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Fuel cells offer great promise for portable electricity generation, but their use is currently limited by their low durability, excessive operating temperatures, and expensive precious metal electrodes. It is therefore essential to develop fuel cell systems that can perform effectively using more robust electrolyte materials, at reasonable temperatures, with lower-cost electrodes. Recently, proton exchange membrane fuel cells have attracted attention due to their generally favorable chemical stability and quick start-up times. However, in most membrane materials, water is required for proton conduction, severely limiting operational temperatures. Here, for the first time it is demonstrated that when acidified, PAF-1 can conduct protons at high temperatures, via a unique framework diffusion mechanism. It shows that this acidified PAF-1 material can be pressed into pellets with high proton conduction properties even at high temperatures and pellet thickness, highlighting the processibility, and ease of use of this material. Furthermore, a fuel cell is shown with high power density output is possible using a non-precious metal copper electrode. Acid-doped PAF-1 therefore represents a significant step forward in the potential for a broad-purpose fuel cell due to it being cheap, robust, efficient, and easily processible.
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Modification and functionalization of porous aromatic framework (PAF) materials have emerged as crucial research directions in various fields. In this study, we employed a hydrothermal method to synthesize a carbon quantum dots (CQDs) solution. By loading different amounts of CQDs onto the surface of PAF-45 material through ultrasonic and hydrothermal treatments, we successfully formed CQDs/PAF-45 composite materials. The introduction of CQDs effectively transformed the hydrophobic nature of PAF-45 into a hydrophilic material, thereby overcoming the challenge of achieving efficient contact between PAF catalysts and reactants in aqueous solutions. In the photocatalytic degradation experiments of Rhodamine B (RhB), tetracycline, CQDs/PAF-45 composite materials surpassed that of the pristine PAF-45 material. Notably, the 1 wt% CQDs/PAF-45 composite material exhibited the highest photocatalytic activity, with degradation efficiencies for Rhodamine B, tetracycline, and phenol approximately 1.4 times, 1.5 times and 1.5 times higher than those of the PAF-45 material, respectively.
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Porous aromatic frameworks (PAFs) are an auspicious class of materials that allow for the introduction of sulfonic acid groups at the aromatic core units by post-synthetic modification. This makes PAFs promising for proton-exchange materials. However, the limited thermal stability of sulfonic acid groups attached to aromatic cores prevents high-temperature applications. Here, we present a framework based on PAF-303 where the acid groups were added as methylene sulfonic acid side chains in a two-step post-synthetic route (SMPAF-303) via the intermediate chloromethylene PAF (ClMPAF-303). Elemental analysis, NMR spectroscopy, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy were used to characterize both frameworks and corroborate the successful attachment of the side chains. The resulting framework SMPAF-303 features high thermal stability and an ion-exchange capacity of about 1.7 mequiv g-1. The proton conductivity depends strongly on the adsorbed water level. It reaches from about 10-7 S cm-1 for 33% RH to about 10-1 S cm-1 for 100% RH. We attribute the strong change to a locally alternating polarity of the inner surfaces. The latter introduces bottleneck effects for the water molecule and oxonium ion diffusion at lower relative humidities, due to electrolyte clustering. When the pores are completely filled with water, these bottlenecks vanish, leading to an unhindered electrolyte diffusion through the framework, explaining the conductivity rise.
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Air self-charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self-charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low-temperature self-charging aqueous Zn-K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)-based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn-ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all-climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self-charging process in the absence of an external power source. Impressively, the air self-charging AZKHBs can achieve a maximum voltage of 1.15â V, an impressive discharge capacity (466.3â mAh g-1), and exceptional self-charging performance even at -40 °C. Therefore, the development of self-charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.
