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Dynamic 3D covalent organic frameworks (dynaCOFs) have shown concerted structural transformation and responses upon adaptive guest adsorption. The multivariate (MTV) strategy incorporating multiple functionalities within a backbone is attractive for tuning the framework flexibility and dynamic responses. However, a major synthetic challenge arises from the different chemical reactivities of linkers usually resulting in phase separation. Here, we report a general synthetic protocol for making 3D MTV-COFs by balancing the linker reactivity and solvent polarity. Specifically, 15 crystalline and phase pure MTV-COF-300 isostructures are constructed by linking a tetrahedral unit with eight ditopic struts carrying various functional groups. We find that the electron-donating groups make the linker reactivity too low to allow the reaction to proceed fully, while the electron-withdrawing groups afford increased reactivity and hardly yield crystalline materials. To overcome the crystallization dilemma, the combination of polar aprotic with nonpolar solvents was used to improve the solubility of oligomers and slow the reaction kinetics in MTV-COF synthesis. We demonstrate the abilities of these MTV-COFs to tune gas dynamic behaviors and the separation of benzene and cyclohexane. These findings reveal the integration of multivariate functionalities into dynaCOFs with on-demand flexibility to achieve dynamic synergism in particular applications, outperforming their pure, monofunctional counterparts.
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In this paper, we investigate a user pairing problem in power domain non-orthogonal multiple access (NOMA) scheme-aided satellite networks. In the considered scenario, different satellite applications are assumed with various delay quality-of-service (QoS) requirements, and the concept of effective capacity is employed to characterize the effect of delay QoS limitations on achieved performance. Based on this, our objective was to select users to form a NOMA user pair and utilize resource efficiently. To this end, a power allocation coefficient was firstly obtained by ensuring that the achieved capacity of users with sensitive delay QoS requirements was not less than that achieved with an orthogonal multiple access (OMA) scheme. Then, considering that user selection in a delay-limited NOMA-based satellite network is intractable and non-convex, a deep reinforcement learning (DRL) algorithm was employed for dynamic user selection. Specifically, channel conditions and delay QoS requirements of users were carefully selected as state, and a DRL algorithm was used to search for the optimal user who could achieve the maximum performance with the power allocation factor, to pair with the delay QoS-sensitive user to form a NOMA user pair for each state. Simulation results are provided to demonstrate that the proposed DRL-based user selection scheme can output the optimal action in each time slot and, thus, provide superior performance than that achieved with a random selection strategy and OMA scheme.
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Adsorption and separation of Xe/Kr are significant for making high-density nuclear energy environmentally friendly and for meeting the requirements of the gas industry. Enhancing the accuracy of the adsorbate model for describing the adsorption behaviors of Xe and Kr in MOFs and the efficiency of the model for predicting the separation potential (SP) value of Xe/Kr separation in MOFs helps in searching for promising MOFs for Xe/Kr adsorption and separation within a short time and at a low cost. In this work, polarizable and transferable models for mimic Xe and Kr adsorption behaviors in MOFs were constructed. Using these models, SP values of 38 MOFs at various temperatures and pressures were calculated. An optimal neural network model called BPNN-SP was designed to predict SP value based on physical parameters of metal center (electronegativity and radius) and organic linker (three-dimensional size and polarizability) combined with temperature and pressure. The regression coefficient value of the BPNN-SP model for each data set is higher than 0.995. MAE, MBE, and RMSE of BPNN-SP are only 0.331, -0.002, and 0.505 mmol/g, respectively. Finally, BPNN-SP was validated by experiment data from six MOFs. The transferable adsorbate model combined with the BPNN-SP model would highly improve the efficiency for designing MOFs with high performance for Xe/Kr adsorption and separation.
