Phosphonium zwitterions for lighter and chemically-robust MOFs: highly reversible H<sub>2</sub>S capture and solvent-triggered release

Reynolds, Joseph E.; Bohnsack, Alisha M.; Kristek, David J.; Gutièrrez-Alejandre, Aı̀da; Dunning, Samuel G.; Waggoner, Nolan W.; Sikma, R. Eric; Ibarra, Ilich A.; Humphrey, Simon M.

doi:10.1039/c9ta05444h

Cited by 23 publications

(18 citation statements)

References 75 publications

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“…1,2 Literature studies detail a broad range of zwitterionic structures as small molecules and as functionalities within macromolecular architectures, including diverse combinations of cations (ammoniums, 3 phosphoniums, 4−6 imidazoliums 7 ) and anions (carboxylates, sulfonates, sulfates, phosphonates, phosphinates, phosphates). 2−11 Investigations of zwitterionic small molecules include their use in metal extraction, 12 self-assembled ionic gels and proton conductivity, 4 catalytic ligands, 6 metal−organic frameworks (MOFs), 13 and interfacial materials for solar cells. 14 Literature examples have demonstrated that phosphonium ions impart improved thermal stability and ion conductivity for both small-molecule and polymeric systems compared to ammonium-based analogues.…”

Section: ■ Introductionmentioning

confidence: 99%

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

et al. 2020

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This manuscript describes a synthetic strategy and structure–property investigation of unprecedented phosphonium-based zwitterionic homopolymers (polyzwitterions) and random copolymers (zwitterionomers). Free radical polymerization of 4-(diphenylphosphino)styrene (DPPS) provided neutral polymers containing reactive triarylphosphines. Quantitative postpolymerization alkylation of these pendant functionalities generated a library of polymers containing various concentrations of neutral phosphines, phosphonium ions, and phosphonium sulfobetaine zwitterions. The zwitterionic homo- and copolymers exhibited significantly higher glass transition temperatures (T g) and enhanced mechanical reinforcement in comparison to neutral and phosphonium analogues. These changes in T g and mechanical properties were attributed to nanoscale morphological domains, which formed due to electrostatic interactions between zwitterionic groups, as revealed by X-ray scattering and broadband dielectric spectroscopy (BDS). BDS revealed increased static dielectric constants (>25) for the phosphonium zwitterionomers compared to ionomeric or neutral analogues. These high static dielectric constants for the solvent-free polyzwitterions supported their stronger polarization response in comparison with polymers containing neutral phosphines and phosphonium ions, and these interactions accounted for morphological differences and enhanced mechanical behavior. This work describes a versatile strategy for modulating electrostatic interactions with tunable mechanical properties for an unprecedented family of zwitterionic polymers.

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Section: ■ Introductionmentioning

confidence: 99%

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

et al. 2020

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“…[21] The adsorption capacity of Mg-Cuk-1 was 1.41 mmol g-1 at a low concentration of 6 vol % H 2 S and increased to 3.1 mmol g -1 at a high concentration of 15 vol % H 2 S. Mg-Cuk-1 also had a flexible structure, and after five H 2 S adsorption-desorption cycles, the crystallinity still remained, because of the weak interaction between Mg-Cuk-1 framework and H 2 S molecules. Reynolds [22] The latter exhibited exceptionally high chemical stability, allowing complete cycle adsorption with a H 2 S capacity of 8.00 mmol g-1 and triggering the release of H 2 S by solvents such as DMF, H 2 O and MeOH (Figure 3). The high H 2 S adsorption capacity of PCM-75 may be caused by the polarization properties of the frameworks, the presence of charged phosphorus species and highly polarized Mg 3 + nodes.…”

