Double-walled Al-based MOF with large microporous specific surface area for trace benzene adsorption

doi:10.21203/rs.3.rs-3453152/v1

Download PDF

Article

Double-walled Al-based MOF with large microporous specific surface area for trace benzene adsorption

https://doi.org/10.21203/rs.3.rs-3453152/v1

This work is licensed under a CC BY 4.0 License

Journal Publication

published 13 Apr, 2024

Read the published version in Nature Communications →

Version 1

posted

You are reading this latest preprint version

Double-walled metal-organic frameworks (MOFs), synthesized using Zn and Co, are potential porous materials for trace benzene adsorption. Aluminum is with low-toxicity and abundance in nature, in comparison with Zn and Co. Therefore, a novel double-walled Al-based MOF, named as ZJU-520(Al), with large microporous specific surface area of 2235 m²/g, pore size distribution in the range of 9.26 – 12.99 Å and excellent thermal-chemical stability, was synthesized in this study. ZJU-520(Al) is consisted by helical chain of AlO₆ clusters and 4,6-Di(4-carboxyphenyl)pyrimidine ligands. It exhibits unprecedented trace benzene adsorption up to 5.98 mmol/g at 298 K and P/P₀ = 0.01. Adsorbed benzene molecules are trapped on two types of sites. One (site I) is near the AlO₆ clusters, another (site II) is near the N atom of ligands, using Grand Canonical Monte Carlo (GCMC) simulations. ZJU-520(Al) also can effectively separate trace benzene from mixed vapor flow of benzene and cyclohexane, due to the adsorption affinity of benzene higher than that of cyclohexane. Therefore, ZJU-520(Al) is a potential adsorbent for trace benzene adsorption and benzene/cyclohexane separation.

Physical sciences/Chemistry/Materials chemistry/Metal–organic frameworks

Physical sciences/Materials science/Nanoscale materials/Organic–inorganic nanostructures

Metal-organic framework

Double-walled structure

Aluminum

Benzene

Adsorption and separation

Double-walled metal-organic frameworks (MOFs), such as BUT-53(Co) to BUT-57(Co) ¹ and BUT-58(Zn) ¹, with highly customizable and tunable porous structure, exhibit excellent trace adsorption for volatile organic compounds (VOCs) such as benzene due to their unique double-walled structure. For example, BUT-54(Co) showed benzene adsorption amount of 4.31 mmol/g at P/P₀ = 0.01 ¹, which is the largest one reported. However, those double-walled MOFs are synthesized using Zn and Co with high price and toxicity. Al element is with low toxicity and abundance in nature ^{2, 3, 4}, compared with Zn and Co. Moreover, the microporous specific surface areas of those reported double-walled MOFs are in the range of 849–1128 m²/g ¹, lower than that of reported Al-based MOFs, such as Al-PyrMOF (1592 m²/g) ⁵, Al-PMOF (1815 m²/g) ⁵ and MOF-519(Al) (2400 m²/g) ⁶, limiting its adsorption for VOCs including benzene ⁷. Therefore, synthesizing double-walled Al-based MOFs with high microporous specific surface area could be a better strategy for trace adsorption of VOCs including benzene.

Herein, a novel double-walled Al-based MOF, named as ZJU-520(Al), was synthesized by helical chain of AlO₆ cluster and 4,6-Di(4-carboxyphenyl)pyrimidine (H₂DBP) ligands in this study. This ZJU-520(Al) is with large microporous specific surface area of 2235 m²/g and pore size distribution (PSD) in the range of 9.26–12.99 Å. It exhibits excellent thermal-chemical stability, showing its framework can remain in the pH range of 4 to 12 and at temperatures up to 550 ℃. Most interestingly, it can adsorb trace benzene up to unprecedented 5.98 mmol/g at P/P₀ = 0.01 and 298 K, and separate trace benzene from mixed vapor flow of benzene and cyclohexane, suggesting that it is a potential adsorbent for trace benzene adsorption/separation.