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Porous aromatic frameworks (PAFs) show promising potential in anionic conduction due to their high stability and customizable functionality. However, the insolubility of most PAFs presents a significant challenge in their processing into membranes and subsequent applications. In this study, continuous PAF membranes with adjustable thickness were successfully created using liquid-solid interfacial polymerization. The rigid backbone and the stable C-C coupling endow PAF membrane with superior chemical and dimensional stabilities over most conventional polymer membranes. Different quaternary ammonium functionalities were anchored to the backbone through flexible alkyl chains with tunable length. The optimal PAF membrane exhibited an OH- conductivity of 356.6â mS â cm-1 at 80 °C and 98 % relative humidity. Additionally, the PAF membrane exhibited outstanding alkaline stability, retaining 95 % of its OH- conductivity after 1000â hours in 1â M NaOH. To the best of our knowledge, this is the first application of PAF materials in anion exchange membranes, achieving the highest OH- conductivity and exceptional chemical/dimensional stability. This work provides the possibility for the potential of PAF materials in anionic conductive membranes.
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Due to the frequent oil/organic solvent leakage, efficient oil/water separation has attracted extensive concern. However, conventional porous materials possess nonpolar building units, which reveal relatively weak affinity for polar organic molecules. Here, two different polarities of superhydrophobic porous aromatic frameworks (PAFs) were synthesized with respective orthoposition and paraposition C=O groups in the PAF linkers. The conjugated structure formed by a large number of alkynyl and benzene ring structures enabled porous and superhydrophobic quality of PAFs. After the successful preparation of the PAF solids, PAF powders were coated on polyester fabrics by a simple dip-coating method, which endowed the resulting polyester fabrics with superhydrophobicity, porosity, and excellent stability. Based on the unique structure, the oil/water separation efficiency of two superhydrophobic flexible fabrics was more than 90% for various organic solvents. Polar LNU-26 PAF showed better separation performance for the polar oils. This work takes the lead in adopting the polar groups as building units for the preparation of porous networks, which has great guiding significance for the construction of advanced oil/water separation materials.
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Porous aromatic framework materials with high stability, sensitivity, and selectivity have great potential to provide new sensors for optoelectronic/fluorescent probe devices. In this work, a luminescent porous aromatic framework material (LNU-23) was synthesized via the palladium-catalyzed Suzuki cross-coupling reaction of tetrabromopyrene and 1,2-bisphenyldiborate pinacol ester. The resulting PAF solid exhibited strong fluorescence emission with a quantum yield of 18.31%, showing excellent light and heat stability. Because the lowest unoccupied molecular orbital (LUMO) of LNU-23 was higher than that of the nitro compounds, there was an energy transfer from the excited LNU-23 to the analyte, leading to the selective fluorescence quenching with a limit of detection (LOD) ≈ 1.47 × 10-5 M. After integrating the luminescent PAF powder on the paper by a simple dipping method, the indicator papers revealed a fast fluorescence response to gaseous nitrobenzene within 10 s, which shows great potential in outdoor fluorescence detection of nitro compounds.
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Nitrocompostos , Paládio , Ésteres , Corantes Fluorescentes , Nitrobenzenos , Porosidade , PósRESUMO
The strong radioactivity of iodine compounds derived from nuclear power plant wastes has motivated the development of highly efficient adsorbents. Porous aromatic frameworks (PAFs) have attracted much attention due to their low density and diverse structure. In this work, an azo group containing PAF solid, denoted as LNU-58, was prepared through Suzuki polymerization of tris-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl)-amine and 3,5-dibromoazobenzene building monomers. Based on the specific polarity properities of the azo groups, the electron-rich aromatic fragments in the hierarchical architecture efficiently capture iodine molecules with an adsorption capacity of 3533.11 mg g-1 (353 wt%) for gaseous iodine and 903.6 mg g-1 (90 wt%) for dissolved iodine. The iodine uptake per specific surface area up to 8.55 wt% m-2 g-1 achieves the highest level among all porous adsorbents. This work illustrates the successful preparation of a new type of porous adsorbent that is expected to be applied in the field of practical iodine adsorption.
