Enhancement mechanism behind the different adsorptive behaviors of nitro/amine modified hypercrosslinked resins towards phenols

Xu, Chao; Jiang, Long; Jin, Chao; Liu, Linjie; Yu, Shitao; Xian, Ming

doi:10.1016/j.jtice.2019.05.004

Cited by 15 publications

(6 citation statements)

References 33 publications

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“…However, the obtained solid products were easily dissolved in acetone, indicating that these were most likely to be lightly crosslinked oligomers. This could be ascribed to inferior catalytic effects of ZnCl 2 in halogenated solvents [24] . This was confirmed here by comparing the BET surface areas of HCPs synthesized in DCE but using ZnCl 2 (Samples 8 and 12) and FeCl 3 (Samples 9 and 13).…”

Section: Resultssupporting

confidence: 71%

“…This could be ascribed to inferior catalytic effects of ZnCl 2 in halogenated solvents. [24] This was confirmed here by comparing the BET surface areas of HCPs synthesized in DCE but using ZnCl 2 (Samples 8 and 12) and FeCl 3 (Samples 9 and 13). Regardless of monomers used, DCX of BCMBP, the BET surface areas of HCPs that were synthesized with ZnCl 2 were lower than those synthesized with FeCl 3 .…”

Section: Hcps Synthesis Via Internal Crosslinking With Dessupporting

confidence: 74%

“…This was intriguing as it is widely accepted that FeCl 3 is a Lewis acid that is more effective for catalyzing Friedel-Crafts reactions than ZnCl 2 . [24] However, this was not the case in this work, when FeCl 3 functioned as both the catalyst and hydrogen bond donor in [ChCl][FeCl 3 ] 2 . This could be ascribed to the difference between the Lewis acidity of these catalysts in ionic liquids.…”

Section: Des Suitability For Various Crosslinking Strategiesmentioning

confidence: 68%

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Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO₂/N₂ Selectivity

Ding,

Chanchaona,

Konstas

et al. 2024

ChemSusChem

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Hypercrosslinked polymers (HCPs) are widely used in ion exchange, water purification, and gas separation. However, HCP synthesis typically requires hazardous halogenated solvents e.g., dichloroethane, dichloromethane and chloroform which are toxic to human health and environment. Herein we hypothesize that the use of halogenated solvents in HCP synthesis can be overcome with deep eutectic solvents (DES) comprising metal halides – FeCl3, ZnCl2 that can act as both the solvent hydrogen bond donor and catalyst for polymer crosslinking via Friedel Crafts alkylation. We validated our hypothesis by synthesizing HCPs in DESs via internal and external crosslinking strategies. [ChCl][ZnCl2]2 and [ChCl][FeCl3]2 was more suitable for internal and external hypercrosslinking, respectively. The specific surface areas of HCPs synthesized in DES were 20 – 60 % lower than those from halogenated solvents, but their CO2/N2 selectivities were up to 453 % higher (CO2/N2 selectivity of poly‐α,α’‐dichloro‐p‐xylene synthesized in [ChCl][ZnCl2]2via internal crosslinking reached a value of 105). This was attributed to the narrower pore size distributions of HCPs synthesized in DESs.

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Section: Resultssupporting

confidence: 71%

Section: Hcps Synthesis Via Internal Crosslinking With Dessupporting

confidence: 74%

Section: Des Suitability For Various Crosslinking Strategiesmentioning

confidence: 68%

See 1 more Smart Citation

Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO₂/N₂ Selectivity

Ding,

Chanchaona,

Konstas

et al. 2024

ChemSusChem

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“…The q max of PS-GA-DCE at 298 K was predicted to be 1052 mg/g; this data outstripped other reported data in the literature (Table S3). The corresponding parameters such as enthalpy (Δ H , kJ/mol), entropy (Δ S , J/(mol·K)), and Gibbs free energy (Δ G , kJ/mol) were computed using the Van't Hoff equation (Figure S4). The calculated Δ H was −14.61 kJ/mol, with its negative value suggesting an exothermic process.…”

Section: Results and Discussionmentioning

confidence: 99%

Multiple Phenolic Hydroxyl-Modified Hyper-Crosslinked Polymers and Their Efficient Adsorptive Removal of o-Nitrophenol from Water

Cao,

Zhong,

Dai

et al. 2023

Ind. Eng. Chem. Res.

