Mesoporous Polymer Research Articles

Construction of a transition-metal-free mesoporous organic phenanthroline-based polymeric catalyst for boosting direct activation of aromatic C–H bonds

A novel transition-metal-free mesoporous organic phenanthroline-based polymer for boosting direct activation of aromatic C–H bonds.

Thermal Behavior, Structure, and Dynamics of Water Confined in Mesoporous Silica Glass and Polymer Gel

Thermal Behavior, Structure, and Dynamics of Water Confined in Mesoporous Silica Glass and Polymer Gel

Palladium/ melamine-based porous network thin film at oil/water interface as effective catalyst for reduction of p-nitrophenol to p-aminophenol and dye degradation

Melamine-based porous network was prepared by the strong binding ability of amino functional groups of melamine with Pd(0) surface and pre-polymerization at the oil-water interface that confirmed by X-ray diffraction analysis. Palladium nanoparticles not only stimulate the pre-polymerization, but also stabilize themselves by this porous structure. Fourier-transform infrared spectroscopy, transmission electron microscopy, field-emission scanning electron microscopy, energy dispersive analysis of X-ray and thermal gravimetric analysis were applied for the catalyst characterization. The as-prepared catalyst forms an inclusion complex according to the host-guest chemistry in the presence of nitrophenols or different dyes. An efficient catalytic activity of this catalyst is due to the entrapment of the guest molecule in the cavity of the mesoporous structure and reaction progress on the Pd(0) nanoparticles surfaces which was approved by Brunauer-Emmett-Teller (BET) analysis. Simple preparation, unique structure and high catalytic reaction rate are some of the considerable advantages of this catalyst that can play key roles in the industrial processes. A practical, cost-effective and facile route for the synthesis of Pd(0)/melamine-based porous network thin film as an applicable catalyst for eliminating the water-pollution is reported. Melamine-based mesoporous polymer network was applied for the stabilization and immobilization of Pd nanoparticles, stimulating the room temperature pre-polymerization at liquid-liquid interface. • Room temperature pre-polymerization at the oil-water interface. • Simple preparation of Pd/melamine-based porous network thin film. • Unique mesoporous structure and high catalytic reaction rate. • Inclusion complex formation by entrapment of dye/nitrophenol molecules. • Eliminating the water-pollution using melamine-based mesoporous Pd-polymer networks.

Functionalized Mesoporous Polymer Ionic Liquids for Efficient Immobilization of Lipase: Effects of Ethyl Oleate

Functionalized Mesoporous Polymer Ionic Liquids for Efficient Immobilization of Lipase: Effects of Ethyl Oleate

Straightforward synthesis of multifunctional porous polymer nanomaterials for CO2 capture and removal of contaminants

A straightforward synthesis of multifunctional mesoporous polymer nanomaterials suitable for the removal of contaminants and CO2 capture is reported.

Direct synthesis of triphenylamine-based ordered mesoporous polymers for metal-free photocatalytic aerobic oxidation

Triphenylamine functionalized ordered mesoporous polymers were synthesized by an evaporation induced self-assembly (EISA) approach and were used as reusable heterogeneous photocatalysts for metal-free photocatalytic aerobic oxidation.

Universality of mesoporous coal gasification slag for reinforcement and deodorization in four common polymers

Mesoporous adsorbents and polymer deodorants are difficult to implement on a large scale because of their complicated preparation methods. Herein, a mesoporous adsorbent (CGSA) with a specific surface area of 564 m2 g−1 and a pore volume of 0.807 cm3 g−1 was prepared from solid waste coal gasification slag using a simple acid leaching process. The adsorption thermodynamics and adsorption kinetics results verified that the adsorption mechanism of propane on CGSA was mainly physisorption. Then the universality of CGSA in different polymers was investigated by introducing CGSA and its commercialized counterparts (CaCO3, and zeolite) into four common polymers. When the filler content was 30 wt%, the average reinforcement effect of CGSA on the tensile, flexural, and impact strengths of the four polymers was 46.68%, 83.62%, and 211.90% higher than that of CaCO3, respectively. Gas chromatography results also showed that CGSA significantly decreased total volatile organic compound emissions from the composites, and its optimal deodorization performance reached 69.58%, 81.33%, and 91.09% for different polymers, respectively, far exceeding that of zeolite. Therefore, this study showed that low-cost, high-performance, and multifunctional mesoporous polymer fillers with excellent universality can be manufactured from solid contaminants.

