Functional Porous Organic Polymers Research Articles

Dual functional porous organic polymer: Reversible iodine capture and selective sensing of picric acid

The development of porous organic materials for removing radiotoxic iodine from nuclear plant waste is significantly relevant to environmental remediation as well as the detection of trace amounts of nitroexplosive picric acid for environmental safety is challenging. To achieve reversible iodine adsorption by the porous material, we have synthesized a highly stable porous organic polymer POF-1 by Schiff base condensation of tris(4-aminophenyl)methane and 2,2′-bithiophene-5,5′-dicarbaxaldehyde under microwave irradiation. POF-1 showed high affinity towards iodine adsorption due to electron-rich sulfur and nitrogen atoms in the porous structure which interact with iodine and form polyiodide ions by electrostatic interactions. POF-1 showed a remarkable iodine uptake capacity of 4.25 g g−1 in the vapor phase and could efficiently remove iodine from an iodine-cyclohexane solution with an adsorption efficiency of 141.0 mg/L. The iodine adsorption follows Langmuir's isothermal model i.e. monolayer adsorption and Pseudo second-order kinetics. POF-1 exhibited good recyclability towards reversible iodine capture even after five cycles. Furthermore, the luminescence characteristic of POF-1 has been employed for the selective detection of picric acid with high sensitivity with a detection limit of 8 μM among a range of nitroaromatic. The Fluorescence quenching mechanism is mainly attributed to photo-induced electron transfer and the inner filter effect.

POP based nitrogen containing anodic materials for high capacity and fast Charge-Discharge applications in LIB

Lithium ion batteries possessing the ability of fast charging without compromising on the reversible capacity are the need of the hour. To this end, there is a need to develop active materials that support this property. Owing to the benefits of structural tunability and the possibility of including various Herero atoms in the structure, organic polymers offer a promising candidacy as anodic active materials. In this study, synthesis of BIAN-Bismarck brown based azo and imine functional porous organic polymer and its application as high capacity anode, delivering 500 mAh/g at 0.4 A/g was presented. Besides, the application as a high capacity anode, BBP was also used as a precursor to derive N-doped carbon labelled as PyBBP600 (pyrolysed at 600) and PyBBP800 (pyrolysed at 800). PyBBP800 delivered excellent rate capability and long cyclability at 4 A/g, delivering 125 mAh/g for 5000 cycles. Thereby the application of organic polymer for high energy and high power applications is presented in this work.

Acetic Anhydride Polymerization as a Pathway to Functional Porous Organic Polymers and Their Application in Acid–Base Catalysis

Acetic anhydride (AA) is usually considered a stable molecule but is shown here to be able to polymerize in closed reactors to a cross-linked polyketone condensate. By using this chemistry, it was possible to copolymerize AA with l-histidine, which gives a nitrogen-doped functional nanoporous polymer that can act as an acid–base heterogeneous catalyst. The polymer acidic and basic sites were screened by running an acetal hydrolysis Knoevenagel condensation reaction cascade to optimize catalyst synthesis. Furthermore, it was possible to catalyze CO2 cycloaddition to epoxides to the corresponding cyclic carbonate with complete conversion without cocatalysts.

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.

Comparison of the use of functional porous organic polymer (POP) and natural material zeolite for nitrogen removal and recovery from source-separated urine

Recovering nitrogen from source-separated urine can offset fertilizer production, reduce the energy consumption associated with wastewater treatment, and help prevent certain pollutants from entering into wastewater treatment plants. This study evaluated the performance of a newly designed porous organic polymer (POP) for removing ammonium (NH4+) from synthetic hydrolyzed urine in comparison with natural clinoptilolite in terms of adsorption capacity (isotherm), adsorption rate (kinetics), regeneration rate, and adsorbent cost. NH4+ removal from hydrolyzed urine using the POP was rapid with a capacity of 74.96 mg/g, which is about five times higher than clinoptilolite (15.42 mg/g). In addition, the predicted capacity of both adsorbents decreased with the number of cycles using an integrated adsorption-regeneration model, but remained at about 83.4% and 21.6% of the pristine POP and clinoptilolite after 24 cycles, respectively. The POP had a higher adsorbent cost than clinoptilolite, however, it can be competitive to clinoptilolite with multiple uses if its production can be scaled up.

