CH4 Uptake Capacity Research Articles

Extreme drought alters methane uptake but not methane sink in semi-arid steppes of Inner Mongolia

Global climate change, particularly drought, is expected to alter grassland methane (CH4) oxidation, a key natural process against atmospheric greenhouse gas accumulation, yet the extent of this effect and its interaction with future atmospheric CH4 concentrations increases remains uncertain. To address this research gap, we measured CH4 flux during an imposed three-month rain-free period corresponding to a 100-year recurrence drought in soil mesocosms collected from 16 different Eurasian steppe sites. We also investigated the abundance and composition of methanotrophs. Additionally, we conducted a laboratory experiment to explore the impact of elevated CH4 concentration on the CH4 uptake capacity of grassland soil under drought conditions. We found that regardless of the type of grassland, CH4 flux was still being absorbed at its peak, meaning that all grasslands functioned as persistent CH4 sinks even when the soil water content (SWC) was <5 %. A bell-shaped relationship between SWC and CH4 uptake was observed in the soils. The average maximum CH4 oxidation rate in the meadow steppe was higher than that in the typical and desert steppe soils during extreme drought. The experimental elevation of atmospheric CH4 concentration counteracted the anticipated reduction in CH4 uptake related to physiological water stress on methanotrophic soil microbes under the drought stress. On the contrary, we found that across the regional scale, nitrogen, phosphorous, and total soil organic content played a crucial role in moderating the duration and magnitude of CH4 uptake with respect to SWC. USC-γ (Upland Soil Cluster γ) and JR-3 (Jasper Ridge Cluster) were the dominant group of soil methanotrophic bacteria in three types of grassland. However, the methanotrophic abundance, rather than the methanotrophic community composition, was the dominant microbiological factor governing CH4 uptake during the drought.

Stepwise Synthesis of Cl-Decorated Trinuclear-Cu Cluster-Based Frameworks for C2H2/C2H4 and C2H2/CO2 Separation.

A novel Cl-decorated trinuclear-Cu cluster-based MOF (NbU-7-Cl, NbU denotes Ningbo University) was synthesized by a stepwise synthesis strategy. Compared to one-step reactions, the strategy of combining cationic templates with single-crystal-to-single-crystal transformation provides more possibilities for the design and postsynthetic modification of multifunctional materials. Note that the chloride ions are attached to the copper ions of the planar trinuclear cluster nodes in a fully symmetric or partially asymmetric manner. The insertion of the chloride ion can alter the overall symmetry and adsorption energy in addition to occupying the appropriate asymmetric orbit and reducing the effective active sites of metal. The activated NbU-7-Cl displays improved C2H2 uptake capacity and C2H2/C2H4 and C2H2/CO2 separation performance, which is proved by breakthrough experiments.

Dual polarization strategy to enhance CH4 uptake in covalent organic frameworks for coal-bed methane purification

The purification of low-grade coal-bed methane is extremely important, but challenging, due to the very similar physical properties of CH4 and N2. Herein, we proposed a dual polarization strategy by employing triazine and polyfluoride sites to construct polar pores in COF materials, achieving the efficient separation of CH4 from N2. As expected, the dual polarized F-CTF-1 and F-CTF-2 exhibit higher CH4 adsorption capacity and CH4/N2 selectivity than CTF-1 and CTF-2, respectively. Especially, the CH4 uptake capacity and CH4/N2 selectivity of F-CTF-2 is 1.76 and 1.42 times than that of CTF-2. This work not only developed promising COF materials for CH4/N2 separation, but also provided important guidance for the separation of other adsorbates with similar properties.

Engineered cellulose-based porous carbon adsorbents for superior gas adsorption and selective separation of CH4/H2 and CH4/N2

