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Water stability and adsorption in metal-organic frameworks.

Highly efficient removal of metal ion pollutants, such as toxic and nuclear waste-related metal ions, remains a serious task from the biological and environmental standpoint because of their harmful effects on human health and the environment. Recently, highly porous metal–organic frameworks (MOFs), with excellent chemical stability and abundant functional groups, have represented a new addition to the area of capturing various types of hazardous metal ion pollutants. This review focuses on recent progress in reported MOFs and MOF-based composites as superior adsorbents for the efficient removal of toxic and nuclear waste-related metal ions. Aspects related to the interaction mechanisms between metal ions and MOF-based materials are systematically summarized, including macroscopic batch experiments, microscopic spectroscopy analysis, and theoretical calculations. The adsorption properties of various MOF-based materials are assessed and compared with those of other widely used adsorbents. Finally, we propose our personal insights into future research opportunities and challenges in the hope of stimulating more researchers to engage in this new field of MOF-based materials for environmental pollution management.

Metal–organic framework-based materials: superior adsorbents for the capture of toxic and radioactive metal ions

Antibiotics and organic explosives are among the main organic pollutants in wastewater; their detection and removal are quite important but challenging. As a new class of porous materials, metal–organic frameworks (MOFs) are considered as a promising platform for the sensing and adsorption applications. In this work, guided by a topological design approach, two stable isostructural Zr(IV)-based MOFs, Zr6O4(OH)8(H2O)4(CTTA)8/3 (BUT-12, H3CTTA = 5′-(4-carboxyphenyl)-2′,4′,6′-trimethyl-[1,1′:3′,1″-terphenyl]-4,4″-dicarboxylic acid) and Zr6O4(OH)8(H2O)4(TTNA)8/3 (BUT-13, H3TTNA = 6,6′,6″-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(2-naphthoic acid)) with the the-a topological structure constructed by D4h 8-connected Zr6 clusters and D3h 3-connected linkers were designed and synthesized. The two MOFs are highly porous with the Brunauer–Emmett–Teller surface area of 3387 and 3948 m2 g–1, respectively. Particularly, BUT-13 features one of the most porous water-stable MOFs reported so far. Interestingly, these MOFs ...

Highly Stable Zr(IV)-Based Metal–Organic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water

Removal of hazardous organics from water using metal-organic frameworks (MOFs): plausible mechanisms for selective adsorptions.

This review article presents the fundamental and practical aspects of water adsorption in Metal–Organic Frameworks (MOFs). The state of the art of MOF stability in water, a crucial issue to many applications in which MOFs are promising candidates, is discussed here. Stability in both gaseous (such as humid gases) and aqueous media is considered. By considering a non-exhaustive yet representative set of MOFs, the different mechanisms of water adsorption in this class of materials are presented: reversible and continuous pore filling, irreversible and discontinuous pore filling through capillary condensation, and irreversibility arising from the flexibility and possible structural modifications of the host material. Water adsorption properties of more than 60 MOF samples are reported. The applications of MOFs as materials for heat-pumps and adsorbent-based chillers and proton conductors are also reviewed. Some directions for future work are suggested as concluding remarks.

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Water adsorption in MOFs: fundamentals and applications

Adsorption and removal of phthalic acid and diethyl phthalate from water with zeolitic imidazolate and metal-organic frameworks.

Adsorptive removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from water with a metal–organic framework

Adsorptive removal of p-arsanilic acid from water using mesoporous zeolitic imidazolate framework-8

The adsorptive removal of organoarsenic compounds such as p-arsanilic acid (ASA) and roxarsone (ROX) from water using metal-organic frameworks (MOFs) has been investigated for the first time. A MOF, iron benzenetricarboxylate (also called MIL-100-Fe) exhibits a much higher adsorption capacity for ASA and ROX than activated carbon, zeolite (HY), goethite, and other MOFs. The adsorption of ASA and ROX over MIL-100-Fe is also much more rapid than that over activated carbon. Moreover, the used MIL-100-Fe can be recycled by simply washing with acidic ethanol. Therefore, it is determined that a MOF such as MIL-100-Fe can be used to remove organoarsenic compounds from contaminated water because of its high adsorption capacity, rapid adsorption, and ready regeneration. Moreover, only one of three analogous MIL-100 species (MIL-100-Fe, rather than MIL-100-Al or MIL-100-Cr) can effectively remove the organoarsenic compounds. This selective and high adsorption over MIL-100-Fe, different from other analogous MIL-100 species, can be explained (through calculations) by the facile desorption of water from MIL-100-Fe as well as the large (absolute value) replacement energy (difference between the adsorption energies of the organoarsenic compounds and water) exhibited by MIL-100-Fe. A plausible adsorption/desorption mechanism is proposed based on the surface charge of the MOFs, FTIR results, calculations, and the reactivation results with respect to the solvents used in the experiments.

Effect of central metal ions of analogous metal-organic frameworks on adsorption of organoarsenic compounds from water: plausible mechanism of adsorption and water purification.

Pyridine (Py) was adsorbed over metal–organic frameworks (MOFs) (UiO-66 and UiO-66-NH2 with different incorporated amino group content) in both vapor and liquid phases to understand the interactions between the basic adsorbate Py and a basic or neutral adsorbent. Py was adsorbed more favorably over UiO-66-NH2 than over the pristine UiO-66. Not only the adsorbed amount of Py but also adsorption kinetics increased with increasing amino group content in UiO-66s, showing that amino groups in the MOFs benefit the adsorption of Py in both vapor and liquid phases. To understand the favorable interaction between Py and basic UiO-66, calculations were also carried out. The results, including calculations, suggested that hydrogen bonding is important for improving the adsorption of Py over UiO-66s. However, the expected repulsive interaction between basic Py and amino groups of UiO-66-NH2 was not observed. Therefore, it is vital that specific interaction mechanisms should be considered in order to understand select...

Beom K. Jung

Papers

Adsorption and removal of phthalic acid and diethyl phthalate from water with zeolitic imidazolate and metal-organic frameworks.

Adsorptive removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from water with a metal–organic framework

Adsorptive removal of p-arsanilic acid from water using mesoporous zeolitic imidazolate framework-8

Effect of central metal ions of analogous metal-organic frameworks on adsorption of organoarsenic compounds from water: plausible mechanism of adsorption and water purification.

Adsorption of Pyridine over Amino-Functionalized Metal–Organic Frameworks: Attraction via Hydrogen Bonding versus Base–Base Repulsion