In the pursuit of fabricating functional ceramic nanostructures, the design of preceramic functional polymers has garnered significant interest. With their easily adaptable chemical composition, molecular structure, and processing versatility, these polymers hold immense potential in this field. Our study succeeded in focusing on synthesizing ferrocene-containing block copolymers (BCPs) based on polyacrylonitrile (PAN). The synthesis is accomplished via different poly(acrylonitrile-block-methacrylate)s via atom transfer radical polymerization (ATRP) and activators regenerated by electron transfer ATRP (ARGET ATRP) for the PAN macroinitiators. The molecular weights of the BCPs range from 44 to 82 kDa with dispersities between 1.19 and 1.5 as determined by SEC measurements. The volume fraction of the PMMA block ranges from 0.16 to 0.75 as determined by NMR. The post-modification of the BCPs using 3-ferrocenyl propylamine has led to the creation of redox-responsive preceramic polymers. The thermal stabilization of the polymer film has resulted in stabilized morphologies based on the oxidative PAN chemistry. The final pyrolysis of the sacrificial block segment and conversion of the metallopolymer has led to the formation of a porous carbon network with an iron oxide functionalized surface, investigated by scanning electron microscopy (SEM), energy dispersive X-ray mapping (EDX), and powder X-ray diffraction (PXRD). These findings could have significant implications in various applications, demonstrating the practical value of our research in convenient ceramic material design.

This paper presents original results from the unique analysis of the porous structure of activated carbons (ACs) produced through the chemical activation of polyethylene terephthalate (PET) and polyacrylonitrile (PAN), as well as from a physical mixture of both polymers. An advanced method of adsorbent surface analysis-more specifically, the new method of numerical clustering-based adsorption analysis regarding the surface heterogeneity, pore geometry and adsorption energy distribution parameters-allowed us to obtain information about the porous structure of the ACs from the synthetic polymers mentioned above. As the results showed, ACs obtained with PAN were characterised by a first adsorbed layer with the highest volume. When the surface heterogeneity, highly desirable in most advanced adsorption processes, is taken into account, the materials with the best surface properties in both potassium carbonate (K2CO3) and potassium hydroxide (KOH) activation processes were the ACs obtained with a mass proportion of PET to PAN of 1:3, which were characterised by a low degree of surface heterogeneity and a first adsorbed layer presenting a relatively large volume.

Polyacrylonitrile (PAN) is an important commercial polymer, bearing atactic stereochemistry resulting from nonselective radical polymerization. As such, an accurate, fundamental understanding of governing interactions among PAN molecular units is indispensable for advancing the design principles of final products at reduced processability costs. While ab initio molecular dynamics (AIMD) simulations can provide the necessary accuracy for treating key interactions in polar polymers, such as dipole-dipole interactions and hydrogen bonding, and analyzing their influence on the molecular orientation, their implementation is limited to small molecules only. Herein, we show that the neural network interatomic potentials (NNIPs) that are trained on the small-scale AIMD data (acquired for oligomers) can be efficiently employed to examine the structures and properties at large scales (polymers). NNIP provides critical insight into intra- and interchain hydrogen-bonding and dipolar correlations and accurately predicts the amorphous bulk PAN structure validated by modeling the experimental X-ray structure factor. Furthermore, the NNIP-predicted PAN properties, such as density and elastic modulus, are in good agreement with their experimental values. Overall, the trend in the elastic modulus is found to correlate strongly with the PAN structural orientations encoded in the Hermans orientation factor. This study enables the ability to predict the structure-property relations for PAN and analogues with sustainable ab initio accuracy across scales.

Dyes, as organic pollutants, are causing increasingly severe environmental problems. Metal-organic frameworks (MOFs) are considered promising dye adsorbents; however, their application is limited due to their powder or solid particle forms and limited reusability. Therefore, this study proposes an innovative approach to develop a novel MOF-based composite aerogel, specifically a HKUST-1/polyacrylonitrile nanofibers/regenerated cellulose (HKUST-1/PANNs/RC) composite aerogel adsorbent, for the adsorption of pollutants in water. This adsorbent was successfully prepared using a simple method combining covalent crosslinking, quick freezing, freeze-drying, in-situ growth synthesis, and solvothermal techniques. The HKUST-1/PANNs/RC composite aerogel exhibits a significantly large specific surface area, which is approximately 64 times greater than that of PANNs/RC (10.45 m2·g-1), with a specific surface area of 669.9 m2·g-1. The PANNs serve as a support framework, imparting excellent mechanical properties to the composite aerogel, enhancing its overall stability and recoverability. Additionally, the composite aerogel contains numerous -COOH and -OH groups on its surface, providing strong acid resistance and facilitating interactions with pollutant molecules through electrostatic interactions, π-π conjugation, n-π* interactions, and hydrogen bonding, thereby promoting the adsorption process. Using methylene blue (MB) as a probe molecule, the study results demonstrate that the HKUST-1/PANNs/RC composite aerogel has an adsorption capacity of 522.01 mg·g-1 for MB (25 h), exhibiting excellent adsorption performance. This composite aerogel shows great potential for application in water pollution control.

