Porous Polymer Adsorbents Research Articles

Nanosecond pulsed discharge plasma modified porous polymer adsorbent materials for efficient removal of low‐concentration bisphenol A in liquid

AbstractThe efficient removal of low‐concentration endocrine disruptors is crucial for the protection of the aquatic environment. In this study, porous polymer adsorbent materials were modified by nanosecond pulsed discharge plasma to achieve efficient adsorption of low‐concentration bisphenol A (BPA). The removal efficiency of BPA reached 99% after 10 min of plasma modification at a pulse peak voltage of 28 kV, which increased by 25.8% compared to the raw materials. This enhancement was attributed to the increase of active sites and oxygen‐containing functional groups. The adsorption behaviors of the porous polymer materials were primarily dominated by monolayer chemisorption. Subsequently, comparative experiments further verified the high‐efficiency adsorption performance of porous polymer materials after plasma treatment.

Highly efficient isolation and purification of high-purity tea saponins from industrial camellia oil production by porous polymeric adsorbents.

Recovery of high-purity tea saponin (TS), a promising non-ionic surfactant with well-documented properties, is one of the major challenges to broadening its industrial applications. In this study, an innovative and sustainable strategy for the highly-efficient purification of TS was developed by using well-designed highly-porous polymeric adsorbents. The prepared Pp-A with controllable macropores (~96 nm) and appropriate surface hydrophobic properties was found more favorable for achieving high adsorption efficiency towards TS/TS-micelles. Kinetic results showed the adsorption follows the pseudo-second-order model (R2 = 0.9800), and the Langmuir model is more qualified to explicate the adsorption isotherms with Qe-TS ~ 675 mg g-1 . Thermodynamic studies revealed the monolayer adsorption of TS was an endothermic process that was conducted spontaneously. Interestingly, ethanol-driven desorption (90% v/v ethanol) of TS was rapidly (< 30 min) complete due to the possible ethanol-mediated disassembling of TS-micelles. A possible mechanism that involves the interactions between the adsorbents and TS/TS-micelles, the formation and disassembling of TS-micelles was proposed to account for the highly efficient purification of TS. Afterwards, Pp-A-based adsorption method was developed to purify TS directly from industrial camellia oil production. Through selective adsorption, pre-washing, and ethanol-driven desorption, the applied Pp-A enabled the direct isolation of high-purity TS (~96%) with a recovery ratio > 90%. Notably, Pp-A exhibited excellent operational stability and is of high potential for long-term industrial application. Results ensured the practical feasibility of the prepared porous adsorbents in purifying TS, and the proposed methodology is a promising industrial-scale purification strategy. © 2023 Society of Chemical Industry.

Synthesis of novel magnetic pitch-based hypercrosslinked polymers as adsorbents for effective recovery of Ag+ with high selectivity

Silver is an important precious metal with superior ductility, electrical and thermal conductivity, photosensitivity, and antibacterial properties. However, without proper recycling and treatment, silver emissions may pose a threat to the human health and subsistence environment due to their toxicity. Therefore, it is environmentally and economically important to recover Ag from waste electronic equipment and anode slime. Herein, carboxyl functionalized modified magnetic nanoparticles (Fe3O4@3-phenylglutaricacid nanoparticles) were designed and prepared to obtain the low-cost magnetic pitch-based HCP adsorbents (MPHCP and P-MPHCP). The novelty of present work is that superior adsorption capacity and magnetic responsiveness of adsorbent can be obtained by a simple one-step Friedel-Crafts reaction with very low-cost raw material. The maximum Ag+ adsorption capacity of MPHCP and P-MPHCP were 321 and 353 mg/g, respectively. The adsorption was completed within a short duration of 15 min for MPHCP and P-MPHCP at an initial Ag+ concentration of 100 mg/L. Moreover, the most selective is P-MPHCP wherein Ag+ is α = 61 times more selective than Pb2+ at a concentration of 100 mg/L.The adsorption capacity of MPHCP and P-MPHCP towards Ag+ still maintains above 89% after ten cycles of adsorption-desorption. This study not only provides new guidance for the development of porous polymeric adsorbents but also provides technical feasibility for the field of recovery and reutilization of precious metals, which has a very extensive practical application prospect.

