Aluminum-based Metal Organic Framework Research Articles

Nonalkaline Fabrication of Al-Based Metal-Organic Frameworks with Tailored Water Sorption Properties via Polymeric Hydroxy-Aluminum Basicity Modulation.

Metal-organic frameworks (MOFs) are porous crystalline materials composed of metallic nodes and organic ligands, demonstrating increasing potential in water harvesting in arid and semiarid regions. This study presents a nonalkaline, water-based, and scalable synthesis strategy designed to adjust the water sorption properties of aluminum-based MOFs (Al-MOFs), specifically, AlFum and MOF-303, by modifying the basicity of the metal source, polymeric hydroxy-aluminum, as an alternative. Characterizations, including X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analyses (TGA), confirmed the successful synthesis of Al-MOFs. The results revealed that high-basicity polymeric hydroxy-aluminum introduced additional mesoscopic intraparticle defects, interparticle voids, and hydrophilic surface sites to the primary microporous Al-MOFs. This led to an enhanced external surface area and uniformity in the particle size. Consequently, the water sorption performance of basicity-modulated Al-MOFs was significantly improved. Specifically, within the typical working humidity between 0.05 and 0.3, using polymeric hydroxy-aluminum of the highest basicity resulted in a 23% and 68% increase in water uptake for AlFum and MOF-303, respectively, achieving capacities of 0.43 and 0.37 g·g-1. Cyclic water adsorption-desorption tests further indicated the hydrolytic stability of prepared Al-MOFs. This study offers a novel approach to engineering MOF properties through metal source modulation, with important implications for applications in water harvesting and heat transfer.

Concurrent conversion of waste cooking oil using Al metal-organic framework and subcritical methanol through esterification/transesterification process

Recently, some scientists have focused on discovering techniques for manufacturing biodiesel on a significant, efficient, and ecologically sustainable scale. Choosing a catalyst is a notable challenge due to the instability and cost feasibility issues connected with newly designed homogeneous and heterogeneous catalysts. This paper describes the synthesis and utilization of aluminum-based metal-organic frameworks (MOFs) as catalysts for the generation of biodiesel from waste cooking oil (WCO). The processes involved in this study are esterification and transesterification, which are carried out using subcritical methanol. The catalyst analysis reveals that the MOFs possess a filamentous structure, with a crystallite size ranging from 300 to 500 nm. Furthermore, these MOFs exhibit thermal stability up to 470 °C. The catalyst underwent examination for biodiesel production from waste cooking oil (WCO), and the resulting biodiesel samples met the standards set by the American Society for Testing and Materials (ASTM). The experiment was devised and fine-tuned to incorporate the three independent variables using a multilevel factorial design, response surface methodology, and a three-way analysis of variance (ANOVA). The FAME conversion peaked at 91.96 %, as determined through statistical analysis of the optimization findings. The corresponding values for the variables were X1: 423.15 K, X2: 1800s, and X3: 28 mol/mol. Based on ANOVA statistics, the experimental and mathematical verification demonstrates a fair correlation between the actual and calculated catalyst performance. The temperature and molar ratio of methanol: WCO significantly affected the FAME conversion.

Mechanism of Enhanced Fluoride Adsorption Using Amino-Functionalized Aluminum-Based Metal–Organic Frameworks

Due to the increasing fluoride concentrations in water bodies, significant environmental concerns have arisen. This study focuses on aluminum-based materials with a high affinity for fluorine, specifically enhancing metal–organic frameworks (MOFs) with amino groups to improve their adsorption and defluorination performance. We systematically investigate the factors influencing and mechanisms governing the adsorption and defluorination behavior of amino-functionalized aluminum-based MOF materials in aqueous environments. An SEM, XRD, and FT-IR characterization confirms the successful preparation of NH2-MIL-101 (Al). In a 10 mg/L fluoride ion solution at pH 7.0, fluoride ion removal efficiency increases with the dosage of NH2-MIL-101 (Al), although the marginal improvement decreases beyond 0.015 g/L. Under identical conditions, the fluoride adsorption capacity of NH2-MIL-101 (Al) is seven times greater than that of NH2-MIL-101 (Fe). NH2-MIL-101 (Al) demonstrates effective fluoride ion adsorption across a broad pH range, with superior fluoride uptake in acidic conditions. At a fluoride ion concentration of 7 mg/L, with 0.015 g of NH2-MIL-101 (Al) at pH 3.0, adsorption equilibrium is achieved within 60 min, with a capacity of 31.2 mg/g. An analysis using adsorption isotherm models reveals that the fluoride ion adsorption on NH2-MIL-101 (Al) follows a monolayer adsorption model, while kinetic studies indicate that the predominant adsorption mechanism is chemical adsorption. This research provides a scientific basis for the advanced treatment of fluoride-containing wastewater, offering significant theoretical and practical contributions.