Volatile organic compounds (VOCs) in the air pose great health risks to humans and the environment. Adsorptive separation technology has proven effective in mitigating VOC pollution, with the adsorbent being the critical component. Therefore, the development of highly efficient adsorbent materials is crucial. Carbon nanofibers, known for their physical-chemical stability and rapid adsorption kinetics, are promising candidates for removing VOCs from the air. However, the relatively simple porous structures and inert surface chemical properties of traditional carbon nanofibers present challenges in further enhancing their application performance further. Herein, a hierarchical porous carbon nanofibrous membrane was prepared using electrospinning technology and a one-step carbonization & activation method. Phenolic resin and polyacrylonitrile were used as co-precursors, with silica nanoparticles serving as the dopant. The resulting membrane exhibited a specific surface area of up to 1560.83 m2/g and surfaces rich in functional O-/N- groups. With a synergistic effect of developed micro- and meso-pores and active chemical surfaces, the carbon nanofibrous membrane demonstrated excellent adsorption separation performance for various VOCs, with comparable adsorption capacities and fast kinetics. Moreover, the membrane displayed remarkable reusability and dynamic adsorption performance for different VOCs, indicating its potential for practical applications.

A lithium titanate-decorated Ti3C2Tx MXene (LTO-MX) composite was synthesized through etching and alkali processes, and subsequently immobilized using polyacrylonitrile (PAN) polymer via a phase inversion method. In the batch study, the strontium adsorption behavior followed the Redlich-Peterson isotherm and the pseudo-second-order kinetic models. The maximum adsorption capacity for strontium reached 24.05 mg/g. Furthermore, a continuous fixed-bed column study was performed using the LTO-MX PAN beads to remove strontium from aqueous solutions. The dynamic behavior of column adsorption was examined under various operating parameters such as initial strontium concentration, flow rate, and bed height. Dynamic modeling was employed to describe adsorption breakthrough properties based on these experimental data. Both the Thomas and Yoon-Nelson models accurately simulated the breakthrough curves. The proposed mechanisms for strontium adsorption included encapsulation, electrostatic attraction, cation exchange, and surface complexation. These results demonstrate the effectiveness of LTO-MX PAN beads as adsorbents for the continuous removal of strontium from radioactive wastewater.

This work aims at the preparation and characterization of dual-layer (DL) nano-fibrous mat (NFM) of hydrophobic and mechanical stable polyacrylonitrile (PAN) nano-fibers (NFs), as a supporter, and polyamide 6 (PA)/chitosan (Ch) NFs as a top hydrophilic coating layer. PAN and PA fibers, as residual wastes from textile processes, were collected and dissolved in their proper solvents. PAN was electro-spuned under certain conditions of electro-spinning (voltage, flow rate, and distance between spinneret and collector) to obtain PAN-NFM. Different ratios of PA/Ch composite were prepared and then electro-spun above the PAN-NFM that was previously prepared to obtain hydrophobic/hydrophilic functional dual-layer nano-fibrous membrane (DLNFM). The efficiency of the prepared DLNFM for capturing dye residues and heavy metals from wastewater was investigated. The viscosities of the prepared composite solutions were measured. The prepared dual-layer nano-fiber membranes (DLNFMs) were chemically and physically characterized by Fourier transform infrared spectroscopy, scanning electron microscope, X-ray diffraction, and thermogravimetric analyzer. The potential of the prepared mats for the adsorption of some heavy metal ions, i.e., Cu+2, Cr+3, and Pb+2 cations in addition to dyes from wastewater was evaluated. The effect of using different concentrations of PA/Ch composite as well as the thickness of the obtained DLNFM on the filtration efficiency was studied. The results of this study show the success of functional DLNFM in dye and heavy metal removal. The maximum removal efficiency of acid dyes was reached to 73.4 % and of reactive dye was approximately 61 % for PAN/PA-1.25%Ch DLNFM after 3 days at room temperature. The removal efficiency percent of heavy metal ions reached to 54 % by DLNFM. Additionally, the results showed that 0.08 mm is the ideal thickness for maximum absorption capacity. This value is correlated with the membrane\'s highest Ch percentage, which is (PAN/PA-1.25%Ch). Furthermore, the results demonstrate that the presence of the Ch polymer strengthened the produced bi-layered membrane to achieve the highest thermal stability when compared to the other nano-fibrous membranes (NFMs), with the breakdown temperature of the Ch functionalized dual-layer membranes (DLMs) reaching approximately 617 °C and a maximum weight loss of 60 %.