One-pot synthesis of nitrogen-doped highly ordered mesoporous polymer nanospheres as a highly efficient catalyst for the water-medium Knoevenagel reactions

One-pot synthesis of nitrogen-doped highly ordered mesoporous polymer nanospheres as a highly efficient catalyst for the water-medium Knoevenagel reactions

Synthesis of reusable cyclodextrin polymers for removal of naphthol and naphthylamine from water.

As one group of important naphthalene derivatives, naphthol and naphthylamine are diffusely employed as dye intermediates. The presence of naphthol and naphthylamine in water systems may pose risks to the environment and public health due to their carcinogenicity. In this study, four mesoporous polymers prepared by β-cyclodextrin derivatives and tetrafluoroterephthalonitrile were obtained and applied to adsorbing 1-naphthylamine, 2-naphthylamine, 1-naphthol, and 2-naphthol from water. The impact of adsorption time, initial concentration of naphthol and naphthylamine, and temperature on the adsorption efficiency of the four polymers were explored separately. The four polymers present fast adsorption kinetics toward naphthol and naphthylamine, attaining 93 ~ 100% of adsorption equilibrium uptake for 1-naphthol, 1-naphthylamine, 2-naphthylamine in 15min, and 87 ~ 90% of equilibrium uptake for 2-naphthol in 15min. The kinetics could be depicted well by the pseudo-second-order kinetic model. The adsorption isotherms of the four polymers toward naphthol and naphthylamine accord with the Redlich-Peterson or Sips model. The maximum adsorption capacities of 1-naphthylamine, 2-naphthylamine, 1-naphthol, and 2-naphthol are 189.9mg/g, 82.8mg/g, 137.7mg/g, and 88.7mg/g, respectively. The adsorption ratio increases fast with reducing the initial concentration of naphthol and naphthylamine, and the adsorption ratio of naphthol and naphthylamine in 5mg/L can achieve over 95% in 25°C. In addition, the four polymers can be effortlessly regenerated by a gentle and simple washing procedure with little reduction in performance. The adsorption performance of the four polymers toward the four naphthalene derivatives can be improved by increasing the adsorption temperature. In conclusion, the prepared β-cyclodextrin polymers exhibit rapid water treatment in removing the four low-concentration naphthalene derivatives with convenient regeneration and good reusability.

Mesoporous Networks of N-Vinylpyrrolidone with (di)Methacrylates as Precursors of Ecological Molecular Imprinted Polymers.

Mesoporous polymer networks were prepared via the cross-linking radical copolymerization of non-toxic hydrophilic N-vinylpyrrolidone (VP) with triethylene glycol dimethacrylate (TEGDM) and poly(ethylene glycol) methyl ester methacrylate (PEGMMA) in bulk, using appropriate soluble and thermodynamically compatible macromolecular additives with a branched structure as porogens. The branched copolymers of various monomer compositions were obtained by radical copolymerization in toluene, controlled by 1-decanethiol, and these materials were characterized by a wide set of physical chemical methods. The specific surface areas and surface morphology of the polymer networks were determined by nitrogen low-temperature adsorption or Rose Bengal (RB) sorption, depending on the copolymer compositions and scanning electron microscopy. The electrochemical properties of RB before and after its encapsulation into a branched VP copolymer were studied on a glassy carbon electrode and the interaction between these substances was observed. Quantum chemical modeling of RB-VP or RB-copolymer complexes has been carried out and sufficiently strong hydrogen bonds were found in these systems. The experimental and modeling data demonstrate the high potency of such mesoporous polymer networks as precursors of molecularly imprinted polymers for the recognition of fluorescent dyes as nanomarkers for biomedical practice.

Design Zwitterionic Amorphous Conjugated Micro‐/Mesoporous Polymer Assembled Nanotentacle as Highly Efficient Sulfur Electrocatalyst for Lithium‐Sulfur Batteries (Adv. Energy Mater. 40/2021)

Zwitterionic Electrocatalysts In article number 2101926, Yongguang Zhang, Xin Wang, Zhongwei Chen and co-workers design a novel zwitterionic conjugated micro/mesoporous polymer on carbon nanotubes as an assembled nanotentacle, serving as a highly efficient sulfur electrocatalyst for Li–S batteries. The zwitterionic engineering provides a new strategic perspective toward rational polysulfide regulation and conversion, holding great promise in promoting the future development of practical Li–S batteries.