Angstrom-Level Tuning in Confined Space of Metal-Organic Framework for Ultra-High Resolution in Gas Chromatographic Separation.

Optimizing the balance between thermodynamic interaction and kinetic diffusion is pivotal to obtaining high-performance gas chromatographic stationary phases. Here, three aluminum-based metal-organic frameworks featuring fym topology were chosen to achieve such balance by refined controlling the thermodynamic interactions toward analytes at angstrom level in a confined space. The CAU-10-H with the middle-sized channels (5.4 Å) provided weak interactions with xylenes because of the benzene ring around the channel, leading to the fastest diffusion. While the MIL-160 provided stronger interactions toward the analytes due to the abundance of O-heterocyclic sites of 2,5-furandicarboxylic acid ligands, resulting in slightly higher diffusion barriers. Thereby, although MIL-160 had a larger channel (5.9 Å) than CAU-10-H, the xylenes still diffused more slowly in MIL-160 than in CAU-10-H. The CAU-10-NH2 with the channel of 4.7 Å provided overstrong thermodynamic interactions and significant stereospecific blockade to the analytes because of the NH2 sites in the confined channels. These factors collectively contributed to achieving the lowest diffusion kinetics. The confined interactions were also proved by molecular dynamics simulation. Furthermore, the application indicated that MIL-160 exhibited the highest separation ability as a GC stationary phase among all reported materials. This strategy offers an approach for developing high-performance MOF stationary phases.

A novel Al-based MOF with straight channel and pocket pore structure for trace benzene adsorption and benzene/cyclohexane separation

Benzene (Bz) vapor poses significant health risks to humans, even at trace concentrations. Additionally, the separation and recycling of Bz and cyclohexane (Cy) is challenging due to their similar kinetic diameters and boiling points. Developing an adsorption-separation material with stronger interactions with Bz than with Cy could serve as a viable strategy for trace Bz adsorption and Bz/Cy separation. In this study, we present a novel aluminum-based metal–organic framework, ZJU-521(Al), composed of tetrakis (4-carboxyphenyl)methane and a helical chain [Al5(OH)7(−COO)8]∞, featuring a simple network of one-way rods and tetrahedra. This framework exhibited a uniform micropore size of 7.23 Å and a specific surface area of 1,248 m2 g−1, demonstrating excellent trace Bz adsorption (4.18 mmol g−1) at P/P0 = 0.01, attributed to its straight channel and orthogonal-array pocket pore structure. The ideal adsorbed solution theory selectivity and separation factor values of ZJU-521(Al) for Bz/Cy were 22.50 and 6.20, respectively, indicating its potential as a material for Bz/Cy separation. Multicomponent simulations showed that Bz molecules were preferentially adsorbed in the pocket due to stronger interactions, such as Al–π interactions. Thus, ZJU-521(Al) exhibits stronger interactions with Bz than with Cy, facilitating effective Bz/Cy separation.