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In this work, hydrothermal technique combined with KOH activation were employed to develop a series of porous carbons (NPCK-x) using tobacco stem as a low-cost carbon source and (NH4)2C2O4 as a novel nitrogen-doping agent. Physicochemical properties of NPCK-x were characterized by Brunauer-Emmett-Teller, field emission scanning electron microscopy, X-ray diffraction, Raman microscope, elemental analysis, and X-ray photoelectron spectroscopy. Results showed that the NPCK-x samples possessed large surface areas (maximum: 2875 m2/g), hierarchical porous structures, and high degree of disorder. N-containing functional groups decomposed during activation process, which could be the dominant reason for appearance of abundant mesopores and well-developed pore structure. Dynamic chlorobenzene adsorption experiments demonstrated that carbon materials with (NH4)2C2O4 modification exhibited higher adsorption capacity (maximum: 1053 mg/g) than those without modification (maximum: 723 mg/g). The reusability studies of chlorobenzene indicated that the desorption efficiency of (NH4)2C2O4 modified porous carbon reached 90.40% after thermal desorption at 100°C under N2 atmosphere. Thomas model fitting results exhibited that the existence of mesopores accelerated the diffusion rate of chlorobenzene in porous carbon. Moreover, Grand Canonical Monte Carlo simulation was conducted to verify that micropores with pore sizes of 1.2-2 nm of the optimized porous carbon were the best adsorption sites for chlorobenzene and mesopores with pore sizes of 2-5 nm were also highly active sites for chlorobenzene adsorption.
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Carbono , Clorobenzenos , Adsorção , PorosidadeRESUMO
Amphiphilic surfactants are widely used as templates to synthesize hierarchically structured zeolites due to their multiple functions; however, piloting such new dual-functional templates is limited by their time-consuming nature and high cost. Herein, a simple organic molecule, without a long hydrophobic alkyl chain, was tailored from a gemini-type, poly-quaternary ammonium surfactant, and effectively used as a dual-porogenic template to synthesize hierarchical MTW zeolite. Upon a range of synthesis parameter optimizations, our detailed characterization suggested that the hierarchical MTW zeolite would completely crystallize within 36â hours from the surface to the inside of quasi-spherical particles through in situ consumption of amorphous silicon and aluminum species; much faster than most of the hierarchical MTW zeolites generated by conventional methods. Moreover, the as-prepared hierarchical MTW zeolite exhibited 4â times higher catalytic performance and lifetime of benzene-propene alkylation compared to conventional MTW zeolite, while the introduced crystalline mesopores are of benefit to diffuse reactants, products, and coke depositions. Our strategy broadens the design of new templates in more effective ways to facilely synthesize versatile hierarchical zeolites for diverse applications, especially for those in which macromolecules are involved.
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Large pore sizes, high pore volumes, facile synthesis conditions, and high space-time yields are recognized as four crucial criteria in the fabrication of metal-organic frameworks (MOFs). However, these four objectives are rarely realized together. Herein, we have developed a simple and versatile method that employs 1,4-butanediamine (BTDM) as a template for rapidly fabricating four stable hierarchically porous MOFs (H-MOFs), including HKUST-1, ZIF-8, ZIF-67, and ZIF-90. The synthesis conditions are simple and facile at room temperature and ambient pressure, and the synthesis time can be shortened to 1 min. The resultant H-MOFs exhibit multimodal hierarchically porous structures with meso- and macropores interconnected with micropores, as well as high pore volumes (0.76 cm3 g-1). The maximum space-time yield for the hierarchically porous HKUST-1 reaches 7.4 × 104 kg m-3 d-1, at least one order of magnitude higher than previous reported yields. Notably, the additive BTDM not only facilitates crystal growth but also guides the formation of meso- and macropores. The synthesis route is highly versatile, as analogues (e.g., tetramethyl-1,3-diaminopropane and tetramethyldiaminomethane) can also be employed as templates to prepare diverse H-MOFs. Furthermore, the porosities of the H-MOFs are readily tuned by controlling the metal source, template amount and type of template. The as-synthesized H-MOFs act as adsorbents with significantly improved performances relative to those of microporous MOFs used for CH4 and CO2 gas storage. This strategy may aid in the large-scale industrial synthesis of desirable H-MOFs for gas storage.