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Iodo , Adsorção , Aminas/química , Iodetos , PorosidadeRESUMO
Lithium-sulfur (Li-S) batteries with high energy density are currently receiving enormous attention. However, their redox kinetics at low temperature is extremely tardy, and polysulfides shuttling is serious at high temperature, which severely hinders the implementation of wide-temperature Li-S batteries. Herein, we propose an all-climate Li-S battery based on an ether-based electrolyte by using a porous sub-nano aromatic framework (SAF) modified separator. It's demonstrated that the fully conjugated SAF-3 with a small pore size (0.97â nm) and narrow band gap (1.72â eV) could efficiently block the polysulfides shuttling at elevated temperature and boost the polysulfides conversion at low temperature. Consequently, the SAF-3 modified cells work well in a wide temperature ranging from -40 to 60 °C. Furthermore, when operated at room temperature, the modified cell exhibits 90 % capacity retention over 100 cycles under high-sulfur loading (5.0â mg cm-2 ) and lean electrolyte (5â µL mg-1 ).
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An ionic porous aromatic framework is developed as a self-degraded template to synthesize the magnetic heterostructure of γ-Fe2O3/WO3·0.5H2O. The Fe3O4 polyhedron was obtained with the two-phase method first and then reacted with sodium tungstate to form the γ-Fe2O3/WO3·0.5H2O hybrid nanostructure. Under the induction effect of the ionic porous network, the Fe3O4 phase transformed to the γ-Fe2O3 state and complexed with WO3·0.5H2O to form the n-n heterostructure with the n-type WO3·0.5H2O on the surface of n-type γ-Fe2O3. Based on a UV-Visible analysis, the magnetic photocatalyst was shown to have a suitable band gap for the catalytic degradation of organic pollutants. Under irradiation, the resulting γ-Fe2O3/WO3·0.5H2O sample exhibited a removal efficiency of 95% for RhB in 100 min. The charge transfer mechanism was also studied. After the degradation process, the dispersed powder can be easily separated from the suspension by applying an external magnetic field. The catalytic activity displayed no significant decrease after five recycles. The results present new insights for preparing a hybrid nanostructure photocatalyst and its potential application in harmful pollutant degradation.
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Nitrogen-rich porous networks with additional polarity and basicity may serve as effective adsorbents for the Lewis electron pairing of iodine molecules. Herein a carbazole-functionalized porous aromatic framework (PAF) was synthesized through a Sonogashira-Hagihara cross-coupling polymerization of 1,3,5-triethynylbenzene and 2,7-dibromocarbazole building monomers. The resulting solid with a high nitrogen content incorporated the Lewis electron pairing effect into a π-conjugated nano-cavity, leading to an ultrahigh binding capability for iodine molecules. The iodine uptake per specific surface area was ~8 mg m-2 which achieved the highest level among all reported I2 adsorbents, surpassing that of the pure biphenyl-based PAF sample by ca. 30 times. Our study illustrated a new possibility for introducing electron-rich building units into the design and synthesis of porous adsorbents for effective capture and removal of volatile iodine from nuclear waste and leakage.
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Solid-state Li-ion batteries (SSLIBs) have recently attracted substantial attention from scientists for the advantages of better safety performance. However, there are still several key challenges in SSLIBs that need to be addressed, such as low energy density, poor thermal stability or cycle stability, and large interface resistance. This contribution introduces a novel SSLIB with a porous aromatic framework (PAF-1) accommodating LiPF6 that was used as the solid-state electrolyte (SSE) replacing the liquid electrolyte and diaphragm of traditional Li-ion batteries. The charge, discharge capacity, rate performance and cycle stability of the SSLIB were remarkably enhanced.