Designing Phenyl Porous Organic Polymers with High-Efficiency Tetracycline Adsorption Capacity and Wide pH Adaptability.

Adsorption is an effective method to remove tetracycline (TC) from water, and developing efficient and environment-friendly adsorbents is an interesting topic. Herein, a series of novel phenyl porous organic polymers (P-POPs), synthesized by one-pot polymerization of different ratios of biphenyl and triphenylbenzene under AlCl3 catalysis in CH2Cl2, was studied as a highly efficient adsorbent to removal of TC in water. Notably, the obtained POPs possessed abundant phenyl-containing functional groups, large specific surface area (1098 m2/g) with abundant microporous structure, high pore volume (0.579 cm3/g), favoring the removal of TC molecules. The maximum adsorption capacity (fitted by the Sips model) could achieve 581 mg/g, and the adsorption equilibrium is completed quickly within 1 h while obtaining excellent removal efficiency (98%). The TC adsorption process obeyed pseudo-second-order kinetics and fitted the Sips adsorption model well. Moreover, the adsorption of POPs to TC exhibited a wide range of pH (2–10) adaptability and outstanding reusability, which could be reused at least 5 times without significant changes in structure and efficiency. These results lay a theoretical foundation for the application of porous organic polymer adsorbents in antibiotic wastewater treatment.

Novel preparation of amidoxime functionalized hyper-cross-linked polymeric adsorbent on the efficient adsorption of uranium in aqueous solution

Herein, a series of novel amidoxime-functionalized porous polymeric adsorbents using dimethoxymethane (FDA) as the external cross-linker and biphenyl and amidoxime-functionalized 1-(benzyloxy)-4-ethylbenzene (BP-AO) as the original monomers were synthesized in one-pot Friedel-Crafts alkylation reactions via a simple “knitting” synthetic strategy. The adsorbents were characterized by FT-IR, solid-state 13 C NMR/MAS spectrum, N 2 adsorption-desorption, etc. The adsorption mechanism was probed by XPS, which suggests that the η 2 complexation between uranium and amidoxime, and the polymers provide an approach to synthesize novel porous materials. The batch adsorption experiments showed that amidoxime hyper-crosslinked polymer-2 (HCPA-2) displays a uranium adsorption capacity of 27.7 mg/g at pH 6. The static adsorption action was more consistent with the Langmuir model and pseudo-second-order kinetics. Ionic competition experiments showed that K d (U(IV)) is as high as 695.94 mL/g and reusable with a removal rate up to 60% after 7 cycles when 0.1 M HNO 3 was used as a stripping agent, which verifies the practical application potential of the materials. • The HCPAs adsorbents with porous structure was synthesized via facile “knitting” strategy. • The HCPAs exhibited high selectivity and long service life. • The adsorption capacity was affected by the specific surface area and amidoxime group content. • The adsorption process was spontaneous and endothermic.

Reflections on the Pharmacotherapy Aspects of Cov-2 Variants

Reflections on the Pharmacotherapy Aspects of Cov-2 Variants

Functional Porous Organic Polymers with Conjugated Triaryl Triazine as the Core for Superfast Adsorption Removal of Organic Dyes.

Developing efficient adsorbents for the removal of water pollutants is of great significance for environmental protection. In this study, conjugated triaryl triazines (CTT), containing intramolecular hydrogen-bonding patterns, were recognized to be intriguing building blocks for the construction of porous organic polymer (POP) adsorbents. These planar monomers with multiple phenolic hydroxyl groups facilitated the formation of aza-linked polymers with hierarchical porous structures, sheet-like morphology, good surface wettability, and high degree of functionality. Such structural characteristics of the CTT-POP adsorbents provided superfast adsorption of various cationic dyes from water. For the adsorption of methylene blue dye, the pseudo-second-order rate constant of CTT-POP-1 is 12.9 g mg-1 min-1, superior to those reported in the existing literature. In addition, CTT-POP-1 can be regenerated at least seven times with no loss in performance, indicating its potential application in water treatment.