Proton-conductive properties of a stable three-dimensional aluminum(III)-organic framework constructed by porphyrinlcarboxylate

The proton conductivity (σ) of the highly stable metal-organic frameworks (MOFs) built by carboxylic acid ligand and aluminum metal has not been fully investigated. Herein, a three-dimensional aluminum-based MOF, [(AlOH)2TCPP]n (namely Al-TCPP) with exceptional structural stability was solvothermally synthesized using an organic multifunctional bridging ligand, meso-tetra(4-carboxyphenyl)porphine (H4TCPP) with a large stiff ring structure and Al(NO3)3⋅9H2O as raw materials. The dependency of σ on temperature and relative humidity (RH) was surveyed using the AC impedance test after the MOF's thermal, water, and chemical stabilities, as well as nitrogen and H2O vapor adsorptions, were all characterized. Experimental results demonstrated that this highly stable MOF with a high specific surface area exhibited impressive proton conductivity, with an optimal σ of 3.2 × 10-4 S/cm under 100 °C/98% RH. Furthermore, the proton-conducting mechanism inside the framework was highlighted using computed activation energy and structural analysis. This study provides new inspiration for designing and searching for high-performance proton-conductive materials.

An ultrasound assisted dispersive micro solid-phase extraction and a composite ionic liquid-metal organic framework for sixteen polycyclic aromatic hydrocarbons analysis in fruit juice and environmental water samples

Aluminum-based metal organic framework composite containing ionic liquid was prepared and used as sorbent for extraction of sixteen polycyclic aromatic hydrocarbons in list of priority pollutants of United States Environmental Protection Agency before their analysis by gas chromatography/mass spectrometry. The dispersive micro solid-phase extraction method, known as a simple and fast method, was preferred as the extraction method. The optimized parameter conditions were 5 mL of sample solution, 10 min sonication by ultrasonic bath, 30 mg of sorbent, 30 °C extraction temperature, 0.1 mL of hexane as elution solvent with 5 min elution time. The suggested method presented that limit of detection and limit of quantification were in the range of 0.01–0.10 μg l-1, and 0.04–0.33 μg L-1, respectively. The intra-day and inter-day repeatability were within the ranges of 1.18–4.88 % and 1.02–5.06 %, respectively. The recoveries for polycyclic aromatic hydrocarbons in peach juice, cherry juice, tap water and rain water samples were obtained in the range of 84.9–99.9 % for spiked 5, 50 and 100 μg l-1 standard polycyclic aromatic hydrocarbons solution.

Aluminium-based metal-organic frameworks for the colorimetric ethephon detection in fruit by paper microsensor

Ethephon (ETH) is a plant growth regulator extensively utilized in agriculture, but its overuse is associated with several health issues. However, detecting ETH sensitively and easily in the field is challenging due to the complexity and time-consuming operation of current approaches. In this study, we synthesized aluminum-based metal-organic frameworks (CAU-1) as fluorescent probes for the detection of ETH in fruit. ETH exposure enhanced and shifted the light green fluorescence of CAU-1 to blue through high absorption of phosphate by electrostatic attraction. We observed a linear correlation between fluorescent intensity and ETH concentration ranging from 2 mg/L to 400 mg/L, with the lowest detection limit at 1 mg/L. This fluorescent analysis exhibited good selectivity towards ETH. To facilitate easy identification of samples in the field, we designed a fluorescent paper-based platform with a logic gate operation, allowing visual distinction of samples containing ETH. We applied this platform to monitor ETH in various fruits, including apples, pears, and tomatoes, through fluorescent spectrum, and visual detection. The platform offered simplicity, speed, ease of use and sensitivity, providing a promising future for ETH detection in agriculture.

Punica grantum peel extract decorated Al-MOF scaffold as Solid-State Sensor/Concentrator for the Sensing/Reduction of Cr(VI) and its extended utility as a corrosion inhibitor in Al-Air batteries