Crystal of ZJU-520(Al) is rod-shaped (Fig. S1), with high purity due to the agreement of the theorical powder X-ray diffraction (PXRD) patterns with the experimental PXRD patterns (Fig. S2). ZJU-520(Al) is in the tetragonal crystal system with I4₁md space group and lattice parameters (a = b = 36.65 Å, c = 10.56 Å), identified by single crystal X-ray diffraction (SC-XRD) analysis (Table S1-3). Each Al³⁺ center, in the helical chain of AlO₆ cluster, is octahedrally coordinated with O atoms from four DBP²⁻ ligands and two bridging hydroxyl anions (Fig. 1), forming the double-walled structure of ZJU-520(Al) (Fig. 1). The distance of double-wall on ZJU-520(Al) is 3.75 Å (Fig. 1), slightly higher than that of BUT-53(Co), i.e., 3.00 Å, similar to that of BUT-54(Co) to BUT-58(Zn) (Fig. S3) ¹. The AlO₆ clusters further coordinate to DBP²⁻ ligands, forming the 3D framework (Fig. 1), identified by the slight blue shift of the peaks of carbonyl group at 1589 cm^− 1 in Fourier-transform infrared spectra of ZJU-520(Al) from that of H₂DBP at 1682 cm^− 1 (Fig. S4). ZJU-520(Al) is with two types of 1D channels, named as A with narrow channel and B with wide channel here (Fig. 1), due to the rotation of AlO₆ clusters with angle about 11.01° (Fig. S5), compared with the AlO₆ clusters of CAU-10(Al) ^{8, 9}. The elemental contents of ZJU-520(Al), including Al, C, O and N, are uniform dispersion and in line with the molecule formula (C₂₁H₁₉AlN₃O₇) obtained from SC-XRD analysis (Table S1), identified by energy dispersive spectroscope (EDS) mapping and EDS linear scans (Fig. S6).

ZJU-520(Al) has special surface area (S_BET) of 2235 m²/g, obtained from nitrogen (N₂) adsorption-desorption isotherm at 77 K (Fig. 2a) by Brunauer-Emmett-Teller (BET) method (Fig. S7), in agreement with the theorical specific surface area of 2348 m²/g from Grand Canonical Monte Carlo (GCMC) simulation ^{10, 11, 12}, larger than the reported double-walled MOFs ¹ in the range of 849–1128 m²/g (Table S4). For example, the S_BET of double-walled ZJU-520(Al) is 1.98 times of that of double-walled BUT-54(Co) (1128 m²/g) and 2.63 times of that of double-walled BUT-58(Zn) (849 m²/g) ¹. The total pore volume of ZJU-520(Al) is 0.84 cm³/g (Fig. S8), in agreement with the calculated theorical pore volume of 0.95 cm³/g by GCMC simulation ¹³. ZJU-520(Al) is a microporous material, identified by its N₂ adsorption-desorption isotherm belonging to type I ^{9, 14, 15} (Fig. 2a) and its pore size distribution (PSD) in the range of 9.26–12.99 Å with pore dimensions centered at 10.96 Å (Fig. S8). It is with two types of microporous channels (Fig. S9) by GCMC simulation, using N₂ as probe ¹⁶. One channel, named as A, is with the distance of 10.76–16.07 Å (Fig. S10a), while another channel, named as B, is slightly larger with the distance of 11.09–16.67 Å (Fig. S10b), in line with the result of PSD (Fig. S8). The interplanar spacing is 12.83 Å along the (2, 2, 0) direction, observed from high-resolution transmission electron microscopy (HRTEM) image (Fig. 2b), in agreement with the theorical interplanar spacing of 12.96 Å (Table S5). Furthermore, the channels along the (2, 2, 0) direction in the two-dimensional image, calculated by the inverse Fourier transformation from amplitudes extracted from HRTEM image ^{17, 18}, is in good agreement with the framework of ZJU-520(Al) (Fig. 2b).

ZJU-520(Al) is with excellent thermal stability, identified by the thermal gravimetric analysis (TGA) ^{12, 19} of activated ZJU-520(Al) up to 550 ℃ (Fig. 2c). The quality of ZJU-520(Al) has decreased by 7.78% as the temperature rises to 100 ℃, which should be attributed to the evaporation of water molecules ^{20, 21}. The framework of ZJU-520(Al) also exhibits excellent chemical stability, identified by the N₂ adsorption-desorption isotherms (Fig. 2a) and PXRD patterns (Fig. 2d) of ZJU-520(Al) without obvious changes, after being treated with water (pH = 7), HCl solution (pH = 4) and NaOH solution (pH = 12). The excellent thermal-chemical stability of ZJU-520(Al) can be attributed to electronic-withdrawing effect of pyrimidine N atoms on H₂DBP ligands (Fig. S11 and Table S6) enhancing the Al – O coordinate bond ^{22, 23}.

