Sequestration of orange G and methylene blue from aqueous solutions using a Co(<scp>ii</scp>) coordination polymer

Fulong, Cressa Ria P.; Cook, Timothy R.

doi:10.1039/c7ra02286g

Cited by 10 publications

(4 citation statements)

References 30 publications

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“…An analysis of the crystal structure reveals that in addition to the PdMOP-like truncated tetrahedral pores, there are two additional pores that give rise to channels through the framework (see Figure ). The orange-colored product started turning light green during filtration and a darker green during activation as a result of solvent removal that prompts a phase transition reported to occur on the surface of the crystals. , The PXRD data supports this phase transition, with significant differences between the pre- and postactivation diffractograms. Since the phase transition was reported to be limited to the surface, we carried out PXRD (Figure ), TGA (Figure S3), and FTIR spectroscopy (Figure S4), along with sorption measurements, anticipating that the core Co Sponge may remain accessible to probing gas molecules.…”

Section: Resultssupporting

confidence: 82%

Metal–Organic Polyhedra and Metal–Organic Frameworks: Understanding How Discrete Versus Extended Structure Impacts Surface Areas and Pore Size Distributions

Welgama,

Avasthi,

Cook

2024

Chem. Mater.

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Certain discrete metal–organic polyhedra (MOPs) contain pores that also appear in extended metal–organic frameworks (MOFs) and MOP-based supramolecular frameworks. Here, we have selected a library of three MOPs (ZrMOP, CuMOP, and PdMOP) and their corresponding MOFs with analogous pores (UiO-66, HKUST-1, and the Co Sponge) to understand how parameters related to their sorption behavior differ. Specifically, we report the BET areas and pore size distributions for all six species. The BET areas for the MOPs follow the same trend as those for their MOF counterparts, with the highest shown by the ZrMOP (379 m2/g) and UiO-66 (1110 m2/g) pair. A discussion of the Zr-based materials includes comparisons to a known ZrMOP-based supramolecular framework that maintains extrinsic porosity via noncovalent interactions. The lowest areas were measured for the PdMOP (33 m2/g) and Co Sponge (80 m2/g) pair, a ramification of a phase transition that occurs during activation. Additionally, pore size distribution measurements suggest that the lower BET areas likely result from inaccessible internal cavities. Although the ZrMOP has the highest area per pore, its BET area is not as high as that of UiO-66 because the pores in an MOF share building blocks, greatly reducing the mass required to support a given number of pores, and the pores pack more tightly in space. MOFs are also more resilient to structural collapse upon activation, though we highlight some interesting examples for a loss of crystallinity that can increase the BET area of certain MOPs. Supramolecular chemistry can further enhance the properties of MOPs, where careful ligand or cage design can promote noncovalent interactions to enforce additional extrinsic porosity. Although MOFs remain top candidates for bulk storage and uptake due to their gravimetric and volumetric areas, for applications in thin films and membranes for separations chemistry, highly dispersed pores are desirable and the higher area per pore of MOPs is advantageous.

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Section: Resultssupporting

confidence: 82%

Metal–Organic Polyhedra and Metal–Organic Frameworks: Understanding How Discrete Versus Extended Structure Impacts Surface Areas and Pore Size Distributions

Welgama,

Avasthi,

Cook

2024

Chem. Mater.

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“…The modularity, tunability, and permanent porosity of these materials make them valuable for a wide range of applications . MOFs have shown potential for the adsorption and photocatalytic degradation of gaseous and aqueous pollutants but are generally limited to the solid phase owing to their insolubility . Since MOPs may be soluble in aqueous or organic solvents, it is possible to study host – guest interactions homogeneously in the solution phase, an approach that has historically prompted their use as nanovessels for chemical reactions. ,− To date, only a limited number of studies have demonstrated their capacity for polyfluorinated compounds, organic dye, and anion pollutant adsorption.…”

Section: Introductionmentioning

confidence: 99%

A Self-Assembled Iron(II) Metallacage as a Trap for Per- and Polyfluoroalkyl Substances in Water

et al. 2020

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An anionic iron(II) tetrahedral molecular cage (FeMOP) was studied for its ability to interact with various per- and polyfluoroalkyl substances (PFASs) in aqueous media. Liquid chromatography tandem mass spectrometry revealed that longer-chain-length (more than six carbons) perfluorocarboxylic, -sulfonic, and fluorotelomers were removed from solution. In contrast, the steric bulk of N-ethyl substituted fluorosulfonamido acetic acid PFASs hindered association with the cage. Solution binding studies in D2O using 19F nuclear magnetic resonance (NMR) titrations and a Job plot show a 1:1 binding stoichiometry for perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA) with an association constant (K a) of <103 and thus a favorable free energy of association (ΔG°). Perfluorononanoic acid (PFNA), on the other hand, forms an insoluble host–guest complex with FeMOP with a 1:1 host–guest ratio. Variable temperature (VT) NMR was used to determine the thermodynamic parameters of binding for a 1:1 FeMOP/PFHpA complex in water using a Curie-like model for fast-exchange processes. The extracted parameters suggest a low binding interaction (K a < 103) driven by an increase in entropy from cage desolvation upon guest binding. The solid-state host–guest complexes formed from solution complexation of PFHxA, PFHpA, and PFNA into the cage were characterized by infrared spectroscopy (FT-IR) and powder X-ray diffraction (PXRD) methods. FT-IR studies suggest an interaction between the fluorocarbon groups of PFASs to the phenylsulfonate functional groups of the ligand. A docking model predicted by computation also indicates this interaction may occur, with the PFASs adsorbing onto the surface of the cage rather than forming a true host–guest complex within the internal cavity. PXRD studies reveal a crystal packing of the complex that is very similar to that of the water-treated FeMOP, with the exception of 1:2 FeMOP/PFNA and 1:1 and 2:1 FeMOP/PFHpA.