Adsorption and separation of methane from turquoise hydrogen and coalbed methane is becoming an important method for using unconventional natural gas. Adsorbent performance determines this technique. In this regard, the cellulose-based (Cell-PC) adsorbents were engineered by a facile process with a one-pot calcination method without solvent and an activating reagent-free like KOH with an economical and green approach for CH4/H2 and CH4/N2 separation. The series of adsorbents were synthesized, such as Cell-100, U-Cell-111, O-Cell-111, O-Cell-112, O-Cell-113, and O-Cell-113-a, from cellulose with urea/oxalic acid and sodium hydrogen carbonate, which helps to create pore structure. All adsorbents were characterized by several techniques, including XRD, SEM, XPS, and BET. All Cell-PC adsorbents were used to systematically investigate adsorption studies for CH4, N2, and H2. The O-Cell-113-a adsorbent demonstrated a superior CH4 uptake capacity of 52.75 cm3/g at 273 K and 37.92 cm3/g at 298 K under 100 kPa. It was attributed to the synergistic role of high surface area, mesopore volume, micropore volume, morphology, and surface functional group. However, the O-Cell-113-a showed lower adsorption for N2 and was unable to adsorb H2 at 298 K, indicating the adsorbent has selective adsorption properties for CH4. Furthermore, the ideal adsorbed solution theory (IAST) model was used to calculate the selectivity of CH4/N2, which was found to be around 13.78 at 273 K and 12.64 at 298 K, which is higher than most previously reported porous carbon. The isosteric heat of adsorption of O-Cell-113-a adsorbent was further calculated for CH4 and N2.

T-type capture site within highly stable bicarbazole-based metal–organic framework for C2H2 purification from CO2 and CH4

It is challenging to achieve high-purity acetylene (C2H2) from the methylene (CH4) and carbon dioxide (CO2), due to their similar molecular structure and physical properties. Adsorption utilized porous materials, such as metal–organic frameworks (MOFs), has been considered as cost- and energy-efficient technology to separate acetylene mixtures. Herein, we reported a highly stable MOF, [Zn6L4(Me2NH2+)4‧3H2O] (named FJU-83), featuring T-shaped functional capture sites explored for acetylene capture and separation. In addition, FJU-83a exhibits not only a high C2H2 uptake capacity of 122.9 cm3/g at 273 K, 1 bar, but also good C2H2/CH4 and C2H2/CO2 selectivity of 24 and 2.9 under moderate temperature and 1 bar, respectively. The high separation efficiency of the C2H2/CH4 and C2H2/CO2 are validated by dynamic fixed bed breakthrough experiments. The single crystal X-ray diffraction studies and Hirshfeld surface analysis revealed that T-type aromatic sites of FJU-83a can separate C2H2 from CH4 and CO2 through multiple C-H∙∙∙π and π∙∙∙π interactions.

High-capacity dynamic exclusion for highly efficient dilute C2H2 separation from CO2 and multicomponent mixture in robust ultramicroporous MOF by topology regulation

Acquiring high C2H2 adsorption capacity and effectively separating it from the most difficult-to-separate byproduct CO2 in a dilute state are crucial for obtaining high productivity/purity monomer for polymers. Here, we address this challenge through topology regulation of fluorinated ultramicroporous metal–organic framework, producing a new hydrolytically stable adsorbent, ZUL-500. Uncovered by X-ray diffraction and modeling, a more favorable spatial distribution of GeF62- anions for C2H2 recognition is realized in sql topological ZUL-500 compare to ZU-32 with the same anion and metal node but pcu topology, offering remarkably increased C2H2 affinity and amplified C2H2/CO2 affinity difference that affords a dynamic exclusion of CO2 but excellent C2H2 adsorption in fixed-bed separation even for industrial-related mixtures (up to 8 components). Excellent values were simultaneously obtained for C2H2 uptake capacity, C2H2/CO2 separation factor and C2H2 productivity, coupled with good mass transfer and recyclability, providing exceptional productivity (2.92 ∼ 3.48 mmol g−1) of high purity (≥99.6%) C2H2 from mixtures.

Sequential Modification Strategy to Construct Crystalline Benzimidazole Covalent Organic Frameworks with Extraordinary Stability and Polymerization Degree