The growing presence of hexavalent chromium in environmental and industrial settings highlights the importance of developing an eco-benign platform for real-time in-situ sensing/screening and decontamination. This research presents a facile and portable solid-state optical sensor using waste Punica Granatum, i.e., pomegranate peel extract (PPE) adorn onto Aluminium-based Metal-Organic Frameworks (Al-MOFs) for the sensing of carcinogenic Cr(VI) and its decontamination to benign Cr(III). The sensor fabrication entails a hydrothermal synthesis to form Al-MOF scaffolds decorated with PPE through direct immobilization. Al-MOF exhibits a large surface area with well-defined pore channels that facilitate PPE’s voluminous/uniform anchoring in restricted orientations to serve as an ion-selective probe for specifically targeting ultra-trace Cr(VI). The surface/structural morphology and porosity of the Al-MOF-PPE material are characterized using scanning/transmission electron microscopy and BET/BJH analysis. The reduction of Cr(VI) by the Al-MOF-PPE is validated by electron spectroscopy for chemical analysis, corroborated by a conspicuous color transition from light yellow to dark brown. The efficient reduction of Cr(VI) by Al-MOF-PPE is achieved at pH 2–3, in the linear response range of 0.3–300 ppb and a detection limit of 0.23 ppb for Cr(VI). The sensory system prefers minimal PPE probe content (4 mg) and sensor dosage (5 mg) for ion-sensing and decontamination studies, highlighting its remarkable operational efficacy. Post Cr(VI) reduction, electrochemical studies confirm the utility of Al-MOF-PPE-Cr(III) as a corrosion inhibitor for metal surfaces. Tafel plots demonstrate that Al-MOF-PPE-Cr(III) exhibits cathodic and anodic inhibition characteristics, ensuring excellent surface protection for aluminum electrodes upto 220 min in Al-air batteries. The proposed Al-MOF-PPE offers dual functionality as a naked-eye platform for Cr(VI) decontamination, and the Al-MOF-PPE-Cr(III) material is an excellent corrosion inhibitor for energy storage devices.

Selective Xenon Recovery Using Aluminum-Based Metal-Organic Frameworks with Conserved Pore Topology.

Xenon (Xe) is a commercially valuable element found in trace amounts in the off-gas from used nuclear fuel. Recovering Xe from these streams provides a cost-effective means to increase its supply. However, achieving high-purity Xe recovery is challenging due to the need for separation from nearly identical krypton (Kr). Metal-organic frameworks (MOFs), a class of crystalline porous materials, show potential to separate Xe and Kr by utilizing differences in their kinetic diameters, allowing for selective separation. In this work, we study the impact of pore aperture and volume on selective Xe recovery using four robust aluminum MOFs: Al-PMOF, Al-PyrMOF, Al-BMOF and MIL-120, all with conserved structural topology. The pore topology in each MOF is dictated by the dimensions of the tetracarboxylate ligand employed, with larger ligands leading to MOFs with increased pore size and volume. Our experimental and computational investigations revealed that MIL-120 exhibits the highest affinity (21.94 kH(Xe) = 21.94 mmol g-1 bar-1) for Xe among all MOFs, while Al-BMOF demonstrates the highest Xe/Kr selectivity of 14.34. We evaluated the potential of both MIL-120 and Al-BMOF for Xe recovery through breakthrough analysis using a mixture of 400 ppm Xe:40 ppm Kr. Our results indicate that due to its larger pore volume, Al-BMOF captured more Xe than MIL-120, demonstrating superior Xe/Kr separation efficiency.

Reusable MOF-Coated Chitosan@Paper Strip Composite for Real-Time Monitoring of Pesticide Pendimethalin and Organoarsenic Feed Additive Roxarsone Levels in Environmental Water, Food, and Vegetable Samples.

An alarming increase in the use of pesticides and organoarsenic compounds and their toxic impacts on the environment have inspired us to develop a selective and highly sensitive sensor for the detection of these pollutants. Herein, a bio-friendly, low-cost Al-based luminescent metal-organic framework (1')-based fluorescent material is demonstrated that helps in sustaining water quality by rapid monitoring and quantification of a long-established pesticide (pendimethalin) and a widely employed organoarsenic feed additive (roxarsone). A pyridine-functionalized porous aluminum-based metal-organic framework (Al-MOF) was solvothermally synthesized. After activation, it was used for fast (<10 s) and selective turn-off detection of roxarsone and pendimethalin over other competitive analytes. This is the first MOF-based recyclable sensor for pendimethalin with a remarkably low limit of detection (LOD, 14.4 nM). Real-time effectiveness in detection of pendimethalin in various vegetable and food extracts was successfully verified. Moreover, the aqueous-phase recyclable detection of roxarsone with an ultralow detection limit (13.1 nM) makes it a potential candidate for real-time application. The detection limits for roxarsone and pendimethalin are lower than the existing luminescent material based sensors. Furthermore, the detection of roxarsone in different environmental water and a wide pH range with a good recovery percentage was demonstrated. In addition, a cheap and bio-friendly 1'@chitosan@paper strip composite was prepared and successfully employed for the hands-on detection of pendimethalin and roxarsone. The turn-off behavior of 1' in the presence of pendimethalin and roxarsone was examined systematically, and plausible mechanistic pathways were proposed with the help of multiple experimental evidences.