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A hierarchically structured beta zeolite with intercrystalline mesopores was successfully synthesized via in situ assembly of nanoparticles by employing a simple organic molecule N2-p-N2, tailored from polyquaternium surfactant, with no hydrophobic long chain. The generated samples were studied by using powder X-ray diffraction (XRD) and nitrogen adsorption/desorption isotherms. Computer simulation, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) technologies were also used. The characterized results show that the tailored template molecule N2-p-N2 without hydrophobic long-chain tail still can direct the zeolite crystallization, while the hydrophobic long-chain tail is not necessary during the mesoporous Beta zeolite formation. The catalytic performances of the sample were studied using alkylation of benzene with propene reaction to evaluate the relationship between the structure and property. The results apparently suggested an overall improved resistance against deactivation as compared to conventional beta zeolite in reactions. Furthermore, this tailored simple organic molecule strategy from dual-functional surfactant for making mesoporous zeolite would offer a new method of synthesizing other hierarchically structured zeolites.
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The mesoporous zeolite is a novel porous material possessing mesopores as well as the inherent micropores of zeolites. This material can exhibit the dual merits of two different pore structures and enable zeolites to have maximum structural functions. During the past few decades, various synthetic strategies have been well developed. However, up to now, there has only been a few attempts to model mesoporous zeolites. In this paper, the structural properties of a mesoporous ZSM-5 type molecular sieve, which has mesopore walls that are made up of ZSM-5 zeolite-like frameworks, were studied using an atomistic model. The full-atom model of the mesoporous ZSM-5 type molecular sieve was constructed using a molecular modeling technique. The structure model was characterized by estimating the nitrogen accessible solvent surface area, small-angle and wide-angle X-ray diffraction patterns, toluene and benzene adsorption. It was found that these simulated results match well with the experimental data. Furthermore, the present approach can be extended to construct other micro-mesoporous molecular sieve structure models in the future.
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Recovering light alkanes from natural gas is a critical but challenging process in petrochemical production. Herein, we propose a postmodification strategy via simultaneous metal/ligand exchange to prepare multivariate metal-organic frameworks with enhanced capacity and selectivity of ethane (C2H6) and propane (C3H8) for their recovery from natural gas with methane (CH4) as the primary component. By utilizing the Kuratowski-type secondary building unit of CFA-1 as a scaffold, namely, {Zn5(OAc)4}6+, the Zn2+ metal ions and OAc- ligands were simultaneously exchanged by other transition metal ions and halogen ligands under mild conditions. Inspiringly, this postmodification treatment can give rise to improved capacity for C2H6 and C3H8 without a noticeable increase in CH4 uptake, and consequently, it resulted in significantly enhanced selectivity toward C2H6/CH4 and C3H8/CH4. In particular, by adjusting the species and amount of the modulator, the optimal sample CFA-1-NiCl2-2.3 demonstrated the maximum capacities of C2H6 (5.00 mmol/g) and C3H8 (8.59 mmol/g), increased by 29 and 32% compared to that of CFA-1. Moreover, this compound exhibited excellent separation performance toward C2H6/CH4 and C3H8/CH4, with high uptake ratios of 6.9 and 11.9 at 298 K and 1 bar, respectively, superior to the performance of a majority of the reported MOFs. Molecular simulations were applied to unravel the improved separation mechanism of CFA-1-NiCl2-2.3 toward C2H6/CH4 and C3H8/CH4. Furthermore, remarkable thermal/chemical robustness, moderate isosteric heat, and fully reproducible breakthrough experiments were confirmed on CFA-1-NiCl2-2.3, indicating its great potential for light alkane recovery from natural gas.