The intriguing proton-conducting and catalytic properties of benzimidazole-functionalized covalent organic frameworks (BIM-COFs) largely depend on their material quality. Here, we report a novel sequential modification (SM) strategy that enables the preparation of extraordinarily stable BIM-COFs with high polymerization degree. As a “proof of principle”, the designed TpBD-BIMSM was successfully synthesized using the SM strategy, which exhibited superior chemical stability (slight structural change after treatment in 6 M HCl or 6 M NaOH). Compared with the counterpart produced by the conventional direct condensation approach (TpBD-BIMDC), TpBD-BIMSM exhibited a higher Brunauer–Emmett–Teller (BET) surface area (213 m2 g–1 vs 52 m2 g–1) and significantly enhanced CO2, CH4, C2H6, and C2H4 uptake capacities. Furthermore, the proton conductivity of TpBD-BIMSM was measured to be 1.2 × 10–2 S cm–1, which is 2 orders of magnitude higher than that of TpBD-BIMDC (7.2 × 10–4 S cm–1) under identical conditions (80 °C and 98% RH) and also ranks it among the highest in all COF-based proton conductors. In addition, TpBD-BIMSM showed a lower activation energy (Ea) value than TpBD-BIMDC (0.16 eV vs 0.20 eV). Such high proton conductivity and low Ea value of TpBD-BIMSM can be attributed to its large surface area and high polymerization degree, which could provide extra proton transfer paths and accelerate proton movement. Furthermore, such a strategy can be readily extended to construct other BIM-COFs (TpOMe-BIMSM) that thus highlights the generality of sequential modification strategy. And this strategy thus paves a new way for constructing stable and highly polymerized BIM-COFs for related applications.

Construction of new multi-cage-based MOFs using flexible triangular ligands for efficient gas adsorption and separation

Designing efficient absorbents for multi-gas adsorption and separation is of critical significance for gas purification in chemical engineering. Multi-cage structure enables sufficient interactions with multi-gas through the restriction effects, which is promising to achieve high multi-gas separation performance. In this work, two isomorphic metal-organic frameworks (MOFs) (SNNU-275, M ​= ​Cu, and SNNU-276, M ​= ​Ni) with three types of cages (octahedral M6L4, cuboctahedral M12L8, and M12L24), which are (3,4)-linked three-dimensional microporous structures formed by stacking M6(TPA)4 octahedral coordination molecular cages are synthesized by using tri(4-pyridyl) amine (TPA) ligands and Cu/Ni metals. TPA is selected as the central ligand due to the small size and flexible characteristics. The synthesized SNNU-275 exhibits a good combination of high C2H2/CO2 adsorption selectivity (28), while high C2H2 uptake capacity (68 ​cm3 ​g−1) is achieved for SNNU-276 with high stability. In addition, SNNU-275 and SNNU-276 exhibited superior uptake capacity for benzene and water vapor. Overall, this work not only provides new triangular tripyridine-based MOFs with multiple cages for efficient gas purification, but also demonstrated that the multicage engineering is a promising strategy for the multicomponent gas separation.

Concurrent Enhancement of Acetylene Uptake Capacity and Selectivity by Progressive Core Expansion and Extra-Framework Anions in Pore-Space-Partitioned Metal-Organic Frameworks.

A multi-stage core-expansion method is proposed here as one component of the integrative binding-site/extender/core-expansion (BEC) strategy. The conceptual deconstruction of the partitioning ligand into three editable parts draws our focus onto progressive core expansion and allows the optimization of both acetylene uptake and selectivity. The effectiveness of this strategy is shown through a family of eight cationic pore-partitioned materials containing three different partitioning ligands and various counter anions. The optimized structure, Co3 -cpt-tph-Cl (Hcpt=4-(p-carboxyphenyl)-1,2,4-triazole, H-tph=(2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene) with the largest surface area and highest C2 H2 uptake capacity (200 cm3 /g at 298 K), also exhibits (desirably) the lowest CO2 uptake and hence the highest C2 H2 /CO2 selectivity. The successful boost in both C2 H2 capacity and IAST selectivity allows Co3 -cpt-tph-Cl to rank among the best crystalline porous materials, ionic MOFs in particular, for C2 H2 uptake and C2 H2 /CO2 experimental breakthrough separation.

De-Linker-Enabled Exceptional Volumetric Acetylene Storage Capacity and Benchmark C2H2/C2H4 and C2H2/CO2 Separations in Metal-Organic Frameworks.

An ideal adsorbent for separation requires optimizing both storage capacity and selectivity, but maximizing both or achieving a desired balance remain challenging. Herein, a de-linker strategy is proposed to address this issue for metal-organic frameworks (MOFs). Broadly speaking, the de-linker idea targets a class of materials that may be viewed as being intermediate between zeolites and MOFs. Its feasibility is shown here by a series of ultra-microporous MOFs (SNNU-98-M, M = Mn, Co, Ni, Zn). SNNU-98 exhibit high volumetric C2H2 uptake capacity under low and ambient pressures (175.3 cm3 cm-3 @ 0.1 bar, 222.9 cm3 cm-3 @ 1 bar, 298 K), as well as extraordinary selectivity (2405.7 for C2H2/C2H4, 22.7 for C2H2/CO2). Remarkably, SNNU-98-Mn can efficiently separate C2H2 from C2H2/CO2 and C2H2/C2H4 mixtures with a benchmark C2H2/C2H4 (1/99) breakthrough time of 2325 min g-1, and produce 99.9999% C2H4 with a productivity up to 64.6 mmol g-1, surpassing values of reported MOF adsorbents.