Ultra-high flux loose nanofiltration membrane based on metal organic framework (CAU-10-H)/P84 co-polyimide for dye/salt fractionation from industrial waste water

In recent times, loose nanofiltration (NF) membranes have gained popularity for the treatment of dye/salt industrial wastewater, primarily owing to their exceptional separation capabilities and economic advantages. However, achieving nanocomposite mixed matrix membranes with ultrahigh water permeance and specific pore and surface characteristics for effective dye and inorganic salt fractionation presents a significant challenge. This study focuses on the development of high-efficiency loose nanofiltration mixed matrix membranes (MMMs) achieved by combining polymers and porous nanoparticles. Metal-organic frameworks (MOFs) hold substantial promise as porous additives in MMMs. However, high-quality MOF-based MMMs for treating dye/salt aqueous solutions are still scarce. In this work, we synthesized an aluminum-based metal-organic framework (CAU-10-H) and utilized it in the fabrication of composite MMMs by blending it with co-polyimide (P84). We successfully created a thin and porous CAU-10-H/P84 layer with a significantly low MOF content (1.5 %) on a nylon support. Our research findings revealed that the optimized membrane exhibited desirable permeance (260.4 LMH/bar) for dye/salt solutions and a pure water permeance of 386.4 LMH/bar. Furthermore, the membrane demonstrated high dye rejection (99.2 % for methyl blue and 99.1 % for Congo red) while maintaining low salt rejection (4.8 % for NaCl and 16.3 % for Na2SO4). Additionally, the composite MMMs exhibited excellent stability throughout a 24-h filtration process. The CAU-10-H/P84 composite MMMs exhibit significant potential for applications in dye/salt fractionation.

A novel anti-CD47 protein antibody and toll-like receptor agonist complex detects tumor surface CD-47 changes in early stage lung cancer by in vivo imaging

CD47, a cell surface protein known for inhibiting phagocytosis, plays a critical role in the tumor microenvironment (TME) and is a potential biomarker for cancer. However, directly applying αCD47, a hydrophilic macromolecular antibody that targets CD47, in vivo for cancer detection can have adverse effects on normal cells, cause systemic toxicities, and lead to resistance against anti-cancer therapies. In this study, we developed a novel complex incorporating aluminum-based metal-organic frameworks (Al-MOF) loaded with indocyanine green (ICG), αCD47, and resiquimod (R848), a hydrophobic small molecule Toll-like receptor 7/8 (TLR7/8) agonist. Upon activation with an infrared 808 nm laser, the nanocomposites exhibited photothermal effects that triggered the release of the loaded reagents, induced ROS production, and induced changes in the TME. This led to the polarization of immune-suppressive M2 macrophages towards an immune-stimulatory M1 phenotype, promoted dendritic cell (DC) maturation, and enabled mature DCs to facilitate antigen presentation, T-cell activation, and critical roles in tumor immunity. Furthermore, in vivo imaging successfully detected the specific binding of αCD47 with CD47 on tumor cells. Overall, the complex composed of αCD47 antibody and toll-like receptor agonist showed promising efficacy in both tumor diagnosis and therapy, providing a potential strategy for detecting early lung cancer and modulating the tumor microenvironment for improved treatment outcomes.

