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      Bimetallic PCN-333 with Modulated Crystallization and a Porosity Structure for a Highly Efficient Removal of Congo Red

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      ACS Omega
      American Chemical Society

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          Abstract

          Bimetallic metal–organic frameworks (BMOFs) have garnered significant attention in the field of environmental remediation due to their more diverse adsorption sites compared to monometallic metal–organic frameworks (MOFs). Different energy barriers must be overcome for different metal ions and organic linkers to form MOFs. However, the impact of the synthesis temperature on the crystallization and porosity structure of BMOFs has been rarely studied. In this work, PCN-333 series-based BMOFs with different Fe/Al ratios were prepared by a solvothermal method at temperatures of both 135 and 150 °C. The synthesis temperature and Fe/Al ratio have significant effects on the crystal structure and specific surface area of bimetallic PCN-333, leading to the different adsorption performance of the PCN-333 for Congo red (CR). The Fe/Al-PCN-333–135(3:1) and Fe-PCN-333–150 exhibited the maximum CR adsorption capacities of 3233 and 3933 mg/g, respectively, surpassing the capacities of most previously documented adsorbents. The Langmuir model and pseudo-second-order kinetics can well describe the adsorption process of CR on Fe/Al-PCN-333–135(3:1) and Fe-PCN-333–150. Combining the isotherm adsorption behavior with the thermodynamic parameters, CR adsorption on BMOFs is a single-layer endothermic chemical adsorption. Furthermore, Fe/Al-PCN-333–135(3:1) and Fe-PCN-333–150 exhibited regenerability and reusability for three cycles with reasonable efficiency. This work is of great significance in the field of engineering BMOF materials to treat dye wastewater.

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          Water adsorption in porous metal-organic frameworks and related materials.

          Water adsorption in porous materials is important for many applications such as dehumidification, thermal batteries, and delivery of drinking water in remote areas. In this study, we have identified three criteria for achieving high performing porous materials for water adsorption. These criteria deal with condensation pressure of water in the pores, uptake capacity, and recyclability and water stability of the material. In search of an excellently performing porous material, we have studied and compared the water adsorption properties of 23 materials, 20 of which are metal-organic frameworks (MOFs). Among the MOFs are 10 zirconium(IV) MOFs with a subset of these, MOF-801-SC (single crystal form), -802, -805, -806, -808, -812, and -841 reported for the first time. MOF-801-P (microcrystalline powder form) was reported earlier and studied here for its water adsorption properties. MOF-812 was only made and structurally characterized but not examined for water adsorption because it is a byproduct of MOF-841 synthesis. All the new zirconium MOFs are made from the Zr6O4(OH)4(-CO2)n secondary building units (n = 6, 8, 10, or 12) and variously shaped carboxyl organic linkers to make extended porous frameworks. The permanent porosity of all 23 materials was confirmed and their water adsorption measured to reveal that MOF-801-P and MOF-841 are the highest performers based on the three criteria stated above; they are water stable, do not lose capacity after five adsorption/desorption cycles, and are easily regenerated at room temperature. An X-ray single-crystal study and a powder neutron diffraction study reveal the position of the water adsorption sites in MOF-801 and highlight the importance of the intermolecular interaction between adsorbed water molecules within the pores.
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            Stable metal-organic frameworks containing single-molecule traps for enzyme encapsulation.

            Enzymatic catalytic processes possess great potential in chemical manufacturing, including pharmaceuticals, fuel production and food processing. However, the engineering of enzymes is severely hampered due to their low operational stability and difficulty of reuse. Here, we develop a series of stable metal-organic frameworks with rationally designed ultra-large mesoporous cages as single-molecule traps (SMTs) for enzyme encapsulation. With a high concentration of mesoporous cages as SMTs, PCN-333(Al) encapsulates three enzymes with record-high loadings and recyclability. Immobilized enzymes that most likely undergo single-enzyme encapsulation (SEE) show smaller Km than free enzymes while maintaining comparable catalytic efficiency. Under harsh conditions, the enzyme in SEE exhibits better performance than free enzyme, showing the effectiveness of SEE in preventing enzyme aggregation or denaturation. With extraordinarily large pore size and excellent chemical stability, PCN-333 may be of interest not only for enzyme encapsulation, but also for entrapment of other nanoscaled functional moieties.
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              Efficient removal of dyes using carboxymethyl cellulose/alginate/polyvinyl alcohol/rice husk composite: Adsorption/desorption, kinetics and recycling studies

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                Author and article information

                Journal
                ACS Omega
                ACS Omega
                ao
                acsodf
                ACS Omega
                American Chemical Society
                2470-1343
                30 January 2024
                13 February 2024
                : 9
                : 6
                : 7173-7187
                Affiliations
                [1]College of Chemistry and Chemical Engineering, Yunnan Normal University , Kunming 650092, China
                Author notes
                [* ]Email: xfzhangkm@ 123456163.com . Tel.: +86-13888430046. Fax: +86-871-65941088.
                Author information
                https://orcid.org/0000-0002-4384-9317
                Article
                10.1021/acsomega.3c09256
                10870413
                38371803
                5919142a-59c6-421f-9710-9c9f629c2ca8
                © 2024 The Authors. Published by American Chemical Society

                Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works ( https://creativecommons.org/licenses/by-nc-nd/4.0/).

                History
                : 20 November 2023
                : 09 January 2024
                : 05 January 2024
                Funding
                Funded by: National Natural Science Foundation of China, doi 10.13039/501100001809;
                Award ID: 21464017
                Funded by: Youth and Middle-Aged Academic and Technical Leaders of Yunnan Province, doi NA;
                Award ID: 202205AC160032
                Funded by: Natural Science Foundation of Yunnan Province, doi 10.13039/501100005273;
                Award ID: 202301AT070071
                Funded by: National Natural Science Foundation of China, doi 10.13039/501100001809;
                Award ID: 21965039
                Funded by: National Natural Science Foundation of China, doi 10.13039/501100001809;
                Award ID: 21564018
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                ao3c09256

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