A superhydrophobic and porous polymer adsorbent with large surface area

A superhydrophobic hypercrosslinked microporous polymer adsorbent, SHMP-1 was synthesized from 1,3,5-trinaphthylbenzene by cross-linking of methylene. SHMP-1 has the largest specific surface area of 2100 m2 g−1 among superhydrophobic materials.

Highly efficacious entrapment of Th (IV) and U (VI) from rare earth elements in concentrated nitric acid solution using a phosphonic acid functionalized porous organic polymer adsorbent

It is challenging to extract Th (IV) and U (VI) from rare earth elements (REEs) in concentrated acidic solution. Herein, a nanoporous polymer adsorbent P (DVB-VPA) bearing phosphonic acid groups has been synthesized by solvothermal copolymerization of divinylbenzene (DVB) and vinylphosphonic acid (VPA). The maximum adsorption capacity (qmax) for Th (IV) and U (VI) onto P (DVB-VPA) was estimated to be 354.6 and 216.5 mg g−1 at 298 K in 4 mol L−1 of hydrogen nitrate media, which were much larger than most of the adsorbents reported previously. Besides, P (DVB-VPA) exhibited a good selectivity for Th (IV) and U (VI) from REEs in concentrated nitric acid solution, since the values of the selectivity for Th (IV) and U (VI) over La (III), Ce (III), Eu (III), Nd (III) and Sm (III) were 82.2% and 72.5%, respectively. XPS analysis revealed that the adsorption mechanism was achieved through the complexation of PO ligands anchored onto the polymer skeleton of P (DVB-VPA) with thorium and uranium. Due to P (DVB-VPA) showed a larger binding force toward Th (IV) than U (VI), both q max and selectivity for Th (IV) in concentrated hydrogen nitrate media was larger than those for U (VI) on P (DVB-VPA), which has been confirmed by DFT calculations.

Static and dynamic filtration of nickel and lead ions by adsorptive membrane induced by POP via layer by layer technique

We examined the ultrafiltration adsoprtive membrane manufacturing and its modification with the porous organic polymer (POP) adsorbent using layer-by-layer technology to removal of nickel and lead heavy metals in the present study. We used the one-step Friedel–Crafts reaction coupled with dimethyl acetal formaldehyde cross linker and iron chloride catalyst for the synthesis of the POP adsorbent. We also used an amino monomer to functionalize this type of polymer, which improved and modified the synthesized polymer for the better removal of heavy metals. The adsorbents and membranes prepared were analyzed and examined by various analytical d evices such as BET, FESEM, EDX, FTIR, AFM and the contact angle testing. In addition, the performance of the synthesized adsorption membrane was examined in the static adsorption system and membrane filtration to removal of the Ni (II) and Pb (II) metal ions. In the batch adsorption studies, the percentages of removal of nickel and lead metals for modified adsorption membrane with the adsorbent POP-NH2 were obtained at ambient temperature and the initial concentration of 20ppm as 0.86 and 0.92, respectively. Also, the maximum adsorption capacity of the Langmuir model in this membrane were calculated as 33.17mgg and 37.8mg/g for Ni (II) and Pb (II) metal[1] ions, respectively. In addition, the percentage of removal of metal ions and flux in the solution passing through the membrane filtration system was analyzed for pure poly ether sulfone (PES) membranes, the multilayer PES/(CHI-ALG)/CHI membrane, and the PES/(CHI-ALG)/CHI/POP-NH2 membrane.