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Environmental factors affecting the photocatalytic oxidation of volatile organic compounds (VOCs) have previously been studied experimentally, but there are few theoretical studies, especially those on surface intermolecular forces. Because of this, it is unclear how multiple coexisting factors impact photocatalytic processes. Herein, comprehensive multi-factorial impact mechanisms of the photocatalytic oxidation of formaldehyde were assessed using experiments and density functional theory simulations. The influence of humidity, concentration, and intermediate formate was investigated using a nano-TiO2 colloid, followed by adsorption and photocatalytic simulations. The maximum photocatalytic reaction rate and degradation efficiency occurred at 50% humidity due to the initially enhanced and then weakened adsorption and photocatalysis of formaldehyde. This stemmed from the increased number of water molecules and the narrower TiO2 band gap at low humidities, as well as the competitive adsorption between formaldehyde and excess water molecules at high humidities. Upon increasing the formaldehyde concentration, its photocatalytic oxidation rate increased due to enhanced adsorption, but weakened photocatalysis decreased the photocatalytic efficiency. The intermediate formate enhanced the adsorption and inhibited photocatalysis and did not significantly change the photocatalytic oxidation rate of formaldehyde upon changing the irradiation time. These findings provide guidance for the photocatalytic oxidation of VOCs produced by industrial air pollution.
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Gases , Titânio , Adsorção , Catálise , Coloides , FormaldeídoRESUMO
A humidity sensor is a crucial device in daily life; therefore, in the present study, a novel humidity sensor was designed to increase its specific surface area to improve its humid sensing capacity and conductivity. Titanium dioxide nanoparticles (TiNP) consisting of zero-dimensional nanospheres and one-dimensional nanotubes were prepared by anodic oxidation. Rod-shaped cellulose nanocrystals (CNCs) with average length and diameter of 60 nm and 800 nm, respectively, were obtained by enzymatic hydrolysis and high pressure homogenization. TiNP/CNC composite films exhibited superior hydrophilicity and large specific surface areas based on Fourier transform infrared spectroscopy and nitrogen adsorption-desorption results. The humidity sensing characteristics of sensors based on TiNP/CNC flexible composite films with varying contents of TiNP were investigated under a relative humidity range of 11-97%. The 6% TiNP/CNC-based humidity sensor exhibited high humidity response, rapid response/recovery speed, and high stability. Furthermore, the humidity sensing mechanism of TiNP/CNC composite films was analyzed based on the density functional theory. TiNP/CNC-based humidity sensors could be applied in flexible and wearable electronics.
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VOCs in paper mills have severely exceeded the emission standards and their photo-catalytic degradations should focus on the experimental and theoretical studies. This work used TiO2 colloid as catalyst to study the photo-catalytic degradations of mixed HCHO and C6H6 at five mixing ratios. The adsorption behaviors of pure forms and mixtures on the TiO2 (101) surface were simulated using density functional theory (DFT), and their catalytic reaction mechanisms were also analyzed. The following results were found: (1) With increasing initial concentration, the enhanced adsorption and easy degradation interpreted the increased degradation rate for pure HCHO, while the counteractions of enhanced adsorption and inhibited catalytic reaction kept the constant degradation rate for pure C6H6. (2) For their mixtures, the HCHO degradation was inhibited at high C6H6 concentration due to the inhibited adsorption and catalytic reaction of HCHO. The C6H6 degradation was slightly weakened at high HCHO concentration and then restored to the normal degradation rate of C6H6, which could be attributed to the weakened adsorption of C6H6 and the easy degradation of HCHO in the initial stage. The combined experimental, simulation, and theoretical results provides sufficient information to understand the photo-catalytic degradation process for mixed gaseous pollutants in different realistic environments.
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Hierarchically porous metal-organic frameworks (MOFs) have recently emerged as a novel crystalline hybrid material with tunable porosity. Many efforts have been made to develop hierarchically porous MOFs, yet their low-energy fabrication remains a challenge and the underlying mechanism is still unknown. In this study, the rapid fabrication of two hierarchically porous MOFs (Cu-BTC and ZIF-8) was carried out at room temperature and ambient pressure for 10 min using a novel surfactant as the template in a (Cu, Zn) hydroxy double salt (HDS) solution, where the (Cu, Zn) HDS accelerated the nucleation of crystals and the anionic surfactants served as templates to fabricate mesopores and macropores. The growth mechanism of hierarchically porous MOFs was analyzed via mesodynamics (MesoDyn) simulation, and then the synthetic mechanism of hierarchically porous MOFs at the molecular level was obtained. The as-synthesized hierarchically porous Cu-BTC showed a high uptake capacity of 646 mg g-1, which is about 25% higher as compared with microporous Cu-BTC (516 mg g-1) for the capture of toluene. This study provides a theoretical basis for the large-scale fabrication of hierarchically porous MOFs and offers a reference for the understanding of their synthetic mechanism.