ZJU-520(Al) can adsorb trace benzene up to 5.98 mmol/g (Q_0.01) at 298 K and P/P₀ = 0.01 (Fig. 3a,b), higher than double-walled BUT-54(Co) (Q_0.01 = 4.31 mmol/g) ¹ and other previously reported benzene adsorbents (Fig. 4a and Table S4), including PAF-1 (Q_0.01 = 3.65 mmol/g) ²⁴, ZJU-620(Al) (Q_0.01 = 3.80 mmol/g) ⁴ and UiO-66(Cu^II) (Q_0.01 = 3.92 mmol/g) ²⁵. Isotherms of benzene adsorption on ZJU-520(Al) are quickly increased at trace concentration and reached a plateau at P/P₀ = 0.10 (Fig. 4b), indicating the high affinity between adsorbates and framework ²⁶. Even at 308 K, ZJU-520(Al) can keep excellent trace benzene adsorption of 3.63 mmol/g (Q_0.01) and rapidly up to 8.09 mmol/g at P/P₀ = 0.02 (Fig. 4b). It also has excellent saturation adsorption capacity for benzene (12.07 mmol/g), toluene (6.91 mmol/g), ethylbenzene (3.76 mmol/g), ortho-xylene (4.01 mmol/g), meta-xylene (3.67 mmol/g), para-xylene (4.45 mmol/g) and cyclohexane (5.27 mmol/g) at 298 K (Fig. 3a,b). Besides, ZJU-520(Al) is with excellent regenerate ability, due to benzene adsorption without obvious loss at least 4 times (Fig. 4c) and its framework with integrality due to the PXRD patterns of ZJU-520(Al) without obvious changes (Fig. S12) after cyclical benzene adsorption-desorption experiments.

The isosteric heat (∆H) values of benzene adsorption on ZJU-520(Al) are modestly high and increased in two steps (Fig. 4d), calculated from the isotherms at four temperatures (Fig. 4b). One step is increased at low benzene adsorption (0.00013–1.10 mmol/g) with the ∆H values of 39.68–41.59 kJ/mol owing to the dominance of guest – host interactions ²⁵. Another step is increased at high benzene adsorption (3.56–9.79 mmol/g) with the ∆H values of 40.02–45.54 kJ/mol due to strong guest – guest interactions, such as the packing of benzene molecules ²⁵. The high ∆H values indicates that strong interaction with benzene molecules existed even at low concentration, in agreement with its type I benzene adsorption isotherm (Fig. 3a). Moreover, the ∆H value at benzene loading of 1.00 mmol/g is 41.58 kJ/mol, close to the other MOFs with excellent trace benzene adsorption, such as UiO-66-defect (47.00 kJ/mol) ²⁵, MFM-300 (Sc) (42.00 kJ/mol) ²⁵ and BUT-67(Zr) (55.00 kJ/mol) ²⁴, indicating that it needs moderate energy for regeneration ²⁷.