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Lithium-ion batteries (LIBs) have revolutionized the energy storage landscape and are the preferred power source for various applications, ranging from portable electronics to electric vehicles. The constant drive and growth in battery research and development aim to enhance their performance, energy density, and safety. Advanced lithium batteries (LIBs) are considered to be the most promising electrochemical storage devices, which can provide high specific energy, volumetric energy density, and power density. However, the trade-off between ionic conductivity and cycling stability is still a major contradiction for SPEs. In this work, a novel hydroxylated PAF-1 was designed and synthesized through post-modification, and the lithium-rich single-ion porous aromatic framework PAF-1-OLi was thereafter prepared by lithiation, achieved with a specific surface area to be 155 m2 g-1 and a lithium content of 2.01 mmol g-1. PAF-1-OLi, lithium bis(trifluoromethanesulfony)limine (LiTFSI), and poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) were compounded to obtain PAF-1-OLi/PVDF by solution casting, which had good mechanical, thermodynamic, and electrochemical properties. The ion conductivity of PAF-1-OLi/PVDF infiltrated with plasticizer was 2.93 × 10-4 S cm-1 at 25 °C. The tLi+ was 0.77, which was much higher than that of the traditional dual-ion polymer electrolytes. The electrochemical window of PAF-1-OLi/PVDF can reach 4.9 V. The Li//PAF-1-OLi/PVDF//LiFePO4 battery initial discharge specific capacity was 147 mAh g-1 and reached 134.9 mAh g-1 after 600 cycles with a capacity retention rate of 91.2%, demonstrating its good cycling stability. The anionic part of lithium salt was fixed on the framework of PAF-1 to increase the Li+ transfer number of PAF-1-OLi/PVDF. The lithium-rich PAF-1-OLi and the LiTFSI provided abundant Li+ sources to transfer, while PAF-1-OLi helped to form a continuous Li+ transport channel, effectively promoting the migration of Li+ in the PAF-1-OLi/PVDF and effectively improving the Li+ conductivity. This study afforded a novel polymer electrolyte based on lithium-rich PAF-1-OLi, which has excellent electrochemical performance, providing a new choice for the polymer electrolyte of lithium batteries.
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The development of robust and efficient porous adsorbents is essential for capturing xenon (Xe) and perfluorinated electron specialty gases (F-gases) in semiconductor exhaust gases, as toxic and corrosive gases coexist in high-temperature plasma degradation off-gases. Herein, two three-dimensional (3D) fluorinated porous aromatic frameworks (PAFs) with abundant fluorine (labeled PAF-4F and PAF-8F) were synthesized. The two PAFs exhibit high IAST selectivity in capturing Xe and F-gases from semiconductor off-gases, as well as excellent physicochemical stability and reusability, which have been collaboratively verified by single-component gas adsorption and regeneration tests, etc. Density functional theory (DFT) simulation revealed that the entry of strongly electronegative fluorine atoms into PAFs causes localized charge separation on the polymer pore surface, resulting in the preferential adsorption of high-polarizability Xe and F-gases via induced electric field gradients. Systematic studies have sufficiently manifested the great potential of fluorine-functionalized porous materials to effectively capture Xe and F-gases, which provides practical insights into the fabrication of highly stable porous adsorbents for harsh operating conditions.
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This work was focused on the mitigation of physical aging in thin-film composite (TFC) membranes (selective layer ~1 µm) based on polymer intrinsic microporosity (PTMSP) by the introduction of both soft, branched polyethyleneimine (PEI), and rigid, porous aromatic framework PAF-11, polymer additives. Self-standing mixed-matrix membranes of thicknesses in the range of 20-30 µm were also prepared with the same polymer and fillers. Based on 450 days of monitoring, it was observed that the neat PTMSP composite membrane underwent a severe decline of its gas transport properties, and the resultant CO2 permeance was 14% (5.2 m3 (STP)/(m2·h·bar)) from the initial value measured for the freshly cast sample (75 m3 (STP)/(m2·h·bar)). The introduction of branched polyethyleneimine followed by its cross-linking allowed to us to improve the TFC performance maintaining CO2 permeance at the level of 30% comparing with day zero. However, the best results were achieved by the combination of porous, rigid and soft, branched polymeric additives that enabled us to preserve the transport characteristics of TFC membrane as 43% (47 m3 (STP)/(m2·h·bar) after 450 days) from its initial values (110 m3 (STP)/(m2·h·bar)). Experimental data were fitted using the Kohlrausch-Williams-Watts function, and the limiting (equilibrium) values of the CO2 and N2 permeances of the TFC membranes were estimated. The limit value of CO2 permeance for neat PTMSP TFC membrane was found to be 5.2 m3 (STP)/(m2·h·bar), while the value of 34 m3(STP)/(m2·h·bar) or 12,600 GPU was achieved for TFC membrane containing 4 wt% cross-linked PEI, and 30 wt% PAF-11. Based on the N2 adsorption isotherms data, it was calculated that the reduction of the free volume was 1.5-3 times higher in neat PTMSP compared to the modified one. Bearing in mind the pronounced mitigation of physical aging by the introduction of both types of fillers, the developed high-performance membranes have great potential as support for the coating of an ultrathin, selective layer for gas separation.