De‐Linker‐Enabled Exceptional Volumetric Acetylene Storage Capacity and Benchmark C2H2/C2H4and C2H2/CO2Separations in Metal–Organic Frameworks

AbstractAn ideal adsorbent for separation requires optimizing both storage capacity and selectivity, but maximizing both or achieving a desired balance remain challenging. Herein, a de‐linker strategy is proposed to address this issue for metal–organic frameworks (MOFs). Broadly speaking, the de‐linker idea targets a class of materials that may be viewed as being intermediate between zeolites and MOFs. Its feasibility is shown here by a series of ultra‐microporous MOFs (SNNU‐98‐M, M=Mn, Co, Ni, Zn). SNNU‐98 exhibit high volumetric C2H2uptake capacity under low and ambient pressures (175.3 cm3 cm−3@ 0.1 bar, 222.9 cm3 cm−3@ 1 bar, 298 K), as well as extraordinary selectivity (2405.7 for C2H2/C2H4, 22.7 for C2H2/CO2). Remarkably, SNNU‐98‐Mn can efficiently separate C2H2from C2H2/CO2and C2H2/C2H4mixtures with a benchmark C2H2/C2H4(1/99) breakthrough time of 2325 min g−1, and produce 99.9999 % C2H4with a productivity up to 64.6 mmol g−1, surpassing values of reported MOF adsorbents.

Efficient C2H2-selective separation in a microporous Zn(II)-based metal-organic framework via the dual-ligand strategy.

Implementing the dual-ligand strategy, a microporous Zn-based MOF 1 with nitro and amino groups was effectively produced. The activated interconnected pores of 1 exhibited high C2H2 uptake capacity and preferential adsorption behaviour for C2H2 over CO2, as identified by the experiments and simulations. This work provides a new approach for designing and synthesizing the MOFs with desired structures and properties by optimizing their pore environment via the dual-ligand strategy.

A Computational Study of the Adsorptive Separation of Methane and Hydrogen in Zeolite Templated Carbons

Combustion of conventional energy sources produces pollutants such as SOx, NOx, and CO; the use of hydrogen and methane can eliminate these harmful emissions. In fuel cell technology and other uses, hydrogen must be refined by extracting methane from the methane/hydrogen combination, produced via dry or steam reforming. This study investigates the adsorption and separation capabilities of recently discovered zeolite-templated carbons (ZTCs) for binary mixtures consisting of hydrogen and methane. To assess the adsorption and separation performances of these carbon-based nanostructures, grand canonical Monte Carlo (GCMC) simulations were used. The simulation results revealed that AFY (|(C6H15N)3(H2O)7|[Co3Al5P8O32]) and RWY (|(C6H18N4)16| [Ga32Ge16S96]) structures could be viable alternatives for applications involving adsorptive gas separation based on selectivity and the CH4 uptake capacity. The selectivity of AFY was calculated to be 176, while its capacity to uptake CH4 was found to be 2.57 mmol/g, the selectivity of RWY was calculated to be 132, and its CH4 uptake was 3.49 mmol/g.

Computational simulation study on adsorption and separation of CH4/H2 in five higher-valency covalent organic frameworks

The density functional theory (DFT) calculation and molecular simulation were implemented to investigate the structural characteristics and the adsorption/separation properties of CH4/H2 on five borophosphonate based higher-valency covalent organic frameworks (BP-COFs). The computed results reveal that five BP-COFs possess the low density, high void fraction, suitable pore size and accessible surface area for CH4 and H2. The grand canonical Monte Carlo (GCMC) simulations indicate that the CH4 uptake capacity is higher than H2 in all five BP-COFs at 298 K and BP-COF-1 and BP-COF-4 possess the better capacity for separating CH4 form CH4/H2 mixture with low CH4 partial pressure. The centroid density distribution profiles display that the preferable sites for CH4 and H2 are both located at the corners formed by the linear ligands and the hexahedron B4P4O12 clusters. This work may provide some inspiration for further exploring higher-valency COFs as gas adsorption/separation media.