Hydroxyl-functionalized linker endows an ultra-microporous aluminum based metal–organic framework with electronegative site for enhancing ethane/ethylene separation

Efficient purification of ethylene (C2H4) from the cracking gas containing a small amount of ethane (C2H6) by selective adsorption of C2H6 is meaningful but remains challenging. Aluminum-based metal–organic frameworks (Al-MOFs) with ultra-microporous structure show preferential adsorption of C2H6 over C2H4, relying on the existence of multiple hydrogen bonding acceptors (e.g., AlO6 polyhedra) for C2H6 molecule in the confined pores. However, most Al-MOFs exhibit limited C2H6/C2H4 selectivity (<2), which lack other strong preferential binding sites for C2H6. Here we report that a hydroxyl functionalized Al-MOF (i.e., CAU-1-OH) exhibits notably improved C2H6/C2H4 selectivity (2.13) and C2H6 uptake (3.95 mmol g−1) at 298 K and 1 bar compared to its amino-functionalized counterpart, CAU-1-NH2. Prior to experiment, theoretical calculations were performed, revealing that O atom from hydroxyl group in CAU-1-OH acts as a fairly strong hydrogen bond acceptor due to its more negative charge than N atom in CAU-1-NH2. The in-situ infrared experiment further confirmed the formation of multiple hydrogen bonds (C–H⋅⋅⋅O) between CAU-1-OH and C2H6 molecules, which plays vital role for C2H6-selective capture. The actual potential for C2H4 purification was fully demonstrated by dynamic breakthrough experiments, in which CAU-1-OH displayed excellent separative performance from C2H6/C2H4 (1/15, v/v) mixture. Moreover, the structural stability and excellent recyclability suggested and the promise for cost-effective industrial application in C2H6/C2H4 separation.

Investigation on open water adsorption performance of multi-walled carbon nanotubes modified MIL-96(Al)

An aluminum-based metal-organic framework material MIL-96(Al) was prepared by solvent-thermal synthesis method, and by adding multi-walled carbon nanotubes (MWCNTs) in the preparation process, MWCNT/MIL-96(Al) composite adsorbent was synthesized for the first time. The morphology of the adsorbents was discussed by scanning electron microscopy (SEM). In adsorption experiments under different working conditions, MIL-96(Al) exhibited a stable equilibrium adsorption capacity, while the addition of only 0.50% mass fraction of multi-walled carbon nanotubes increased equilibrium adsorption capacity by approximately 30%. The enhancement ratio of six composite adsorbents compared to MIL-96(Al) in equilibrium adsorption capacities was almost constant under different working conditions. The adsorption rate of MIL-96(Al) could reach up to 0.573 g g−1 h, while that of the composite adsorbents under the same conditions was 0.763 g g−1 h. MIL-96(Al) could be completely desorbed within 40 min at 110 °C, and the optimal desorption temperature of MWCNT/MIL-96(Al) was reduced to 100 °C. The cyclic stability of the seven adsorbents was also confirmed through cyclic regeneration experiments. The experimental results indicated that the MWCNT/MIL-96(Al) composite adsorbent was a potential adsorbent for solar-driven atmospheric water harvesting in arid regions.

A Porous Carbazolic Al-MOF for Efficient Aerobic Photo-Oxidation of Sulfides into Sulfoxides under Air.

A robust, microporous, and photoactive aluminum-based metal-organic framework (Al-MOF, LCU-600) has been assembled by an in situ-formed [Al3O(CO2)6] trinuclear building unit and a tritopic carbazole ligand. LCU-600 shows a high water stability and permanent porosity for N2 and CO2 adsorption. Notably, the incorporation of photoresponsive carbazole moieties into LCU-600 makes it a highly efficient and recyclable photocatalyst for aerobic photo-oxidation of sulfides into sulfoxides under an air atmosphere at room temperature. Mechanism investigations unveil that photogenerated holes (h+), superoxide radical anion (O2•-), and singlet oxygen (1O2) are critical active spices for the photo-oxidation reaction performed in an air atmosphere.

Harvesting Water from Air with High-Capacity, Stable Furan-Based Metal-Organic Frameworks.