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A novel type of anti and syn isomers of a pentacyclic compound consisting of two thiophene rings and one pyrrole ring were efficiently synthesized from benzo[b]thiophene, and the anti isomer exhibits better charge transport and OFET properties compared with the syn isomer and its N-hexyl substitution.
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The separation of ethane from ethylene using cryogenic distillation is an energy-intensive process in the industry. With lower energetic consumption, the adsorption technology provides the opportunities for developing the industry with economic sustainability. We report an iron-based metal-organic framework PCN-245 with interpenetrated structures as an ethane-selective adsorbent for ethylene/ethane separation. The material maintains stability up to 625 K, even after exposure to 80% humid atmosphere for 20 days. Adsorptive separation experiments on PCN-245 at 100 kPa and 298 K indicated that ethane and ethylene uptakes of PCN-245 were 3.27 and 2.39 mmol, respectively, and the selectivity of ethane over ethylene was up to 1.9. Metropolis Monte Carlo calculations suggested that the interpenetrated structure of PCN-245 created greater interaction affinity for ethane than ethylene through the crossing organic linkers, which is consistent with the experimental results. This work highlights the potential application of adsorbents with the interpenetrated structure for ethane separation from ethylene.
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Developing metal-organic frameworks (MOFs) with moisture-resistant feature or moisture-enhanced adsorption is challenging for the practical CO2 capture under humid conditions. In this work, under humid conditions, the CO2 adsorption behaviors of two iron-based MOF materials, PCN-250(Fe3) and PCN-250(Fe2Co), were investigated. An interesting phenomenon is observed that the two materials demonstrate an unusual moisture-enhanced adsorption of CO2. For PCN-250 frameworks, H2O molecule induces a remarkable increase in the CO2 uptake for the dynamic CO2 capture from CO2/N2 (15:85) mixture. For PCN-250(Fe3), its CO2 adsorption capacity increases by 54.2% under the 50% RH humid condition, compared with that under dry conditions (from 1.18 to 1.82 mmol/g). Similarly, the CO2 adsorption uptake of PCN-250(Fe2Co) increases from 1.32 to 2.23 mmol/g, exhibiting a 68.9% increase. Even up to 90% RH, for PCN-250(Fe3) and PCN-250(Fe2Co), obvious increases of 43.7 and 70.2% in the CO2 adsorption capacities are observed in comparison with those under dry conditions, respectively. Molecular simulations indicate that the hydroxo functional groups (µ3-O) within the framework play a crucial role in improving CO2 uptake in the presence of water vapor. Besides, partial substitution of Fe3+ by Co2+ ions in the PCN-250 framework gives rise to a great improvement in CO2 adsorption capacity and selectivity. The excellent moisture stability (stable even after exposure to 90% RH humid air for 30 days), superior recyclability, as well as moisture-enhanced feature make PCN-250 as an excellent MOF adsorbent for CO2 capture under humid conditions. This study provides a new paradigm that PCN-250 frameworks can not only be moisture resistant but can also subtly convert the common negative effect of moisture to a positive impact on improving CO2 capture performance.