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Herein, three multiple phenolic hydroxyl aromatic compounds, namely, p-dihydroxybenzene (PD), 1,3,5-trihydroxybenzene (TB), and gallic acid (GA), were applied as the chemical modifiers and incorporated into initial polymers via nucleophilic substitution, hence creating intermediates with different phenolic hydroxyls (−OH). Thereafter, Friedel−Crafts alkylation resulted in multiple phenolic −OH-modified hyper-cross-linked polymers (HCPs), namely, PS−PD-DCE, PS-TB-DCE, and PS-GA-DCE. The final polymers exhibited a high Brunauer−Emmett−Teller (BET) surface area (S BET : 504−573 m 2 /g), large pore volume (V total : 0.48−0.54 cm 3 /g), and plentiful phenolic −OH (acidic exchange capacity: 1.2−2.6 mmol/g). The adsorption experiments revealed that PS-GA-DCE with the highest phenolic −OH was the most efficient adsorbent for the adsorption of o-nitrophenol from aqueous solutions, and the predicted maximum capacity (q max ) at 298 K was 1052 mg/g according to the Langmuir model, surpassing the data of most synthetic adsorbents in previous studies. The micropore diffusion model and the intraparticle diffusion model effectively elucidated the kinetic data. 5% of sodium hydroxide desorbed o-nitrophenol from the polymers completely, and the equilibrium capacity dropped to 85.5% after five repeated adsorption−desorption cycles. The adsorption mechanism revealed that hydrogen bonding was primarily responsible for the adsorption, with micropore filling serving as an additional contributing factor. These results provide valuable insights into the synthesis and application of chemically modified polymers for the enhanced adsorption performance.

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“…Conforming to Langmuir model indicate that the thermodynamic parameters for the adsorption of BNAP, PA and GA on β-CD-PS were calculated based on the Vant-Hoff equation [41] .…”

Section: The Adsorption Of the Acid Compound On β-Cd-psmentioning

confidence: 99%

Fabrication of O-enriched macroporous polymer for the efficient adsorption organic acid from aqueous solution

Fu,

Gong,

et al. 2023

J Polym Res

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Herein, an oxygen-rich polymer, namely, β-CD-PS was gained according to one-step nucleophilic substitution, and it was used to adsorb organic acids from aqueous solution. The nucleophilic substitution brought abundant functional -OH groups (the oxygen contents were 9.04 wt%,) to the polymer, and increased the hydrogen bonding between the polymer and the adsorbate. The adsorption results showed that the capacities of organic acids on β-CD-PS were much greater than chloromethylated polystyrene (CMPS). The maximum adsorption capacities of salicylic acid (SA), pyrogallic acid (PA), βnaphthol (NAP), 1,1'-bi-2-naphthol (BNAP) and gallic acid (GA) were 407.47 mg/g, 312.42 mg/g, 246.39 mg/g, 320.75 mg/g and 254.40mg/g, respectively. Langmuir model was more t for the adsorption of BNAP, PA, and GA, and Freundlich model was more suited to the adsorption of PHE, NAP, and SA. Thermodynamic analysis showed that the adsorption is a spontaneous process, furthermore, the exothermic occurred between the adsorption site and SA, NAP, and phenol (PHE) and the endothermic occurred between the adsorption site and BNAP, PA and GA. The adsorption kinetics results indicated that the time for the equilibrium of SA, PA, GA, and NAP was about 100 min, while BNAP required more time.Moreover, the adsorption of SA on β-CD-PS could achieve most adsorption at high concentrations and complete removal at low concentrations. The organic acids adsorbed on the polymer could be eluted by anhydrous alcohol and 0.01 mol/L NaOH. The β-CD-PS exhibited superior adsorption e ciency, reproducibility, and reusability, demonstrating their excellent performance for the adsorption of organic acids, and analysis of the adsorption mechanism revealed that the -OH groups played a signi cant role due to the strong hydrogen bonding interaction.

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Enhancement mechanism behind the different adsorptive behaviors of nitro/amine modified hypercrosslinked resins towards phenols

Cited by 15 publications

References 33 publications

Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO₂/N₂ Selectivity

Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO₂/N₂ Selectivity

Multiple Phenolic Hydroxyl-Modified Hyper-Crosslinked Polymers and Their Efficient Adsorptive Removal of o-Nitrophenol from Water

Fabrication of O-enriched macroporous polymer for the efficient adsorption organic acid from aqueous solution

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Enhancement mechanism behind the different adsorptive behaviors of nitro/amine modified hypercrosslinked resins towards phenols

Cited by 15 publications

References 33 publications

Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO2/N2 Selectivity

Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO2/N2 Selectivity

Multiple Phenolic Hydroxyl-Modified Hyper-Crosslinked Polymers and Their Efficient Adsorptive Removal of o-Nitrophenol from Water

Fabrication of O-enriched macroporous polymer for the efficient adsorption organic acid from aqueous solution

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Product

Resources

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Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO₂/N₂ Selectivity

Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO₂/N₂ Selectivity