Triptycene based fluorinated polymers with improved carbon dioxide capture and hydrogen/methane storage

The use of direct arylation polymerization (DArP) as a viable strategy to obtain porous organic polymers (POPs) has not been explored to its full potential. Instead, other strategies (such as conventional cross-coupling reactions) are usually employed to yield POPs that employ expensive organometallic monomers whose syntheses require multiple steps. Herein, using DArP, three fluorinated porous organic polymers (fPOPs: TFPP1, TFPP2 and TFPP3) were obtained that represent unique examples of triptycene motif containing fluorine rich network polymers. These thermally stable polymers (Td > 400 °C with high char yields at 800 °C) are predominantly microporous with high surface areas (up to 1295 m2/g) and thus satisfy the requirement for facilitating superior adsorption of small gas molecules. The recorded CO2, CH4, and H2 uptake capacities of fPOPs are superior than several previously reported fluorinated/non-fluorinated POPs. High CO2 uptake capacities of fPOPs are due to the incorporation of ample triptycene motifs and polar C–F bonds in the polymeric backbone. Overall, the high thermal stability, surface area and sorption capacities demonstrated by these fluorinated polymers render them potential materials for the applications in capture of CO2 and storage of CH4/H2.

Regulating C2H2/CO2 adsorption selectivity by electronic-state manipulation of iron in metal-organic frameworks

The separation of C2H2 from C2H2/CO2 mixture is of great importance, yet highly challenging in the petrochemical industry due to their similar physicochemical properties. While open-metal sites (OMSs) in metal-organic frameworks (MOFs) are known to possess high affinity toward C2H2, its selective adsorption performance regulated by the electronic state of the same OMSs remains unexplored. Here, we report a metal electronic-state manipulation approach to construct a pair of isostructural Fe-MOFs, namely LIFM-26(Fe[II]/Fe[III]) and LIFM-27(Fe[III]) with different Fe[II] or Fe[III] oxidation states on the Fe centers, which display mixed-valent Fe[II]/Fe[III] centers in the former and sole Fe[III] centers in the latter. Remarkably, LIFM-26(Fe[II]/Fe[III]) shows significantly enhanced C2H2 uptake capacity than LIFM-27(Fe[III]), attested by adsorption isotherms and IAST calculations, as well as simulated and experimental breakthrough experiments. Furthermore, in situ infrared (IR) and molecular calculations unveil that the presence of Fe[II] in LIFM-26(Fe[II]/Fe[III]) results in stronger Fe[II]–C2H2 interactions than Fe[III]–C2H2, which plays a key role in the C2H2/CO2 separation.

Facile synthesis of highly moisture-resistant Mg-MOF-74 by coating hexagonal boron nitride (h-BN)

In the current research, the moisture-resistant of Mg-MOF-74 was successfully improved by coating with two-dimensional (2-D) hexagonal boron nitride (h-BN) during the facile hydrothermal synthesis process. Both TEM and SEM results revealed that 2-D h-BN is coated on Mg-MOF-74’s surface. The crystal structure, morphology, surface area, thermal stability and CH4 uptake capacity of Mg-MOF-74 were not drastically influenced by coating with h-BN as examined by XRD, FTIR, SEM, and TEM. Further, the coated Mg-MOF-74 demonstrated better stability than uncoated Mg-MOF-74, when being exposed to high humidity, in terms of surface area and CH4 uptake capacity. It was observed that the coated Mg-MOF-74 with 1 ​wt % h-BN has reached to 1959 ​m2 ​g−1 surface area and CH4 uptake capacity of 43 ​cm3 ​g−1 after exposure to high humidity for a duration of 1 month. Thus, this research work has opened a new window towards the improvement of the water stability of Mg-MOF-74.

Accelerated Discovery of CH4 Uptake Capacity Metal–Organic Frameworks Using Bayesian Optimization

AbstractHigh‐throughput computational studies for discovery of metal–organic frameworks (MOFs) for separations and storage applications are often limited by the costs of computing thermodynamic quantities. Recent such studies at the time of writing may use ab initio results for a narrow selection of MOFs or empirical force‐field methods for larger selections. Here, a proof‐of‐concept study is conducted using Bayesian optimization on CH4 uptake capacity of hypothetical MOFs for an existing dataset (Wilmer et al., Nature Chem. 2012, 4, 83). It is shown that less than 0.1% of the database needs to be screened with the Bayesian optimization approach to recover the top candidate MOFs. This opens the possibility for efficient screening of MOF databases using accurate ab initio calculations for future adsorption studies on a minimal subset of MOFs. Furthermore, Bayesian optimization and the surrogate model presented here can offer interpretable material design insights and the framework will be applicable in the context of other target properties.