Grand Canonical Monte Carlo (GCMC) simulations are performed to gain insight into the benzene adsorption sites on ZJU-520(Al). Before GCMC simulation, the partial charges of ZJU-520(Al) are extracted from density-derived electrostatic and chemical (DDEC) method ^{28, 29} (Fig. S13 and Table S7) for electrostatic interactions. The simulated benzene adsorption isotherm on ZJU-520(Al) is well consistent with the experimental results at low to middle pressures (Fig. S14), but slightly smaller than the experimental results at high pressures, due to the condensation of benzene vapor ³⁰. For example, the theorical benzene adsorption is 6.29 mmol/g at P/P₀ = 0.01 and 298 K, in agreement with the experimental value (5.98 mmol/g) (Fig. 3a). There exist two types of benzene binding conformations, i.e., site I near the AlO₆ clusters and site II near the N atom of ligands (Fig. 5a,b and Movie S1 for P/P₀ = 0.01), due to host – guest interactions (Fig. 4d, in blue area), identified by the slices of calculated potential field. As is also observed for toluene adsorption (Fig. S15, Movies S2). With the P/P₀ up to 0.10, benzene molecules also can be adsorbed in the center of channel of ZJU-520(Al) (Fig. 5c), due to strong guest – guest interactions (Fig. 4d, in pink area). Benzene molecules, in channel A and B of ZJU-520(Al), preferentially adsorb in site I (Fig. 5a) due to Al – π interactions ³¹ and C – H ⋯ X interactions, and then, with the increasing of P/P₀, such as up to 0.01, to occupy the site II (Fig. 5b) due to C – H ⋯ N interactions ^{1, 32}. Taking benzene molecules in channel A at P/P₀ = 0.01 and 298 K for example, benzene molecules in site I bound to Al atoms of AlO₆ clusters through Al – π interactions ³¹ with the distance of 5.98–8.16 Å (Fig. 5d and Fig. S16a, in bule lines), and also bound to the C – H sectors of ligands through C – H(L) ⋯ π(Bz) interactions ³³ with the distance of 3.13–4.95 Å (Fig. 5d and Fig. S16b, in pink lines), where H(L) represents the H atom of DBP ligands and Bz represents benzene molecules. Moreover, benzene molecules also could bind to ligands through C – H(Bz) ⋯ π(L) interactions with the distance of 3.90–5.79 Å (Fig. 5d and Fig. S16c, in green lines), where H(Bz) represents the H atom of benzene molecules. For site II, benzene molecules bound to N atoms of ligands through C – H(Bz) ⋯ N(L) interactions ¹ with the distance of 2.63–4.57 Å (Fig. 5d and Fig. S16d, in red lines), where N(L) represents the N atom of DBP ligands. In addition, benzene molecules in site I and site II are all interacted with other guest molecules, through C – H(Bz) ⋯ π(Bz) interactions with the distance of 3.92–5.52 Å (Fig. 5e and Fig. S16e, in purple lines). Therefore, the host – guest interactions and guest – guest interactions drive the benzene adsorption by ZJU-520(Al), even at P/P₀ up to 0.01.

The preferential adsorption of benzene molecules in site I (Fig. 5a) also can be explained by the calculated binding energy (–69.68 kJ/mol) between benzene molecules and ZJU-520(Al), which is higher than that in site II (–46.23 kJ/mol). The binding energy is calculated based on the low-energy structure role of ZJU-520(Al) with adsorbed benzene molecules, using the density functional theory (DFT) calculation method ^{34, 35, 36, 37}. Benzene molecules in site I have stronger charge density than that in site II, making benzene molecules preferentially adsorb in site I rather than site II especially at trace concentration (Fig. 5a,b), due to the electron accumulation ³⁸ in the center of benzene molecule (site I) and depletion ¹ that of benzene molecule (site II and center) (Fig. S17).