A TEMPO-Functionalized Ordered Mesoporous Polymer as a Highly Active and Reusable Organocatalyst.

The properties of high stability, periodic porosity, and tunable nature of ordered mesoporous polymers make these materials ideal catalytic nanoreactors. However, their application in organocatalysis has been rarely explored. We report herein for the first time the incorporation of a versatile organocatalyst, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), into the pores of an FDU-type mesoporous polymer via a pore surface engineering strategy. The resulting FDU-15-TEMPO possesses a highly ordered mesoporous organic framework and enhanced stability, and shows excellent catalytic activity in the selective oxidation of alcohols and aerobic oxidative synthesis of 2-substituted benzoxazoles, benzimidazoles and benzothiazoles. Moreover, the catalyst can be easily recovered and reused for up to 7 consecutive cycles.

Synthesis and application of amine‐sulfone‐rich mesoporous organic polymer for the ultrafast removal of both cationic and anionic organic pollutants from industrial wastewaters

AbstractWater pollution is becoming an up‐rising threat to the environment and human being in recent years and turning to a major global challenge. The wastewaters released by the textile and dyestuff industries are one of the major sources of contamination. The aim of this work is preparation of stable, reusable, and fast adsorbent for complete removal of both cationic and anionic pollutants from industrial wastewaters. To obtain these goals, an amine‐sulfone‐rich mesoporous organic polymer (Daps‐POP) was synthesized, structurally characterized and applied for removing of methylene blue (MB) and direct blue 108 (DB‐108) as cationic and anionic model dye pollutants, respectively. The affecting variables on the adsorption process were optimized and the possible adsorbate‐adsorbent interactions were identified. The synthesized Daps‐POP was applied to industrial wastewaters and presents complete removal of model dye pollutants proving the idea of using POPs in industrial wastewater treatments. The equilibrium adsorption capacity (qe) found to be 48.1 mg.g−1 and 25.64 mg.g−1 for MB and DB‐108, respectively. The adsorption takes place in only 5 min for both dyes. Moreover, the reusability of the Daps‐POP was successful during three consecutive runs corroborating its promising application in industrial water treatment.

Design Zwitterionic Amorphous Conjugated Micro‐/Mesoporous Polymer Assembled Nanotentacle as Highly Efficient Sulfur Electrocatalyst for Lithium‐Sulfur Batteries

AbstractThe commercial application of lithium‐sulfur (LiS) batteries is seriously hampered by the sluggish redox kinetics and the shuttle effect of lithium polysulfides (LiPSs). In this study, a novel conjugated micro/mesoporous polymer (ST‐CMP) is developed by rational design of the organic condensation reaction of squaric acid and 1,3,5‐Tris(4‐aminophenyl)benzene, which can uniformly wrap onto carbon nanotube (CNT) as assembled nanotentacle, serving as the highly efficient sulfur electrocatalyst for LiS batteries. In this composite, the cross‐linked CNT conductive network significantly improves the electron transfer and reaction kinetics of active materials. In addition, the ST‐CMP assembled nanotentacle prevents the restacking or aggregation of ST‐CMP, favoring the exposure of active sites on ST‐CMP for efficient LiPSs chemical interaction. The abundant polymeric zwitterions in ST‐CMP with uniformly distributed positively polarized N atoms and negatively polarized O atoms can not only empower comprehensive regulation of LiPSs adsorption, but also simultaneously allow accelerated LiPSs catalytic conversion, rendering admirable redox reaction kinetics. With these merits, the obtained S/ST‐CMP@CNT composites exhibit a high initial specific capacity of 1307 mAh g−1 at 0.2 C with an ultralow capacity fading rate of 0.047% per cycle after 500 cycles at 1 C, exhibiting great potential in developing LiS batteries with decent performance.