Eco-Friendly Fabrication of a Highly Selective Amide-Based Polymer for CO2 Capture

© 2019 American Chemical Society. Porous polymeric adsorbents for CO2 capture (HCP-MAAMs) were fabricated by copolymerization of methacrylamide (MAAM) and ethylene glycol dimethacrylate using acetonitrile and azobisisobutyronitrile as a porogen and initiator, respectively. The X-ray photoelectron and Fourier transform infrared spectra revealed a high density of amide groups in the polymer matrix of HCP-MAAMs, which enabled high selectivity to CO2. The polymer BET surface area and total pore volume was up to 277 m2 g-1 and 0.91 cm3 g-1, respectively. The highest CO2 uptake at 273 K and 1 bar CO2 pressure was 1.45 mmol g-1, and the heat of adsorption was 27-35 kJ mol-1. The polymer with the lowest cross-linking density exhibited an unprecedented CO2/N2 selectivity of 394 at 273 K. Life cycle assessment revealed a lower environmental impact of HCP-MAAMs compared to molecularly imprinted polymers. HCP-MAAMs are eco-friendly CO2 adsorbents owing to their low regeneration energy, environmentally benign fabrication process, and high selectivity.

All-in-One Porous Polymer Adsorbents with Excellent Environmental Chemosensory Responsivity, Visual Detectivity, Superfast Adsorption, and Easy Regeneration.

It remains a formidable challenge to construct advanced adsorbents with superb adsorption, environmental stimuli response, and real-time detection capability for efficiently treating contaminants from complex environmental systems. A novel class of an all-in-one microporous adsorbent that simultaneously has excellent environmental chemosensory responsivity, visual detectivity, superfast micropollutant adsorption, as well as easy regeneration is reported herein. The advanced microporous adsorbent discussed in this study presents a hairy nanospherical morphology composed of a hairy stimuli-responsive polymeric shell and a shell-assisted superadsorptive microporous core. The adsorbent not only exhibits a valuable capability of pollutant detection by visible fluorescence quenching, but can also remove organic micropollutants from polluted water with super-rapid speed (79%, 98%, and 100% of its equilibrium uptake in 7 s, 10 s, and 2 min, respectively) and excellent recyclability (>96%). More importantly, the adsorbent still shows unimpeded adsorption performance in the flow-through adsorption tests (15 mL min-1 ), indicating a very appealing application prospect.

Development of magnetic porous coordination polymer adsorbent for the removal and preconcentration of Pb(II) from environmental water samples

A novel porous coordination polymer adsorbent (BTCA-P-Cu-CP) based on a piperazine(P) as a ligand and 1,2,4,5-benzenetetracarboxylic acid (BTCA) as a linker was synthesized and magnetized to form magnetic porous coordination polymer (BTCA-P-Cu-MCP). Fourier transform infrared (FTIR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), field emission scanning electron microscope(FESEM), energy-dispersive X-ray spectroscopy(EDS), CHN, and Brunauer-Emmett-Teller(BET) analysis were used to characterize the synthesized adsorbent. BTCA-P-Cu-MCP was used for removal and preconcentration of Pb(II) ions from environmental water samples prior to flame atomic absorption spectrometry(FAAS) analysis. The maximum adsorption capacity of BTCA-P-Cu-MCP was 582mgg-1. Adsorption isotherm, kinetic, and thermodynamic parameters were investigated for Pb(II) ions adsorption. Magnetic solid phase extraction (MSPE) method was used for preconcentration of Pb(II) ions and the parameters influencing the preconcentration process have been examined. The linearity range of proposed method was 0.1-100μgL-1 with a preconcentration factor of 100. The limits of detection and limits of quantification for lead were 0.03μgL-1 and 0.11μgL-1, respectively. The intra-day (n = 7) and inter-day (n = 3) relative standard deviations (RSDs) were 1.54 and 3.43% respectively. The recoveries from 94.75 ± 4 to 100.93 ± 1.9% were obtained for rapid extraction of trace levels of Pb(II) ions in different water samples. The results showed that the BTCA-P-Cu-MCP was steady and effective adsorbent for the decontamination and preconcentration of lead ions from the aqueous environment.