Separating benzene (Bz) from cyclohexane (Cy) is a very difficult work in industry such as nylon production ^{21, 39}, due to similar boiling points of Bz (353.25 K) with Cy (353.85 K) ⁴⁰ and similar kinetic diameters of Bz (5.90 Å) with Cy (6.20 Å) ⁴¹ (Fig. 6a). Adsorption of benzene by ZJU-520(Al) (5.98 mmol/g), at 298 K and P/P₀ = 0.01, is 2.56 times that of cyclohexane (2.33 mmol/g) (Fig. 3a). The ideal adsorbed solution theory (IAST) selectivity ^{27, 42} of Bz/Cy mixture at vapor volume of 50/50 by ZJU-520(Al) is 29.86 (Fig. S18), exceeding that by CUB-5 (4.2) ⁴³, MFOF-1 (5.3) ⁴⁴ and Mn-TCNQ-bpy (15.2) ⁴⁴. In the breakthrough experiments of Bz/Cy (5/95, in red line) and Bz/Cy (1/99, in black line) mixture vapor (Fig. 6b), pure cyclohexane elutes with high-purity firstly, whereas trace benzene still is adsorbed in the fixed bed and retained with a longer time course (Fig. 6b), further indicating its excellent trace benzene separation from mixed vapors of Bz/Cy. ZJU-520(Al) is also with excellent recyclability for Bz/Cy separation at least 4 times (Fig. 6c). Excellent Bz/Cy separation of ZJU-520(Al) could be attributed to the higher adsorption affinity with benzene than cyclohexane molecules, identified by the higher ∆H of benzene than that of cyclohexane at trace adsorption of benzene and cyclohexane less than 3.89 mmol/g (Fig. S19a), calculated from benzene isotherms (Fig. 4b) and cyclohexane isotherms (Fig. S19b) at various temperatures. Using multicomponent GCMC simulations of benzene and cyclohexane adsorptions ⁴⁵, the adsorption site of cyclohexane is near the AlO₆ cluster due to C – H(Cy) ⋯ N(L) interactions with the distance of 3.20–5.54 Å (Fig. 6d and Fig. S20a, in black lines) and C – H(Cy) ⋯ π(L) interactions with the distance of 2.59–4.83 Å (Fig. 6d and Fig. S20b, in orange lines), where H(Cy) represents the H atom of cyclohexane molecules, while the adsorbed benzene molecules interact with ZJU-520(Al) through multiple interactions, including Al – π interaction with the distance of 5.67–6.73 Å (Fig. 6e and Fig. S21a, in blue lines), C – H(L) ⋯ π(Bz) interactions with the distance of 3.11–6.00 Å (Fig. 6e and Fig. S21b, in pink lines), C – H(Bz) ⋯ π(L) interactions with the distance of 3.21–4.91 Å (Fig. 6e and Fig. S21c, in green lines), C – H(Bz) ⋯ N(L) with the distance of 3.09–6.37 Å (Fig. 6e and Fig. S21d, in red lines) and π(Bz) ⋯ π(L) interactions with the distance of 3.81–7.33 Å (Fig. 6e and Fig. S21e, in brown lines). Therefore, ZJU-520(Al) exhibits more multiple interactions with benzene than that with cyclohexane, resulting in the excellent Bz/Cy separation of ZJU-520(Al), even at trace benzene concentration.

ZJU-520(Al), as a novel double-walled Al-based MOF, exhibits large microporous specific surface area of 2235 m²/g, PSD in the range of 9.26–12.99 Å and excellent thermal-chemical stability. It is with trace benzene adsorption of 5.98 mmol/g, at 298 K and P/P₀ = 0.01, which is the largest one reported. There exist two types of sites for benzene adsorption, site I near the AlO₆ clusters due to Al – π interactions and site II near the N atom of ligands due to C – H ⋯ X interactions, such as C – H(L) ⋯ π(Bz), C – H(Bz) ⋯ π(L) and C – H(Bz) ⋯ N(L) interactions, using GCMC simulations. ZJU-520(Al) can separate trace benzene from mixed vapor flow of benzene and cyclohexane effectively, due to the higher adsorption affinity of benzene compared to cyclohexane. Furthermore, it is with good recyclability for trace benzene adsorption and separation of benzene/cyclohexane at least 4 times. Therefore, ZJU-520(Al) can be a potential material for trace benzene adsorption and benzene/cyclohexane separation.

Acknowledgements

This work was supported partly by the National Key Research and Development Program of China (2021YFC1809204), the National Natural Science Foundation of China (42192573, 21621005 and U21A20163), and the Fundamental Research Funds for the Central Universities (226-2022-00212).