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Simultaneously capturing organic pollutants and heavy metal can greatly reduce the water remediation time and cost, however it is still a great challenge presently. Herein, two novel thiol/methylthio-functionalized porous aromatic frameworks were synthesized as sorbents via the Sonogashira-Hagihara reaction of 1,3,5-triethynylbenzene and 1,3,5-tris(4-bromophenyl) benzene, the subsequent chloromethylation of the phenyl rings, and the final nucleophile substitution of -Cl groups by NaSH/NaSMe. These two sorbents were characterized by FT-IR spectra, energy dispersive X-ray spectra, scanning electron microscope, nitrogen adsorption analysis, thermo-gravimetric analysis, and elemental analyses. Adsorption experiments displayed that new sorbents had high uptake abilities and fast adsorption kinetics for aromatic pollutants and mercury (II) (Hg(II)). The maximum adsorption capacity (Qmax) of toluene and m-xylene on both new sorbents were 531.9-571.4 mg/g with the kinetic binding rate constants (kobs) of 0.00276-0.02422 g/mg/min, and the Qmax values of Hg(II) were 148.1-180.3 mg/g with kobs of 0.00592-0.01573 g/mg/min. Moreover, new sorbents indicated high simultaneous uptake abilities for these pollutants with good reusability, and finally they were successfully applied to the simultaneous remediation of these pollutants in two simulated sewages with high and low concentration, indicating their great practical application potential in wastewater remediation.
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Poluentes Ambientais , Mercúrio , Poluentes Químicos da Água , Adsorção , Cinética , Porosidade , Espectroscopia de Infravermelho com Transformada de Fourier , Compostos de Sulfidrila , Água , Poluentes Químicos da Água/análiseRESUMO
Highly efficient removal of bilirubin from blood by hemoperfusion for liver failure therapy remains a challenge in the clinical field due to the low adsorption capacity and slow adsorption kinetics of currently used bilirubin adsorbents (e.g., activated carbon and ion-exchange resin). Recently, porous aromatic frameworks (PAFs) with high surface areas, tunable structures, and remarkable stability provide numerous possibilities to obtain satisfying adsorbents. Here, a cationic PAF with more mesopores, named iPAF-6, is successfully constructed via a de novo synthetic strategy for bilirubin removal. The prepared iPAF-6 exhibits a record-high adsorption capacity of 1249 mg g-1 and can adsorb bilirubin from 150 mg L-1 to normal concentration in just 5 min. Moreover, iPAF-6 shows a removal efficiency of 96% toward bilirubin in the presence of 50 g L-1 bovine serum albumin. It is demonstrated that positively charged aromatic frameworks and large pore size make a significant contribution to its excellent adsorption ability. More notably, iPAF-6/polyethersulfone composite fibers or beads are fabricated for practical hemoperfusion adsorption, which also show better removal performance than commercial adsorbents. This work can offer a new possibility for designing PAF-based bilirubin adsorbents with an appealing application prospect.