Nanohybrid assemblies provide an effective platform for integrating the intrinsic properties of individual components into microscale fibers. In this study, a novel approach for creating mechanically and environmentally stable MXene fibers through the synergistic assembly of MXene and polyacrylonitrile (PAN), is introduced. Unlike fibers generated via a conventional stabilization process, which relies on air-based stabilization to transform the PAN molecules into ring structures fundamental to carbon fibers, the hybrid fibers are annealed in an Ar atmosphere. This unique approach suggests MXene can serve as an oxygen provider that is essential for stabilizing PAN. As a result, significantly improved interfiber compactness is achieved and the oxidation stability of MXene is enhanced under atmospheric conditions. The resulting fibers exhibit exceptional stability, even after extended exposure to high humidity and elevated temperatures. This highlights the suitability of the thermally annealed MXene-PAN (T-MX-PAN) fibers as robust electric heating elements. Notably, these fibers consistently generate heat over 1800 bending cycles. When integrated into fabrics, they demonstrate the capability to generate sufficient heat for melting ice and rapid evaporation. This study highlights the potential of T-MX-PAN fibers as next-generation wearable heaters and offers valuable insights into advancing wearable technology in demanding environments.

This paper reports the successful fabrication of a new nanofibrous membrane, F-PI/PAN, through electrospinning of polyacrylonitrile (PAN) and fluorinated polyimide (F-PI). The nanofibrous membrane exhibits comprehensive properties for high-temperature filtration and robust PM2.5 (particulate matter with an aerodynamic equivalent diameter of 2.5 microns or less) removal. The introduction of F enhances the hydrophobicity of the PI. The relationship between the hydrophobic performance and the filtration performance of particles is investigated. The chemical group of the composite membrane was demonstrated using FITR, while the surface morphology was investigated using field emission scanning electron microscopy. The TGA results indicated good thermal stability at 300 °C. Various ratios of F-PI membranes were prepared to characterize the change in properties, with the optimal mass ratio of F-PI being 20 wt%. As the proportion of F-PI increases, its mechanical and filtration efficiency properties and hydrophobicity become stronger. The contact angle reaches its maximum of 128 ± 5.2° when PAN:F-PI = 6:4. Meanwhile, when PAN:F-PI = 8:2, the filtration efficiency reaches 99.4 ± 0.3%, and the elongation at break can reach 76%. The fracture strength can also reach 7.1 MPa, 1.63 times that of the pure PAN membrane.

The rheological properties, spinnability, and thermal-oxidative stabilization of high-molecular-weight linear polyacrylonitrile (PAN) homopolymers (molecular weights Mη = 90-500 kg/mol), synthesized via a novel metal-free anionic polymerization method, were investigated to reduce coagulant use, enable solvent recycling, and increase the carbon yield of the resulting carbon fibers. This approach enabled the application of the mechanotropic (non-coagulating) spinning method for homopolymer PAN solutions in a wide range of molecular weights and demonstrated the possibility of achieving a high degree of fiber orientation and reasonable mechanical properties. Rheological analysis revealed a significant increase in solution elasticity (G\') with increasing molecular weight, facilitating the choice of optimal deformation rates for effective chain stretching prior to strain-induced phase separation during the eco-friendly spinning of concentrated solutions without using coagulation baths. The possibility of collecting ~80 wt% of the solvent at the first stage of spinning from the as-spun fibers was shown. Transparent, defect-free fibers with a tensile strength of up to 800 MPa and elongation at break of about 20% were spun. Thermal treatment up to 1500 °C yielded carbon fibers with a carbon residue of ~50 wt%, in contrast to ~35 wt% for industrial radically polymerized PAN carbonized under the same conditions.