We synthesized two isoreticular furan-based metal-organic frameworks (MOFs), MOF-LA2-1(furan) and MOF-LA2-2(furan) with rod-like secondary building units (SBUs) featuring 1D channels, as sorbents for atmospheric water harvesting (LA = long arm). These aluminum-based MOFs demonstrated a combination of high water uptake and stability, exhibiting working capacities of 0.41 and 0.48 gwater/gMOF (under isobaric conditions of 1.70 kPa), respectively. Remarkably, both MOFs showed a negligible loss in water uptake after 165 adsorption-desorption cycles. These working capacities rival that of MOF-LA2-1(pyrazole), which has a working capacity of 0.55 gwater/gMOF. The current MOFs stand out for their high water stability, as evidenced by 165 cycles of water uptake and release. MOF-LA2-2(furan) is the first aluminum MOF to employ a double 'long arm' extension strategy, which is confirmed through single-crystal X-ray diffraction (SCXRD). The MOFs were synthesized by using a straightforward synthesis route. This study offers valuable insights into the design of durable, water-stable MOFs and underscores their potential for efficient water harvesting.

Enhancing CO2/N2 and CH4/N2 separation performance by salt-modified aluminum-based metal-organic frameworks.

The energy-saving separation of CO2/N2 and CH4/N2 in the energy industry facilitates the reduction of greenhouse gas emissions and replenishes energy resources, but is a challenging separation process. The trade-off between adsorption capacity and selectivity of the adsorbents is one of the key bottlenecks in adsorption separation technologies' large-scale application in the above separation task. Herein, we introduced a series of fluoroborate or fluorosilicate salts (Cu(BF4)2, Zn(BF4)2 and ZnSiF6) into the open coordination nitrogen sites of aluminum-based metal-organic frameworks (MOF-253) to create multiple binding sites to simultaneously enhance the adsorption capacity and selectivity for the target gas. By the synergistic adsorption effect of metal ions (Cu2+ or Zn2+) and fluorinated anions (BF4- or (SiF6)2-), the single-component adsorption capacity and selectivity of salt-modified MOF-253 (MOF-253@Cu(BF4)2, MOF-253@Zn(BF4)2 and MOF-253@ZnSiF6) for CO2 and CH4 were effectively improved when compared to pristine MOF-253 at 298 K and 1 bar. In addition, the salt-modified MOF-253 has a moderate adsorption heat (<30 kJ mol-1) which could be rapidly regenerated at low energy by evacuation desorption. As confirmed by the ambient breakthrough experiments of MOF-253 and MOF-253@ZnSiF6, the real separation performance for both CO2/N2 (1/4) and CH4/N2 (1/4) was obviously improved. This work provides a feasible post-modification strategy on uncoordinated sites of the framework to improve adsorption separation performance and promote the development of ideal adsorbents with a view to realizing their application in the energy industry.

A robust aluminum-octacarboxylate framework with scu topology for selective capture of sulfur dioxide

A novel 4,8-c scu-type aluminum-based metal–organic framework shows a robust structure, reversible SO2 adsorption with high capacity, and high SO2/N2, SO2/CO2, and SO2/CH4 selectivities.

Separation of High-Purity C2H2 from Binary C2H2/CO2 Using Robust Al-Based MOFs Comprising Nitrogen-Containing Heterocyclic Dicarboxylate.

In this study, three nitrogen-containing aluminum-based metal-organic frameworks (Al-MOFs), namely, CAU-10pydc, MOF-303, and KMF-1, were investigated for the efficient separation of a C2H2/CO2 gas mixture. Among these three Al-MOFs, KMF-1 demonstrated the highest selectivity for C2H2/CO2 separation (6.31), primarily owing to its superior C2H2 uptake (7.90 mmol g-1) and lower CO2 uptake (2.82 mmol g-1) compared to that of the other two Al-MOFs. Dynamic breakthrough experiments, using an equimolar binary C2H2/CO2 gas mixture, demonstrated that KMF-1 achieved the highest separation performance. It yielded 3.42 mmol g-1 of high-purity C2H2 (>99.95%) through a straightforward desorption process under He purging at 298 K and 1 bar. To gain insights into the distinctive characteristics of the pore surfaces of structurally similar CAU-10pydc and KMF-1, we conducted computational simulations using canonical Monte Carlo and dispersion-corrected density functional theory methods. These simulations revealed that the secondary amine (C2N-H) groups in KMF-1 played a more significant role in differentiating between C2H2 and CO2 compared to that of the N atoms in CAU-10pydc and MOF-303. Consequently, KMF-1 emerged as a promising adsorbent for the separation of high-purity C2H2 from binary C2H2/CO2 gas mixtures.