A novel functional porous organic polymer for the removal of uranium from wastewater

Abstract A solid porous adsorbent with amino and carboxyl is developed successfully via one-pot Friedel-Crafts alkylation reaction. The resulting materials are highly chemically stable and the surface area can be changed by different ratios of initial aromatic monomers. The critical factors effect adsorption performances such as temperature, contact time, ionic strength and pH are studied by using batch adsorption experiments. The adsorption process is fast and can be well simulated with the pseudo-second-order model, yielding a rate constant of 1.31 × 10−3 min−1. The sorption isotherms are correlated with the Langmuir isotherms, according to which the highest adsorption amount (46.74 mg g−1) is measured at pH 8 under 308 K. According to FT-IR and XPS analysis, uranium is chelated by amino and carboxyl groups, indicating that the addition of tryptophan significantly increases the adsorption capacity. These results provide a new design strategy for the development of novel adsorbents for the recovery of uranium (VI).

Functional porous organic polymer with high S and N for reversible iodine capture

Abstract Nuclear waste such as radioactive iodine has been received worldwide attention because of the effects of radiation on biological health. The efficient capture of radioactive iodine is of great importance for the safe utilization of nuclear energy. In this study, a functional porous organic polymer (P-TzTz) with high sulfur and nitrogen contents was synthesized by the catalyst-free hydrothermal process of dithiocarbanate (DTO) and benzo[1,2-b:3,4-b′:5,6-b″]trithiophene-2,5,8-tricarbaldehyde (BTT-THO) in N,N-dimethylformamide under N2 atmosphere. This tailor-made amorphous polymer exhibits high affinity and adsorption capacity for iodine owing to its effective electron-rich sorption sites, π-conjugated structure and hierarchically porous structure. P-TzTz displays an excellent reversible iodine uptake with capacity of 326 wt% for volatile iodine. After five cycles of volatile iodine adsorption, P-TzTz almost retains the same adsorption capacity with the original adsorbent. In addition, P-TzTz also exhibits excellent adsorptive performance for the removal of iodine from iodine/cyclohexane solution with an adsorption capacity of 494.09 mg g−1, suggesting that P-TzTz may be also an effective adsorbent for the removal of iodine from solution.

Irreversible tautomerization as a powerful tool to access unprecedented functional porous organic polymers with a tris(β-keto-hydrazo)cyclohexane subunit (TKH-POPs).

Porous organic polymers (POPs) have received much attention, due to their multiple potential applications and flexibility in chemical structure design. Creation of a novel chemical structure has been the central task in the research of POPs, which are usually constructed by direct coupling polymerizations. The fascinating rearrangement/tautomerization could lead to some novel structures, which are hard to access by conventional direct coupling polymerizations. Herein, the tautomerization from tris(β-hydroxyl-azo)benzene to the tris(β-keto-hydrozo)cyclohexane structure has been proved unambiguously based on an advanced 2D NMR technique such as 15N-1H-HSQC and 1H-1H-NOESY. The crucial tautomerization was used to synthesize TKH-POPs for the first time. The as-synthesized TKH-POP-1 was found to have an adsorption capacity as high as 66.3 mmol g-1 (at 273 K and P/P0 = 0.98) towards acetonitrile vapor, which was the highest among all the reported materials. The general and flexible strategy to make functional POPs with tunable pores such as ultramicropores, micropores and mesopores will help develop interesting functional POPs in the near future.

Functional Porous Organic Polymers Comprising a Triaminotriphenylazobenzene Subunit as a Platform for Copper-Catalyzed Aerobic C–H Oxidation

Developing functional porous materials as a platform for the heterogeneous catalytic oxidation reaction provides a good way to solve the high environmental issues resulted by traditional oxidation ...

Design and Catalytic Application of Functional Porous Organic Polymers: Opportunities and Challenges.

This review article encompasses the progress and conventional overview of current research activities of porous organic polymers (POPs), especially in catalysis, as they have garnered colossal interest in the scientific fraternity due to their intriguing characteristic features. Various synthetic strategies with possible modification of functionality of POPs have been used to improve the catalytic efficiency towards value-added chemicals production. Accordingly, this review article is mainly focused on the design, development of various functionalized POPs by employing Friedel-Crafts alkylation, FeCl3 assisted oxidative polymerisation and polymerisation in nonaqueous medium, and a comprehensive understanding in potential catalytic applications namely, acetalization, hydrodeoxygenation (HDO), hydrogenation, coupling, photocatalytic hydrogen evolution and biomass conversion towards the production of value-added chemicals in biodiesel and chemical industries.