Section: Pore Structuresmentioning

confidence: 99%

Research Progress of Hydrogen Sulfide Adsorption Based on MOFs

Liu

2021

ChemistrySelect

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Adsorption method is one of the main technologies for hydrogen sulfide treatment. Developing an adsorbent with good selectivity, large adsorption capacity, stability and good regeneration is the key to the removal of hydrogen sulfide by adsorption method. Compared with the traditional adsorbents, Metal-organic frameworks (MOFs) have a large specific surface area, a variety of framework structures, adjustable pore sizes and functionality, showing significant advantages in the adsorption of hydrogen sulfide. In this paper, the research progress of hydrogen sulfide adsorption based on MOFs in recent years was summarized. The influences of pore structure and unsaturated metal sites on the hydrogen sulfide adsorption performance of MOFs were discussed, and the strategies of functionalized groups and preparation of composites were proposed to improve the hydrogen sulfide adsorption performance of MOFs. Finally, the problems and challenges in the future industrial application of MOFs as low concentration hydrogen sulfide adsorbents were pointed out.

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“…The use of organophosphine linkers for the preparation of various multifunctional porous coordination polymers dates back to 2008. Since then, a number of materials were designed, especially by Humphrey and co‐workers (phosphine coordination materials, PCMs) . It should be noted they generally comprise carboxylic groups coordinating metal secondary building units (SBUs).…”

Section: Introductionmentioning

confidence: 99%

Boronate Covalent and Hybrid Organic Frameworks Featuring P^III and P=O Lewis Base Sites

Pacholak

Gontarczyk

Kamiński

et al. 2020

Chemistry A European J

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Two covalent organic frameworks comprising Lewis basic P III centers and Lewis acidic boron atoms were prepared by poly-condensation reactions of newly obtained tris(4-diisopropoxyborylphenyl)phosphine with 2,3,6,7,10,11hexahydroxytriphenylene and 2,3,6,7-tetrahydroxy-9,10-dimethylanthracene. Obtained materials exhibit significant sorption of dihydrogen (100 cm 3 g À1 at 1 bar at 77 K), methane (20 cm 3 g À1 at 1 bar at 273 K) and carbon dioxide (50 cm 3 g À1 at 1 bar at 273 K). They were exploited as solidstate ligands for coordination of Pd 0 centers. Alternatively, in a bottom-up approach, boronated phosphine was treated with Pd 2 dba 3 and poly-condensated, yielding hybrid materials where the polymer networks are formed by means of covalent boronate linkages and coordination PÀPd bonds. In addition, the analogous materials based on phosphine oxide were synthesized. The DFT calculations on framework-guest interactions revealed that the behavior of adjacent boron and phosphorus/phosphine oxide centers is reminiscent of that found in Frustrated Lewis Pairs and may improve sorption of selected molecules.

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Phosphonium zwitterions for lighter and chemically-robust MOFs: highly reversible H₂S capture and solvent-triggered release

Abstract: The tetrahedral zwitterion of tetrakis(p-carboxyphenyl) phosphonium is employed as a unique building block for robust and lighter MOFs that tolerate sorption of acidic gases including H2S.

Cited by 23 publications

References 75 publications

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

Research Progress of Hydrogen Sulfide Adsorption Based on MOFs

Boronate Covalent and Hybrid Organic Frameworks Featuring P^III and P=O Lewis Base Sites

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Phosphonium zwitterions for lighter and chemically-robust MOFs: highly reversible H2S capture and solvent-triggered release

Abstract: The tetrahedral zwitterion of tetrakis(p-carboxyphenyl) phosphonium is employed as a unique building block for robust and lighter MOFs that tolerate sorption of acidic gases including H2S.

Cited by 23 publications

References 75 publications

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

Research Progress of Hydrogen Sulfide Adsorption Based on MOFs

Boronate Covalent and Hybrid Organic Frameworks Featuring PIII and P=O Lewis Base Sites

Contact Info

Product

Resources

About

Phosphonium zwitterions for lighter and chemically-robust MOFs: highly reversible H₂S capture and solvent-triggered release

Boronate Covalent and Hybrid Organic Frameworks Featuring P^III and P=O Lewis Base Sites