QSARs to predict adsorption affinity of organic micropollutants for activated carbon and β-cyclodextrin polymer adsorbents

The removal of organic micropollutants (MPs) from water by means of adsorption is determined by the physicochemical properties of the adsorbent and the MPs. It is challenging to predict the removal of MPs by specific adsorbents due to the extreme diversity in physicochemical properties among MPs of interest. In this research, we established Quantitative Structure–Activity Relationships (QSARs) between the physicochemical properties of a diverse set of MPs and their distribution coefficients (KD) measured on coconut shell activated carbon (CCAC) and porous β-cyclodextrin polymer (P-CDP) adsorbents. We conducted batch experiments with a mixture of 200 MPs and used the data to calculate KD values for each MP on each adsorbent under conditions of infinite dilution (i.e., low adsorbate concentrations). We used computational software to calculate 3656 molecular descriptors for each MP. We then developed and applied a model-selection workflow to identify the most significant molecular descriptors for each adsorbent. The functional stability and predictive power of the resulting QSARs were confirmed with internal cross validation and external validation. The applicability domain of the QSARs was defined based on the most significant molecular descriptors selected into each QSAR. The QSARs are predictive tools for evaluating adsorption-based water treatment processes and provide new insights into CCAC and P-CDP adsorption mechanisms.

Interconnected superporous adsorbent prepared via yeast-based Pickering HIPEs for high-efficiency adsorption of Rb+, Cs+ and Sr2+

High internal phase emulsions (HIPEs) template method is an emerging effective method of fabricating high-efficiency, orderly porous polymer adsorbents, but the conventional HIPEs template requires harmful surfactants, so the development of surfactant-free green emulsion templates become the subject of great significance. Herein, we prepared a green surfactant-free oil-in-water (O/W) Pickering HIPEs stabilized solely with non-toxic caustic-pretreated yeast (P-Yeast), and used it as template to prepare a novel adsorbent (P-Yeast-PAA) with interconnected superporous structure by a one-step solution polymerization of acrylic acid (AA) monomers in the emulsion. Interestingly, the surfactant-free Pickering-HIPEs exhibited superior stability due to the fine affinity between P-Yeast and AA monomer, and the pore structure of the adsorbent can be easily regulated by changing the contents of the monomer or the particles used for stabilizing the emulsion. In addition, the adsorbents prepared from P-Yeast based emulsion template have interconnected pore structure, which are significantly superior to other Pickering-HIPEs templates which are hard to form a similar pore structure. The open-cell superporous adsorbent containing a large number of COO− functional group has a fast capture rate and strong adsorption capability for radioactive Rb+, Cs+ and Sr2+ ions, and the saturated adsorption capacities are 179.69 mg/g (2.10 mmol/g), 229.52 mg/g (1.73 mmol/g) and 166.81 mg/g (1.90 mmol/g), and the equilibrium adsorption time are 30, 40 and 20 min, respectively. The porous adsorbent also has excellent regeneration ability and reusability, and maintains a high adsorption capacity after repeated use of five adsorption-desorption cycles. This study provides an environmentally-friendly and promising strategy for fabricating the interconnected superporous adsorbent for adsorption removal of radioactive metal ions.

Fabrication of sustainable organometallic polymeric adsorbents for remediation of fluoride from water: A novel approach

In this work, we have synthesised a series of crosslinked porous polymeric adsorbents poly(zirconyl methacrylate-co-methylmethacrylate) (p(ZrDMA-co-MMA)) by polymerising the organometallic vinyl monomer via suspension polymerisation. The novel adsorbents have been investigated for defuoridation of drinking water using batch and continuous mode experiments. The effects of different parameters such as initial fluoride concentration, adsorbent dosage, pH and co-ion concentration were extensively studied to investigate the adsorption capacity in field water.The fluoride adsorption was found to be maximum at neutral pH where 96.54% fluoride removal was achieved.The equilibrium data were fitted well with Freundlich and Langmuir adsorption isotherms, and it was found that fluoride sorption on ZrMA5 followed pseudo-second order kinetics with a correlation coefficient of 0.99. Further, the adsorption kinetics was studied by both reaction based and diffusion-based models, and results indicate both the surface adsorption as well as intraparticle diffusion contributes to rate-determining step. The unique approach to incorporate zirconium metal ions into polymeric moiety in the form of the organometallic vinyl monomer has delivered safe and potable treated water by curbing the commonly encountered problem of leaching of metal ions when metal is loaded/coated/impregnated onto the polymeric moiety.