Fine pore engineering in a series of isoreticular metal-organic frameworks for efficient C2H2/CO2 separation

The separation of C2H2/CO2 is not only industrially important for acetylene purification but also scientifically challenging owing to their high similarities in physical properties and molecular sizes. Ultramicroporous metal-organic frameworks (MOFs) can exhibit a pore confinement effect to differentiate gas molecules of similar size. Herein, we report the fine-tuning of pore sizes in sub-nanometer scale on a series of isoreticular MOFs that can realize highly efficient C2H2/CO2 separation. The subtle structural differences lead to remarkable adsorption performances enhancement. Among four MOF analogs, by integrating appropriate pore size and specific binding sites, [Cu(dps)2(SiF6)] (SIFSIX-dps-Cu, SIFSIX = SiF62-, dps = 4.4’-dipyridylsulfide, also termed as NCU-100) exhibits the highest C2H2 uptake capacity and C2H2/CO2 selectivity. At room temperature, the pore space of SIFSIX-dps-Cu significantly inhibits CO2 molecules but takes up a large amount of C2H2 (4.57 mmol g−1), resulting in a high IAST selectivity of 1787 for C2H2/CO2 separation. The multiple host-guest interactions for C2H2 in both inter- and intralayer cavities are further revealed by dispersion-corrected density functional theory and grand canonical Monte Carlo simulations. Dynamic breakthrough experiments show a clean C2H2/CO2 separation with a high C2H2 working capacity of 2.48 mmol g−1.

Rational regulation of acetylene adsorption and separation for ultra-microporous copper-1,2,4-triazolate frameworks by halogen hydrogen bonds.

It is well known that the introduction of exposed fluorine (F) sites into metal-organic frameworks (MOFs) can effectively promote acetylene (C2H2) adsorption via C-H⋯F hydrogen bonds. However, such super strong hydrogen bonding interactions usually lead to very high acetylene adsorption enthalpy and thus require more energy during the adsorbent regeneration process. As the same group elements, chlorine (Cl), bromine (Br) and iodine (I) also can act as hydrogen bond acceptors but with relatively weak forces. So, it is speculated that the decoration of Cl, Br or I sites on the pore surface of MOF adsorbents may enhance acetylene adsorption but with lower energy consumption. Herein, ultra-microporous MOFs constructed by Cu4X4 (X = Cl, Br, I) motifs and 1,2,4-triazolate linkers, namely, [Cu8X4(TRZ)4]n (TRZ = 3,5-diethyl-1,2,4-triazole or detrz for SNNU-313-X, and 3,5-dipropyl-1,2,4-triazole or dptrz for SNNU-314-X), provide an ideal platform to investigate the effect of C-H⋯X (X = Cl, Br, I) hydrogen bonding on C2H2 adsorption and purification performance. Benefiting from the small pore size and pore environment, the C2H2 uptake and separation properties of this series of MOFs are systematically regulated. Detailed gas adsorption results show that with the same organic linker, the C2H2 uptake and separation (C2H2/C2H4 and C2H2/CO2) performance decrease clearly with the electronegativity of halogen ions (SNNU-313-Cl > SNNU-313-Br > SNNU-313-I). With the same halogen ion, the gas adsorption decreases with the bulk of decorated alkyl groups (SNNU-313-Cl > SNNU-314-Cl). Remarkably, SNNU-313/314 series MOF adsorbents exhibit moderate C2H2 uptake capacity and high separation ability, but the C2H2 adsorption enthalpies are much lower than those of MOF materials with exposed F sites. Dynamic fixed-bed column breakthrough experiments and Grand Canonical Monte Carlo (GCMC) simulations further indicate the critical effects of halogen hydrogen bonds on acetylene adsorption and separation. Overall, this work demonstrated an effective regulation of acetylene adsorption and separation by rational C-H⋯X hydrogen bonding, which may provide a new route for the exploration of energy-efficient acetylene adsorbent materials.