He, T. et al. Trace removal of benzene vapour using double-walled metal-dipyrazolate frameworks. Nature Materials 21, 689 – 695 (2022).
Lenzen, D. et al. A metal-organic framework for efficient water-based ultra-low-temperature-driven cooling. Nature Communications 10, 1 – 9 (2019).
Woellner, M. et al. Adsorption and detection of hazardous trace gases by metal-organic frameworks. Advanced Materials 30, 1704679 – 1704685 (2018).
Hu, L. et al. A novel aluminum-based metal-organic framework with uniform micropores for trace BTEX adsorption. Angewandte Chemie International Edition 62, e202215296 (2023).
Boyd, P. G., Chidambaram, A., García-Díez, E., Ireland, C. P. & Smit, B. Data-driven design of metal-organic frameworks for wet flue gas CO₂ capture. Nature 576, 253 – 256 (2019).
Zheng, Z., Zhang, O., Borgs, C., Chayes, J. T. & Yaghi, O. M. ChatGPT chemistry assistant for text mining and the prediction of MOF synthesis. Journal of the American Chemical Society 145, 18048 – 18062 (2023).
Wang, H., Lustig, W. P. & Li, J. Sensing and capture of toxic and hazardous gases and vapors by metal-organic frameworks. Chemical Society Reviews 47, 4729 – 4756 (2018).
Pei, J. et al. Dense packing of acetylene in a stable and low-cost metal-organic framework for efficient C₂H₂/CO₂ separation. Angewandte Chemie International Edition 60, 25068 – 25074 (2021).
Lenzen, D. et al. Scalable green synthesis and full-scale test of the metal-organic framework CAU-10-H for use in adsorption-driven chillers. Advanced Materials 30, 1705869 – 1705878 (2018).
Ghalei, B. et al. Enhanced selectivity in mixed matrix membranes for CO₂ capture through efficient dispersion of amine-functionalized MOF nanoparticles. Nature Energy 2, 17086 – 17095 (2017).
Vismara, R. et al. CO₂ adsorption in a robust iron(III) pyrazolate-based MOF: Molecular-level details and frameworks dynamics from powder X-ray diffraction adsorption isotherms. Advanced Materials 12, 2209907 – 2209923 (2023).
Knebel, A. & Caro, J. Metal-organic frameworks and covalent organic frameworks as disruptive membrane materials for energy-efficient gas separation. Nature Nanotechnology 17, 911 – 923 (2022).
Cho, H. S. et al. Isotherms of individual pores by gas adsorption crystallography. Nature Chemistry 11, 562 – 570 (2019).
Wang, Z. et al. Microporous polymer adsorptive membranes with high processing capacity for molecular separation. Nature Communications 13, 4169 – 4178 (2022).
Zhang, J. et al. Embedded nano spin sensor for in situ probing of gas adsorption inside porous organic frameworks. Nature Communications 14, 4922 – 4932 (2023).
Connolly, M. L. Solvent-accessible surfaces of proteins and nucleic acids. Science 221, 709 – 713 (1983).
Ikezoe, Y., Washino, G., Uemura, T., Kitagawa, S. & Matsui, H. Autonomous motors of a metal-organic framework powered by reorganization of self-assembled peptides at interfaces. Nature Materials 11, 1081 – 1085 (2012).
Song, Y. et al. High-yield solar-driven atmospheric water harvesting of metal-organic framework derived nanoporous carbon with fast-diffusion water channels. Nature Nanotechnology 17, 857 – 863 (2022).
Matemb Ma Ntep, T. J. et al. When polymorphism in metal-organic frameworks enables water sorption profile tunability for enhancing heat allocation and water harvesting performance. Advanced Materials 12, 2211302 – 2211316 (2023).
Cui, P. F., Liu, X. R., Lin, Y. J., Li, Z. H. & Jin, G. X. Highly selective separation of benzene and cyclohexane in a spatially confined carborane metallacage. Journal of the American Chemical Society 144, 6558 – 6565 (2022).
Yao, H. et al. Adsorptive separation of benzene, cyclohexene, and cyclohexane by amorphous nonporous amide naphthotube solids. Angewandte Chemie International Edition 59, 19945 – 19950 (2020).
Howarth, A. J. et al. Chemical, thermal and mechanical stabilities of metal-organic frameworks. Nature Reviews Materials 1, 15018 – 15028 (2016).
Yuan, S. et al. Stable metal-organic frameworks: Design, synthesis, and applications. Advanced Materials 30, 1704303 – 1704323 (2018).
Xie, L., Liu, X., He, T. & Li, J. Metal-organic frameworks for the capture of trace aromatic volatile organic compounds. Chem 4, 1911 – 1927 (2018).
Han, Y. et al. Control of the pore chemistry in metal-organic frameworks for efficient adsorption of benzene and separation of benzene/cyclohexane. Chem 9, 739 – 754 (2023).