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“…Metal–organic frameworks (MOFs) and porous coordination polymers (CPs) have unique properties including high surface area and structural flexibility, which have endowed them widespread application ranging from gas storage and separations, − chemical sensing, − drug delivery, to catalysis. , They have received considerable attention as powerful sorbents for different types of hazardous materials, namely because of their well-defined pore structures, high porosity, and tunable chemical properties. − Therefore, the adsorption and recycling of organic dyes using MOFs and derived materials have become hot research topics. Generally, the adsorption performance of porous MOFs is closely associated with their high specific surface area, size and shape of pores, and presence of adjustable functional groups, thus allowing the use of MOFs as promising materials for the removal of dyes from wastewater. − For example, a high adsorption capacity of MOF-235 was reported for cationic and anionic dyes, while methylene blue (MB) and methyl orange (MO) can be efficiently adsorbed by UiO-66, MIL-100(Cr), and MIL-100(Fe) .…”

Section: Introductionmentioning

confidence: 99%

Covalent Construction of Sustainable Hybrid UiO-66-NH₂@Tb-CP Material for Selective Removal of Dyes and Detection of Metal Ions

Zhang¹,

Jiang²,

Kirillov

et al. 2019

ACS Sustainable Chem. Eng.

103

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The development of quick and effective strategies for the removal of organic dyes and the detection of metal ions in aqueous solutions remains a challenge for protecting the public health and environment. Multifunctional materials that combine both the dye-adsorption and pollutant-detection functions rarely have been explored. In this work, a 2D Tb(III) coordination polymer (Tb-CP) was directly assembled on the Zr(IV)-based UiO-66-NH2 matrix through covalent grafting, resulting in the new hybrid UiO-66-NH2@Tb-CP material. Benefiting from the porous structure of the parent UiO-66-NH2 matrix, the unique luminescent signal of Tb-CP, and the good structure and solvent stability, the fabricated UiO-66-NH2@Tb-CP material features a great potential for several cycles of absorption and release of organic dyes. Given the presence of Tb-CP, the resulting surface of UiO-66-NH2@Tb-CP has more positive charge exposing active sites and exhibits a particularly high and quick absorption (397.31 mg·g–1) of the Coomassie brilliant blue (R250) organic dye in aqueous solution, along with the fast desorption ability. More significantly, after absorption and desorption of different organic dyes, UiO-66-NH2@Tb-CP can be further used for detecting Cu2+ or Ce3+ ions via Tb(III) luminescence quenching. All processes from the absorption and desorption of organic dyes to the detection of metal ions are reversible, are efficient, and fit a requirement for new sustainable materials. The excellent performance of UiO-66-NH2@Tb-CP benefits from a high Brunauer–Emmett–Teller (BET) surface area of UiO-66-NH2 as well as a strong interaction between the two components of this hybrid material. “Tea bag” experiments further confirmed the efficiency and simplicity of the practical application of UiO-66-NH2@Tb-CP for the adsorption and desorption of the R250 dye, which can be monitored by the naked eye. The present work thus represents a unique example of the hybrid, covalently bound MOF-based material that can simultaneously be used as the sustainable and easily recoverable absorption material for toxic dyes and the luminescent probe for the quantitative recognition of metal cations in aqueous solutions. The present study provides new perspectives for the design of multifunctional MOF-based materials for applications in sustainable chemistry.

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Sequestration of orange G and methylene blue from aqueous solutions using a Co(ii) coordination polymer

Abstract: A Co(ii) coordination polymer acts as a sponge for organic dye molecules, removing them from aqueous solutions.

Cited by 10 publications

References 30 publications

Metal–Organic Polyhedra and Metal–Organic Frameworks: Understanding How Discrete Versus Extended Structure Impacts Surface Areas and Pore Size Distributions

Metal–Organic Polyhedra and Metal–Organic Frameworks: Understanding How Discrete Versus Extended Structure Impacts Surface Areas and Pore Size Distributions

A Self-Assembled Iron(II) Metallacage as a Trap for Per- and Polyfluoroalkyl Substances in Water

Covalent Construction of Sustainable Hybrid UiO-66-NH₂@Tb-CP Material for Selective Removal of Dyes and Detection of Metal Ions

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Sequestration of orange G and methylene blue from aqueous solutions using a Co(ii) coordination polymer

Abstract: A Co(ii) coordination polymer acts as a sponge for organic dye molecules, removing them from aqueous solutions.

Cited by 10 publications

References 30 publications

Metal–Organic Polyhedra and Metal–Organic Frameworks: Understanding How Discrete Versus Extended Structure Impacts Surface Areas and Pore Size Distributions

Metal–Organic Polyhedra and Metal–Organic Frameworks: Understanding How Discrete Versus Extended Structure Impacts Surface Areas and Pore Size Distributions

A Self-Assembled Iron(II) Metallacage as a Trap for Per- and Polyfluoroalkyl Substances in Water

Covalent Construction of Sustainable Hybrid UiO-66-NH2@Tb-CP Material for Selective Removal of Dyes and Detection of Metal Ions

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Covalent Construction of Sustainable Hybrid UiO-66-NH₂@Tb-CP Material for Selective Removal of Dyes and Detection of Metal Ions