Systematic evaluation of water adsorption in isoreticular UiO-type metal–organic frameworks

Lu, Feng-Fan; Gu, Xiao-Wen; Wu, Enyu; Li, Bin; Qian, Guodong

doi:10.1039/d2ta07392g

Cited by 28 publications

(22 citation statements)

References 84 publications

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“…Furthermore, the amplitude of the OW•••µ ( -OH RDF is significantly higher compared to that of the OW•••Olinker RDF, thus confirming that the µ ( -OH is the most favorable binding site at low RH. This finding is consistent with previous computational studies showing that water preferentially binds to the μ3-OH in UiO-66 13,21,25,26. Moreover, this aligns with the experimental observation that µ ( -OH is the primary adsorption site for water in MOF-801, a MOF containing the same inorganic SBUs as UiO-66 11.…”

supporting

confidence: 92%

“…-OH) incorporated within the framework. [18][19][20][21] In spite of these promising features, the application of MOFs in water harvesting technologies is still an emerging area of research and more fundamental insights into the adsorption mechanisms are required in order to scale up this technology.…”

Section: Introductionmentioning

confidence: 99%

“…Previous computational studies of UiO-66 have employed generic force fields 13,21,24,25 to conduct molecular dynamics (MD) simulations aimed at understanding the key water-MOF interactions and the diffusion process of water across the MOF cavities. Caratelli et al also performed a vibrational spectroscopy study of water within defective UiO-66 using ab initio MD simulations.…”

Section: Introductionmentioning

confidence: 99%

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Computational Insights into the Interaction of Water with the UiO-66 Metal-Organic Framework and Its Functionalized Derivatives

Zhang

Paesani

Lessio

2023

Preprint

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The UiO-66 metal-organic framework (MOF) has been identified as a promising hydrophilic material for water harvesting. Recent studies show that its water uptake ability at low relative humidity (RH) can be improved by incorporating hydrophilic functional groups into the framework. In this work, we provide computational insights into the adsorption of water in UiO-66 and its functionalized derivatives to reveal the role played by different adsorption sites and functional groups in the adsorption mechanism. We started by developing molecular models for UiO-66, UiO-66-NH2, UiO-66-OH, and UiO-66-(OH)2 compatible with the MB-pol data-driven many-body potential of water. We then benchmarked these models against ab initio data. We used these models to perform molecular dynamics simulations and calculate radial distribution functions, IR spectra, and two-dimensional density distribution maps for water in the MOFs. These results consistently show that the μ3-OH sites are the preferential interaction sites for water in UiO-66 and all its variants, and the formation of localised water clusters inside the octahedral pores is responsible for the abrupt step in the experimental adsorption isotherms. Furthermore, the presence of functional groups in the framework allows water to cluster in the octahedral pores at lower RH, thus making the MOF a more efficient water harvester. Overall, this study provides molecular-level insights into the pore filling process of UiO-66 and its functionalized derivatives, which are needed for the design of efficient water harvesting materials based on MOFs.

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supporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Computational Insights into the Interaction of Water with the UiO-66 Metal-Organic Framework and Its Functionalized Derivatives

Zhang

Paesani

Lessio

2023

Preprint

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“…Metal-organic framework (MOF) nanomaterials, such as MOF-PNIPAM membranes [ 8 ], ZIF-8 MOF [ 9 ], PCL/MOF-545 [ 10 ], HKUST-1 [ 11 ], and ZIF-8 [ 12 ], are widely used for drug delivery, diagnosis [ 13 , 14 ], as adsorbents [ 15 ], and for photocatalysis, for the removal of sulfonamide, CIP, and tetracycline antibiotics, respectively, from an aqueous solution through the adsorption technique. In addition, MOFs have attracted significant attention in photocatalysis technology, due to their semiconductor-like behavior, which transfers photogenerated charges to the reactive sites of a ligand-to-metal charge transfer (LMCT) for the in-situ decomposition of organic compounds, to form CO 2 and water [ 16 ].…”

Section: Introductionmentioning

confidence: 99%

Enhanced Visible-Light-Responsive Photocatalytic Degradation of Ciprofloxacin by the CuxO/Metal-Organic Framework Hybrid Nanocomposite