Yang, K. & Xing, B. Adsorption of organic compounds by carbon nanomaterials in aqueous phase: Polanyi theory and its application. Chemical Reviews 110, 5989 – 6008 (2010).
Hu, Y. et al. New-generation anion-pillared metal-organic frameworks with customized cages for highly efficient CO₂ capture. Advanced Functional Materials 56, 2213915 – 2213926 (2023).
Moghadam, P. Z. et al. Computer-aided discovery of a metal-organic framework with superior oxygen uptake. Nature Communications 9, 1378 – 1389 (2018).
Gong, W. et al. Creating optimal pockets in a clathrochelate-based metal-organic framework for gas adsorption and separation: Experimental and computational studies. Journal of the American Chemical Society 144, 3737 – 3745 (2022).
Yang, Q. et al. Capillary condensation under atomic-scale confinement. Nature 588, 250 – 253 (2020).
Wei, D. et al. Ion-migration inhibition by the cation-π interaction in perovskite materials for efficient and stable perovskite solar cells. Advanced Materials 30, 1707583 – 1707594 (2018).
Vornholt, S. M. & Morris, R. E. Separating out the middle. Nature Materials 18, 910 – 911 (2019).
Li, W. B. et al. Fluorescence enhancement of a metal-organic framework for ultra-efficient detection of trace benzene vapor. Angewandte Chemie International Edition 56, e202303500 (2023).
Wang, Y. et al. Construction of fluorinated propane-trap in metal-organic frameworks for record polymer-grade propylene production under high humidity conditions. Advanced Materials 35, 2207955 – 2207963 (2023).
Vogel, D. J., Rimsza, J. M. & Nenoff, T. M. Prediction of reactive nitrous acid formation in rare-earth MOFs via ab initio molecular dynamics. Angewandte Chemie International Edition 60, 11514 – 11522 (2021).
Yang, S. et al. Preparation of highly porous metal-organic framework beads for metal extraction from liquid streams. Journal of the American Chemical Society 142, 13415 – 13425 (2020).
Zheng, B. et al. Quantum informed machine-learning potentials for molecular dynamics simulations of CO₂’s chemisorption and diffusion in Mg-MOF-74. ACS Nano 17, 5579 – 5587 (2023).
Li, J. et al. Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO₂ photoreduction to CH₄. Nature Catalysis 4, 719 – 729 (2021).
Zhao, X., Wang, Y. X., Li, D. S., Bu, X. H. & Feng, P. Y. Metal-organic frameworks for separation. Advanced Materials 30, 1705189 – 1705198 (2018).
Zhou, J., Yu, G., Li, Q., Wang, M. & Huang, F. Separation of benzene and cyclohexane by nonporous adaptive crystals of a hybrid[3]arene. Journal of the American Chemical Society 142, 2228 – 2232 (2020).
Bury, W., Walczak, A. M., Leszczyński, M. K. & Navarro, J. A. R. Rational design of noncovalent diamondoid microporous materials for low-energy separation of C6-hydrocarbons. Journal of the American Chemical Society 140, 15031 – 15037 (2018).
Li, S., Han, W., An, Q. F., Yong, K. T. & Yin, M. J. Defect engineering of MOF-based membrane for gas separation. Advanced Functional Materials 10, 2303447 – 2303456 (2023).
Macreadie, L. K. et al. CUB-5: A contoured aliphatic pore environment in a cubic framework with potential for benzene separation applications. Journal of the American Chemical Society 141, 3828 – 3832 (2019).
Mukherjee, S. et al. Advances in adsorptive separation of benzene and cyclohexane by metal-organic framework adsorbents. Coordination Chemistry Reviews 437, 213852 – 213865 (2021).
Zhang, C. et al. Enantiomeric MOF crystals using helical channels as palettes with bright white circularly polarized luminescence. Advanced Materials 32, 2002914 – 2002923 (2020).

There is NO Competing Interest.

Movie1ZJU520Benzene.mp4
MovieS1
Movie2ZJU520Toluene.mp4
MovieS2
SI.docx
Supporting Information
GraphicalAbstract.png
Graphical Abstract Double-walled Al-based MOF, named as ZJU-520(Al), with large microporous specific surface area of 2235 m²/g, can adsorb trace benzene up to unprecedented 5.98 mmol/g at 298 K and P/P₀ = 0.01.

Download PDF

Journal Publication

published 13 Apr, 2024

Read the published version in Nature Communications →

Version 1

posted

You are reading this latest preprint version

Double-walled Al-based MOF with large microporous specific surface area for trace benzene adsorption

Status:

Journal Publication

Version 1

Abstract

Figures

1. Introduction

2. Results and Discussion

3. Conclusion

Declarations

Acknowledgements

References

Additional Declarations

Supplementary Files

Status:

Journal Publication

Version 1