Magnetically separable mesoporous alginate polymer beads assist adequate removal of aqueous methylene blue over broad solution pH

Adsorption is a promising technology for removal of organic and inorganic contaminants from soil and water system. In this study, magnetically separable mesoporous polymeric beads (NiZnFe4O4-HNT@alg) were synthesised for efficient removal of methylene blue (MB, cationic dye) under broad solution pH (from pH 3.41 to pH 8.43). Alginate biopolymer were used to stabilize halloysite nanotubes (HNTs) and nickel zinc iron oxide nanoparticles (NiZnFe4O4 < 100 nm). NiZnFe4O4 was incorporated onto the polymer beads to generate the adsorbents' magnetic properties and catalytic degradability. The adsorbent (NiZnFe4O4-HNT@alg) have higher surface area (122.43 m2/g), suitable mesoporosity (~6.68 nm), larger pore volume (0.11 cm3/g), and abundance of active sites, enabling high adsorption capacity (264 mg/g) of MB. The abundance of hydroxyl, carboxyl, and siloxane groups enabled cationic dye sorption through ionic interaction. The removal efficiency of MB was ~99% under a wide solution pH range from 10 mg/L of MB, in which the adsorbent dose was 2 g/L. Both Langmuir (R2 = 0.99; p < 0.001) and Freundlich (R2 = 0.99; p < 0.001) isotherm models fitted well, whereas trends of kinetics model fitting are pseudo-second-order (R2 = 0.99) > intraparticle diffusion (R2 = 0.93) > pseudo-first-order (R2 = 0.87). Energy-dispersive X-ray spectroscopy (EDS) elemental mapping demonstrated that MB has a co-distribution with silicon, aluminium, and alginate carbon phase but is limited with iron and nickel, indicating HNTs and alginate polymer performed as sorption sites, whereas NiZnFe4O4 performed as a catalyst. The presence (post-sorption) and absence (pre-sorption) of inorganic, total carbon or total organic carbon content at different solution pH, contact time, and initial concentration of MB demonstrated that the adsorbent act as a catalyst as well for degradation of MB. NiZnFe4O4-HNT@alg triggers efficient removal of MB with the assist of adsorption and catalytic degradation at broad solution pH. A comparison in removal of MB by various adsorbents including, biochars, clays, activated carbon, nanoparticles, polymers, nano composites, graphene oxides, carbon nanotubes, and polymer beads with the result of this study were performed, illustrating competitive sorption capacity of NiZnFe4O4-HNT@alg.

Adsorption of Selected Heavy and Precious Metals from Simulated Wastewater Using Fabricated Polyacrylonitrile (PAN) and Poly(4-Vinylpyridine) (P4VP) Monoliths

Adsorption has become an attractive method for the extraction and recovery of metals from wastewater effluents. This study involved the fabrication of mesoporous neat polyacrylonitrile (PAN) monoliths and composite polymer monoliths of PAN and poly-4-vinylpyridine (P4VP) as adsorbents for toxic elements (As(V), Cr(VI)) and the recovery of PGMs(Ru(III), Rh(III), Pd(II)) from simulated wastewater solutions. Fabrication of the mesoporous polymer monoliths was conducted using the non-solvent induced phase separation method (NIPS). The monoliths were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and Brunauer–Emmett–Teller (BET). Adsorption studies were conducted using crushed monoliths saturated in 1 mg·L−1 simulated wastewater solutions. Spectroscopic analyses of the resulting filtrates were conducted using inductively coupled plasma-optical emission spectrometry (ICP-OES). In this study, the NIPS method was successfully optimized and mesoporous PAN, as well as composite polymer monoliths, were successfully fabricated. A concentration of 1 mg·L−1 of Ru(III) and Pd(II) was completely adsorbed by both monoliths. The mesoporous composite polymer monoliths exhibited the highest adsorption capacity for Rh(III), As(V), and Cr(VI). The mesoporous polymer monoliths showed great potential for use as wastewater cleaning aids as well as remediators of precious metals.

Probe decorated porous silica and polymer monoliths as solid-state optical sensors and preconcentrators for the selective and fast recognition of ultra-trace arsenic ions

In this work, we manifested a new approach in designing solid-state colorimetric sensors for the selective optical sensing of As3+. The sensor fabrication is modulated using, (i) a cubic mesopores of ordered silica monolith, and (ii) a bimodal macro-/meso-porous polymer monolith, as hosting templates that are immobilized with a tailor-made chromoionophoric probe (DFBEP). The surface morphology and structural dimensions of the monolith templates and the sensor materials are characterized using p-XRD, XPS, FE-SEM-EDAX, HR-TEM-SAED, FT-IR, TGA, and BET/BJH analysis. The sensing components such as pH, probe content, sensor dosage, kinetics, temperature, analyte concentration, linear response range, selectivity, and sensitivity are optimized to arrive at the best sensing conditions. The silica and polymer-based monolithic sensors show a linear spectral response in the concentration range of 2–300 and 2–200 ppb, with a detection limit of 0.87 and 0.75 ppb for As3+, respectively. The real-time ion-monitoring propensity of the sensors is tested with spiked synthetic and real water samples, with a recovery efficiency of ≥99.1% (RSD ≤1.57%). The sensors act as both naked-eye optical sensors and preconcentrators, with a response time of ≤2.5 min. The molecular and photophysical properties of the DFBEP-As3+ complex are studied by TD-DFT calculations, using the B3LYP/6–31G (d,p) method.