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Triazine rings-containing porous aromatic framework (PAF-56p) was synthesized through a Friedel-Crafts reaction and investigated as a coating for the stir bar sorptive extraction (SBSE) of interest triazines. The triazine rings and conjugated groups in PAF-56p could interact with triazine rings-containing herbicides by hydrophobic and π-π interactions. The PAF-56p coated stir bar showed superior extraction performance over commercial PDMS and EG coated stir bar in terms of extraction efficiency and dynamics towards six triazine herbicides with different polarity. Based on it, a method by combining PAF-56p-SBSE with high performance liquid chromatography (HPLC)-diode array detector (DAD) was established for the analysis of six target triazine herbicides, including simazine, atrazine, ametryn, prometon, prometryne and prebane. The affecting factors of SBSE were investigated by single-factor test. Under the optimized conditions, the limits of detection of the proposed method were ranged from 0.037 to 0.089 µg/L with the linear range within 0.1-200 µg/L for six triazine herbicides. High enrichment factors (EFs) of 61.8-89.5-fold (theoretical EF is 100-fold) were achieved. The developed PAF-56p-SBSE-HPLC-DAD method was successfully applied for trace triazine herbicides analysis in maize and maize leaf samples, with recoveries in the range of 86.5-115% and 85.1-114% for spiked maize and maize leaf samples, respectively.
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Técnicas de Química Analítica/métodos , Cromatografia Líquida de Alta Pressão , Herbicidas/análise , Triazinas/análise , Zea mays/química , Técnicas de Química Analítica/instrumentação , Herbicidas/isolamento & purificação , Limite de Detecção , Porosidade , Reprodutibilidade dos Testes , Triazinas/isolamento & purificaçãoRESUMO
To move nuclear as a primary energy source, uranium resources must be secured beyond what terrestrial reserves can provide. Given the vast quantity of uranium naturally found in the ocean, adsorbent materials have been investigated to recover this vital fuel source. Amidoxime (AO) has been found to be the state-of-the-art functional group for this purpose, however, improvements must still be made to overcome the issues with selectively capturing uranium at such a low concentration found in the ocean. Herein, we report PAF-1 as a platform to study the effects of two amidoxime ligands. The synthesized adsorbents, PAF-1-CH2NHAO and PAF-1-NH(CH2)2AO, with varying chain lengths and grafting degrees, were investigated for their uranium uptakes and kinetic efficiency. PAF-1-NH(CH2)2AO was found to outperform PAF-1-CH2NHAO, with a maximum uptake capacity of 385 mg/g and able to reduce a uranium-spiked solution to ppb level within 10 min. Further studies with PAF-1-NH(CH2)2AO demonstrated effective elution for multiple adsorption cycles and showed promising results for uranium recovery in the diverse composition of a spiked seawater solution. The work presented here moves forward design principles for amidoxime-functionalized ligands and provides scope for strategies to enhance the capture of uranium as a sustainable nuclear fuel source.
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In this study, a solid-phase extraction-high performance liquid chromatography (SPE-HPLC) method was developed for the determination of Para Red, Orange â ¡ sodium salt, Sudan â , and Sudan â ¡ in paprika powder based on a self-made porous aromatic framework-6 (PAF-6) solid-phase extraction cartridge. The major factors affecting the extraction efficiency and adsorption capacity of this solid-phase extraction were evaluated. Under optimized conditions, the limits of detection (LODs) and limits of quantification (LOQs) of the four target analytes ranged from 1.5 to 7.0 µg/L and 5.0 to 22.1 µg/L, respectively. The recoveries were in the range of 76.5-89.8%, and the relative standard deviation (RSD) was not more than 5.3% (n=6). Moreover, quantum chemistry calculations were performed to investigate the molecular interaction mechanism between the PAF-6 and target analytes. The results indicated that the target molecules could be stably adsorbed onto the PAF-6. The method is accurate, reliable, and sensitive, and can be successfully applied to detect the four azo dyes in paprika powder.