtain high separation efficiency. Herein, this problem can be addressed by controlling host‐guest interactions using Lewis basic sites modulation. A precise steric design of channel pores using an amino group as additional interacting sites enables the synergetic increase in C3H6 adsorption while suppressing the C3H8 adsorption, resulting in a quasi‐molecular‐sieving effect. Among them, TYUT‐23 has a perfect pore size that fits minimum cross‐sectional dimensions of C3H6, affording exceptional binding affinity for the C3H6 molecule. It adsorbs a large amount of C3H6 (2.5 mmol g−1) and concurrently exhibits both remarkably high IAST selectivity (71) under ambient conditions. Equimolar C3H6/C3H8 breakthrough experiments also prove the prominent separation performance of TYUT‐23 for the production of high‐purity C3H6. The C3H6 adsorption/separation mechanism has been investigated using C3H6‐loaded single‐crystal structure analysis. This material demonstrates the potential of optimizing host‐C3H6 interactions using Lewis basic site modulation in industrial separations.