Tsai

Huang²,

Horng³

et al. 2023

Nanomaterials

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Ciprofloxacin (CIP) is a commonly used antibiotic, however, once in the environment, it is highly toxic with a poor biodegradability. Given these attributes, an effective strategy for the removal of CIP is urgently needed for the protection of water resources. Herein, a novel copper metal-organic framework (CuxO/MOF) multifunctional material has been produced, in this work, by the calcination of Cu-MOF urea at 300 °C, in the presence of a 5% H2 atmosphere. The morphological, structural, and thermal properties of the prepared CuxO/MOF were determined through various techniques, and its photocatalytic behavior was investigated for the degradation of CIP under visible-light irradiation. The prepared CuxO/MOF bifunctional material is presented as a graphitic carbon-layered structure with a particle size of 9.2 ± 2.1 nm. The existence of CuO-Cu2O-C, which was found on the CuxO/MOF surface, enhanced the adsorption efficiency and increased the photosensitivity of CuxO/MOF, towards the degradation of CIP in aqueous solutions. The tailored CuxO/MOF, not only shows an excellent CIP degradation efficiency of up to 92% with a constant kinetic rate (kobs) of 0.048 min−1 under visible light, but it can also retain the stable photodegradation efficiency of >85%, for at least six cycles. In addition, CuxO/MOF has an excellent adsorption capacity at pH 6.0 of the maximum Langmuir adsorption capacity of 34.5 mg g−1 for CIP. The results obtained in this study demonstrate that CuxO/MOF is a reliable integrated material and serves as an adsorbent and photocatalyst, which can open a new pathway for the preparation of visible-light-responsive photocatalysts, for the removal of antibiotics and other emerging pollutants.

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“…Propylene (C 3 H 6 ) is widely used in the production of various chemicals and is mostly produced from the cracking of large hydrocarbon molecules or crude oil in the petrochemical industry, during which propyne (C 3 H 4 ) and propane (C 3 H 8 ) are always produced as undesirable byproducts . The highly efficient removal of C 3 H 4 or C 3 H 8 from the C 3 H 4 /C 3 H 6 or C 3 H 6 /C 3 H 8 mixture is of high importance but challenging because of the similar boiling points and molecular sizes of the three hydrocarbons. , Therefore, many studies have been devoted to exploring more effective C 3 H 6 purification technologies. , Compared with traditional gas separation methods (cryogenic distillation or catalytic partial hydrogenation), a physical adsorption method based on porous materials is regarded to be environmentally friendly and energy efficient. − Metal–organic frameworks (MOFs) − consisting of metal centers/clusters and organic ligands have emerged as a type of unique porous material in the past two decades − and widely explored for gas separation − owing to their advantages, including structural diversity, adjustable pore size, and designable adsorption sites. ,, …”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Propyne/Propylene Separation in a “Flexible-Robust” and Hydrolytically Stable Cu(II)-MOF

Liu

Zhang

et al. 2023

Inorg. Chem.

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Propyne/propylene separation is important in the petrochemical industry but challenging due to their similar physical properties and close molecular sizes. Metal–organic frameworks (MOFs) are a class of promising adsorbents for light hydrocarbon separations. Among them, the so-called “flexible-robust” MOFs combine the advantages of flexibility and rigidity in structure and could show enhanced gas separation selectivity as well as improved gas uptake at low pressure. Interpenetrated MOFs offer a platform to explore the “flexible-robust” feature of MOFs based on their subnetwork displacement in the process of gas adsorption. Herein, we present two hydrolytically stable MOFs (BUT-308 and BUT-309) with interpenetrated structures and fascinating propyne/propylene separation performance. BUT-308 is composed of interpenetrated 2D Cu(BDC-NH2)BPB layers (H2BDC-NH2 = 2-aminobenzene-1,4-dicarboxylic acid; BPB = 1,4-bis(4-pyridyl)benzene), while BUT-309 consists of twofold interpenetrated 3D pillared-layer Cu2(BDC-NH2)2(BPB-CF3) nets (BPB-CF3 = 2-trifluoromethyl-1,4-bis(4-pyridyl)benzene). Gas adsorption measurements showed that BUT-309 was a “flexible-robust” adsorbent with multistep adsorption isotherms for C3H4 rather than C3H6 at a wide temperature range. The guest-dependent pore-opening behavior endows BUT-309 with high potential in the C3H4/C3H6 separation. The C3H4 adsorption measurements of BUT-309 at 273–323 K showed that the lowering of the temperature induced the pore-opening action at lower pressure. Column breakthrough experiments further confirmed the capability of BUT-309 for the efficient removal of C3H4 from a C3H4/C3H6 binary gas, and the C3H6 processing capacity at 273 K (15.7 cm3 g–1) was higher than that at 298 K (35.2 cm3 g–1). This work shows a rare example of “flexible-robust” MOFs and demonstrated its high potential for C3H4/C3H6 separation.

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Systematic evaluation of water adsorption in isoreticular UiO-type metal–organic frameworks

Abstract: Water adsorption in porous materials is important for many applications including heat allocation, dehumidification, thermal batteries, and water harvesting from air. While porous MOFs have been demonstrated as promising adsorbents...

Cited by 28 publications

References 84 publications

Computational Insights into the Interaction of Water with the UiO-66 Metal-Organic Framework and Its Functionalized Derivatives

Computational Insights into the Interaction of Water with the UiO-66 Metal-Organic Framework and Its Functionalized Derivatives

Enhanced Visible-Light-Responsive Photocatalytic Degradation of Ciprofloxacin by the CuxO/Metal-Organic Framework Hybrid Nanocomposite

Highly Efficient Propyne/Propylene Separation in a “Flexible-Robust” and Hydrolytically Stable Cu(II)-MOF

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