Methotrexate-loaded porous polymeric adsorbents as oral sustained release formulations

Methotrexate as a model drug with poor aqueous solubility was adsorbed into porous polymeric adsorbents, which was used as oral sustained release formulations. In vitro release assay in simulated gastrointestinal fluids showed that the methotrexate-loaded adsorbents showed distinct sustained release performance. The release rate increased with increase in pore size of the adsorbents. In vivo pharmacokinetic study showed that the maximal plasma methotrexate concentrations after oral administration of free methotrexate and methotrexate-loaded DA201-H (a commercial porous polymeric adsorbent) to rats occurred at 40min and 5h post-dose, respectively; and the plasma concentrations decreased to 22% after 5h for free methotrexate and 44% after 24h for methotrexate-loaded DA201-H, respectively. The load of methotrexate into the porous polymeric adsorbents not only resulted in obvious sustained release, but also enhanced the oral bioavailability of methotrexate. The areas under the curve, AUC0–24 and AUC0-inf, for methotrexate-loaded DA201-H increased 3.3 and 7.7 times, respectively, compared to those for free methotrexate.

Substitution Effect Guided Synthesis of Task-Specific Nanoporous Polycarbazoles with Enhanced Carbon Capture

Controlled synthesis of efficient CO2 adsorbents with high porosities and CO2 binding affinities remains a challenge. Herein, we report the use of a substituent effect to develop a novel family of porous organic polymers for enhanced carbon capture. Based on the in silico-aided design strategy, the task-specific polymeric adsorbent derived from a 2,6-carbazole-substituted pyridinic scaffold exhibits a superior uptake of CO2, which reaches as high as 5.76 mmol g–1 at 273 K and 1 bar and ranks among the best by porous polymeric CO2 adsorbents. This approach not only enables us to achieve a very high CO2 capture for porous polymers but also provides tunable control of polymeric architectures and, in turn, their properties.

Rapid extraction of uranium ions from seawater using novel porous polymeric adsorbents

Nanoporous polymeric networks, are firstly exploited for uranium capture from seawater. Amidoxime PIM-1 is capable of uptake 95% of uranium in 24 h, and the U extraction efficiency is to be intact throughout three cycles of sorbent regeneration.

Factors Affecting Pheromone Production by the Pepper Weevil, Anthonomus eugenii Cano (Coleoptera: Curculionidae) and Collection Efficiency.

Several factors affecting pheromone production by male pepper weevils, Anthonomus eugenii Cano (Coleoptera: Curculionidae) as well as collection efficiency were investigated. Factors studied included: porous polymer adsorbents (Tenax versus Super Q), male age, time of day, male density, and male diet. Super Q was found to be a superior adsorbent for the male-produced alcohols and geranic acid as well as the plant-produced E-β-ocimene. Pheromone production increased with male age up to about age 15 days old and then tapered off. Male pepper weevils produced the highest amount of pheromone between noon and 2 pm (i.e., 4 to 6 h after “lights on”) and were producing ca. 800 ng/h during this period. Thereafter, pheromone production decreased and was extremely low during the scotophase (i.e., ca. 12 ng/h). Male pepper weevil density had a significant effect on both release rate and pheromone composition. Pheromone production on a per male basis was highest for individual males and the percentage of geranic acid in the blend was lowest for individual males. Male pepper weevils produced only extremely low amounts of pheromone when feeding on artificial diet; however, they produced very high amounts when on fresh peppers. Together, this information will be useful in designing better attractant lures for pepper weevils.