Feasibility Study on the Design and Synthesis of Functional Porous Organic Polymers with Tunable Pore Structure as Metallocene Catalyst Supports.

Porous organic polymers (POPs) are highly versatile materials that find applications in adsorption, separation, and catalysis. Herein, a feasibility study on the design and synthesis of POP supports with a tunable pore structure and high ethylene-polymerization activity was conducted by the selection of functional comonomers and template agents, and control of cross-linking degree of their frameworks. Functionalized POPs with a tunable pore structure were designed and synthesized by a dispersion polymerization strategy. The functional comonomers incorporated in the poly(divinylbenzene) (PDVB)-based matrix played a significant role in the porous structure and particle morphology of the prepared polymers, and a specific surface area (SSA) of 10–450 m2/g, pore volume (PV) of 0.05–0.5 cm3/g, bulk density with a range of 0.02–0.40 g/cm3 were obtained by the varied functional comonomers. Besides the important factors of thermodynamic compatibility of the selected solvent system, other factors that could be used to tune the pore structure and morphology of the POP particles have been also investigated. The Fe3O4 nanoaggregates as a template agent could help improve the porous structure and bulk density of the prepared POPs, and the highly cross-linking networks can dramatically increase the porous fabric of the prepared POPs. As for the immobilized metallocene catalysts, the pore structure of the prepared POPs had a significant influence on the loading amount of the Zr and Al of the active sites, and the typically highly porous structure of the POPs would contribute the immobilization of the active species. High ethylene-polymerization activity of 8033 kg PE/mol Zr h bar was achieved on the POPs-supported catalysts, especially when high Al/Zr ratios on the catalysts were obtained. The performance of the immobilized metallocene catalysts was highly related to the pore structure and functional group on the POP frameworks.

Direct aerobic oxidative homocoupling of benzene to biphenyl over functional porous organic polymer supported atomically dispersed palladium catalyst

Synthesis of biphenyl directly from the oxidative coupling of benzene with O2 as the sole oxident is an atom-efficiency and environmental-friendly route, which is however unattainable as yet due to the most inert nature of sp2 CH bond in benzene ring, especailly for recyclable heterogeneous catalysis. In this work, single atomic dispersed palladium(II)-porous organic polymer (POP) catalyst with a high loading (>2wt%) was constructed by anchoring Pd(II) species on the task-specifically designed POP support tethered with carboxyl acid and sulfonic acid groups. It exhibited efficient activity in the heterogeneous aerobic oxidative coupling of benzene with O2, giving the highest biphenyl yield of 26.1% so far. The high electrophilicity of thus anchored single atomic Pd(II) species is demonstrated, endowing the unprecedentedly maximum turnover number (TON) of 487 and turnover frequency (TOF) of 352h−1 that expletively exceeds 15 and 88 times of previous heterogeneous catalyst. The catalyst can be facilely recycled and reused, and readily extendable to the conversion of other nonactivated arenes into corresponding biaryls. The designing strategy of POP materials developed in the study may provide a platform towards stable single atomic dispersed noble metal species with desirable electrophilicity as efficient catalysts for more sustainable CC formation-involved organic transformations.

Retracted Article: Potential applications of functional porous organic polymer materials

Recent development of functional porous organic polymers for application in gas storage/separation, catalysis, environmental remediation and sensing has been reviewed.

Retraction: Potential applications of functional porous organic polymer materials

Retraction of ‘Potential applications of functional porous organic polymer materials’ by Weijie Zhang et al., J. Mater. Chem. A, 2017, 5, 8795–8824.

Synthesis and characterization of functional porous organic polymers as efficient metallocene catalyst supports

Porous P(HEMA-co-DVB) particles with tunable pore structure and morphology were prepared by a dispersion polymerization strategy.

ChemInform Abstract: Functional Porous Organic Polymers for Heterogeneous Catalysis

AbstractReview: 65 refs.

Functional porous organic polymers for heterogeneous catalysis

Porous organic polymers (POPs), a class of highly crosslinked amorphous polymers possessing nano-pores, have recently emerged as a versatile platform for the deployment of catalysts. The bottom-up approach for porous organic polymer synthesis provides the opportunity for the design of polymer frameworks with various functionalities, for their use as catalysts or ligands. This tutorial review focuses on the framework structures and functionalities of catalytic POPs. Their structural design, functional framework synthesis and catalytic reactions are discussed along with some of the challenges.