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Three hierarchical porous zeolites (H-*BEA, H-MTW, and H-*MRE) were successfully synthesized with the assistance of designed cationic surfactants under hydrothermal synthesis conditions. The as-synthesized zeolite samples can be easily regulated by changing the number of long hydrophobic n-alkyl chains. Also, we investigated the relationship between the length of the surfactant and the formation of the microporous structure of the zeolite. Furthermore, the alkylation of benzene with propene was performed as a probe reaction to evaluate the catalytic performance of the synthesized hierarchical zeolites. The resulting materials were characterized by using a complementary combination of techniques, that is, X-ray powder diffraction, N2 adsorption-desorption isotherms, scanning electron microscopy, transmission electron microscopy, Fourier transform IR spectroscopy, 28 Si and 27 Al MAS NMR spectroscopies, thermogravimetric analysis, and computer simulation. These analysis results indicated that quaternary ammonium surfactants acted as organic structure-directing agents (OSDAs) in the formation of these hierarchical zeolite samples, whether the surfactant had long hydrophobic tail groups or not. The simulation results indicated that the organic molecules with no long hydrophobic chain could lead to the synthesis of zeolite through charge control, and the hydrophobic molecules with long hydrophobic chains could form zeolites through orbital control. These hierarchical zeolites showed improved catalytic activity towards the industrially relevant alkylation of benzene with propene compared with conventional zeolites with the same frameworks. More importantly, the success of using quaternary ammonium surfactants with no hydrophobic n-alkyl tail group in the synthesis of hierarchically structured mesoporous zeolites provides a new pathway for the synthesis of hierarchical porous materials by a soft-templating method.
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This work mainly involves the study of desorption kinetics of phenol from polymeric resins under the influence of an ultrasound field. A new phase equilibrium-kinetics model (PEKM), for estimation of diffusion coefficient was proposed, kinetic experiments of phenol desorption on NKA-II resin in the presence and the absence of ultrasound were separately conducted, and diffusion coefficients of phenol within an adsorbent particle were estimated by means of proposed PEKM. Results showed that the use of ultrasound could enhance the diffusion of phenol within the resin. The diffusion coefficient of phenol in the resin in an ultrasonic field increased by an order of magnitude in comparison with the diffusion coefficient in the absence of ultrasound. The more intense the ultrasonic field the larger was the diffusion coefficient.
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The adsorption and separation properties of benzene and toluene on the zirconium-based frameworks UiO-66, -67, -68, and their functional analogues UiO-Phe and UiO-Me2 were studied using grand canonical Monte Carlo simulations, density functional theory, and ideal adsorbed solution theory. Remarkable higher adsorption uptakes of benzene and toluene at low pressures on UiO-Phe and -Me2 were found compared to their parent framework UiO-67. It can be ascribed to the presence of functional groups (aromatic rings and methyl groups) that significantly intensified the adsorption, majorly by reducing the effective pore size and increasing the interaction strength with the adsorbates. At high pressures, the pore volumes and accessible surfaces of the frameworks turned out to be the dominant factors governing the adsorption. In the case of toluene/benzene separation, toluene selectivities of UiOs showed a two-stage separation behavior at the measured pressure range, resulting from the greater interaction affinities of toluene at low pressures and steric hindrance effects at high pressures. Additionally, the counterbalancing factors of enhanced π delocalization and suitable pore size of UiO-Phe gave rise to the highest toluene selectivity, suggesting the ligand functionalization strategy could reach both high adsorption capacity and separation selectivity from aromatic mixtures at low concentrations.
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The adsorptive separation properties of M-BTC isostructural series (M = Ti, Fe, Cu, Co, Ru, Mo) for methanol-acetone mixtures were investigated by using various computational procedures of grand canonical Monte Carlo simulations (GCMC), density functional theory (DFT), and ideal adsorbed solution theory (IAST), following with comprehensive understanding of adsorbate-metal interactions on the adsorptive separation behaviors. The obtained results showed that the single component adsorptions were driven by adsorbate-framework interactions at low pressures and by framework structures at high pressures, among which the mass effects, electrostatics, and geometric accessibility of the metal sites also played roles. In the case of methanol-acetone separation, the selectivity of methanol on M-BTCs decreased with rising pressures due to the pressure-dependent separation mechanisms: the cooperative effects between methanol and acetone hindered the separation at low pressures, whereas the competitive effects of acetone further resulted in the lower selectivity at high pressures. Among these M-BTCs, Ti and Fe analogues exhibited the highest thermodynamic methanol/acetone selectivity, making them promising for adsorptive methanol/acetone separation processes. The investigation provides mechanistic insights on how the nature of metal centers affects the adsorption properties of MOFs, and will further promote the rational design of new MOF materials for effective gas mixture separation.