A mesoporous polymer bearing 3D-Triptycene, –OH and azo- functionalities: Reversible and efficient capture of carbon dioxide and iodine vapor

Coal-fired power plants are the highest contributors to global electricity generation. Flue gases from thermal power plants are rich in carbon dioxide. Thus, thermal plants also contribute substantially to the annual increase in the concentration of atmospheric CO 2 (greenhouse gas) which in turn leads to increased global warming and ocean acidification. Solutions to these problems are either capture of carbon dioxide from flue gas or exploring alternative sources of power generation such as nuclear energy. However, volatile radioactive byproducts produced in nuclear plants need to be arrested by a suitable adsorbent. Herein, for the first time, we report a triptycene-based hypercrosslinked porous polymer ( TBHCP-OH ) that contains CO 2 -philic groups (–OH and –N N–). It was obtained using a simple Friedel–Crafts alkylation reaction. Mesoporous TBHCP-OH has high CO 2 capture capacity (87.6 mg/g) and excellent iodine vapor uptake capacity (2600 mg/g). This iodine uptake capacity is the highest among all triptycene based polymers reported till date. This may be attributed to the ample supramolecular interactions between arene/heteroatoms (O and N in TBHCP-OH ) and iodine. The facile and simple synthesis of TBHCP-OH as well as its ability to efficiently capture pollutants renders it a promising material for environmental remediation. • Design of a new triptycene based monomer with active CO2-philic (–N N– and –OH) and N2-phobic (azo) groups. • Facile synthesis of a mesoporous triptycene polymer ( TBHCP-OH ) with azo and phenolic functionalities via knitting strategy. • TBHCP-OH shows high CO 2 uptake of 8.76 wt.% at 273 K and 1 bar pressure which is comparable with monoethanolamine. • TBHCP-OH selectively captures CO 2 over N 2 at 1 bar which improves at higher temperature [273K (23) and 298 K (28)]. • High I 2 vapor adsorption capacity of TBHCP-OH (up to 2600 mg/g) is best among triptycene based polymers.

Microwave-assisted Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones Using Acid-Functionalized Mesoporous Polymer

Background: In recent years, 3,4-dihydro-pyrimidin-2-(1H)-ones (DHPMs) have attracted significant attention due to their diverse range of biological properties such as antibacterial, antiviral, antitumor, anti-inflammatory, calcium channel blocking activities, etc. Taking into account, in this present work, a polymer-based solid acid catalyst is employed for the microwaveassisted synthesis of DHPMs. Introduction: Multicomponent reactions (MCRs) are attracting utmost attention as they promote the formation of several bonds in a single process with diverse advantages. Biginelli reaction is the top-ranked example of MCR for the synthesis of dihydropyrimidinones (DHPMs). Solid catalysts are considered a significant tool for MCRs as they are non-toxic, easy to handle, reusable, and have high selectivity and easy separation process. Methods: DHPMs synthesis was carried out using acid-functionalized mesoporous polymer (AFMP) catalyst under microwave irradiation and solvent-free condition. Results: AFMP showed good to excellent DHPMs yield (89-98%) under the optimized reaction conditions: 1:1:1.2 molar ratio of aldehyde/ethyl acetoacetate/urea, catalyst loading of 6 wt.% (with respect to aldehyde), the temperature of 80 °C and microwave power of 500 W. Conclusion: We have successfully utilized microwave-assisted AFMP catalyst for the synthesis of DHPMs under solvent-free conditions via the Biginelli approach. The catalyst is recyclable and reusable in up to 5 consecutive reaction cycles with no significant loss in catalytic activity.

A Cationic Polymerization Strategy to Design Sulfonated Micro–Mesoporous Polymers as Efficient Adsorbents for Ammonia Capture and Separation

A Cationic Polymerization Strategy to Design Sulfonated Micro–Mesoporous Polymers as Efficient Adsorbents for Ammonia Capture and Separation