碱性膜燃料电池阳极碳酸化模型研究

碱性聚电解质燃料电池（APEFC）近年来取得了可观的进展,但是在使用空气作为氧化剂工作时仍然面临着性能损失. 文献中已有多个理论试图解释性能损失的来源,但是缺乏定量化的分析. 本文根据实验发现和热力学及阳极反应的动力学分析,提出了分层的阳极碳酸化模型和方程组.模型的定量化模拟结果进一步和实验结果进行验证,提出了电池性能损失的可能原因.     

Needle-free electrospinning of nanofibrillated cellulose and graphene nanoplatelets based sustainable poly (butylene succinate) nanofibers

Sustainable materials have slowly overtaken the nanofiber research field while the tailoring of their properties and the upscaling for industrial production are some of the major challenges. We report preparation of nanofibers that are bio-based and biodegradable prepared from poly (butylene succinate) (PBS) with the incorporation of nanofibrillated cellulose (NFC) and graphene nanoplatelets (GN). NFC and GN were combined as hybrid filler, which led to the improved morphological structure for electrospun nanofibers. A needleless approach was used for solution electrospinning fabrication of nanofiber mesh structures to promote application scalability. The polymer crystallization process was examined by differential scanning calorimetry (DSC), the thermal stability was evaluated by thermal gravimetric analysis (TGA), while the extensive investigation of the nanofibers structure was carried out with scanning electron microscopy (SEM) and atomic force microscopy (AFM). NFC and GN loadings were 0.5 and 1.0 wt %; while poly (ethylene glycol) (PEG) was employed as a compatibilizer to enhance fillers’ interaction within the polymer matrix. The interactions in the interface of the fillers and matrix components were studied by FTIR and Raman spectroscopies. The hybrid filler approach proved to be most suitable for consistent and high-quality nanofiber production. The obtained dense mesh-based structures could have foreseeable potential application in biomedical field like scaffolds for the tissue and bone recovery, while other applications could focus on filtration technologies and smart sensors.     

Polymer Networks: From Plastics and Gels to Porous Frameworks

Polymer networks, which are materials composed of many smaller components—referred to as “junctions” and “strands”—connected together via covalent or non‐covalent/supramolecular interactions, are arguably the most versatile, widely studied, broadly used, and important materials known. From the first commercial polymers through the plastics revolution of the 20^th century to today, there are almost no aspects of modern life that are not impacted by polymer networks. Nevertheless, there are still many challenges that must be addressed to enable a complete understanding of these materials and facilitate their development for emerging applications ranging from sustainability and energy harvesting/storage to tissue engineering and additive manufacturing. Here, we provide a unifying overview of the fundamentals of polymer network synthesis, structure, and properties, tying together recent trends in the field that are not always associated with classical polymer networks, such as the advent of crystalline “framework” materials. We also highlight recent advances in using molecular design and control of topology to showcase how a deep understanding of structure–property relationships can lead to advanced networks with exceptional properties.     

Polymer Nanocontainers for Intracellular Delivery

Carriers for intracellular delivery are required to overcome limitations of therapeutic agents such as low specificity, systemic toxicity, high clearance rate, and low therapeutic index. Nanocontainers comprised of an aqueous core and a polymer shell have received increasing attention because they readily combine stimuli response to improve intracellular payload release and surface modification to enhance selectivity towards the desired region of action. This Minireview summarizes the design and properties of polymer nanocontainers for intracellular delivery, classified according to the polymer architecture.     

A Molecular Strategy to Lock‐in the Conformation of a Perylene Bisimide‐Derived Supramolecular Polymer

Locking‐in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)‐derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure–function relationships. Experiments that exploit variable‐temperature ground‐state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non‐covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid‐state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non‐covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100‐mV stabilization of the conduction band energy when compared to that recorded for the non‐covalent assembly.     

Excitation‐Dependent Long‐Life Luminescent Polymeric Systems under Ambient Conditions

Organic room temperature luminescent materials present a unique phosphorescence emission with a long lifetime. However, many of these materials only emit single blue or green color in spite of external stimulation, and their color tunability is limited. Herein, we report a rational design to extend the emission color range from blue to red by controlling the doping of simple pyrene derivatives into a robust polymer matrix. The integration of these pyrene molecules into the polymer films enhances the intersystem crossing pathway, decreases the first triplet level of the system, and ensures the films show a sensitive response to excitation energy, finally yielding excitation‐dependent long‐life luminescent polymeric systems under ambient conditions. These materials were used to construct anti‐counterfeiting patterns with multicolor interconversion, presenting a promising application potential in the field of information security.     

Chemical modification of carbon fiber with diethylenetriaminepentaacetic acid/halloysite nanotube as a multifunctional interfacial reinforcement for silicone resin composites

In the present research, a multifunctional hierarchical reinforcement was prepared by chemical modification of carbon fibers (CFs) with halloysite nanotubes (HNTs) by the bridging diethylenetriaminepentaacetic acid (DTPA) for improving interfacial microstructures and properties of composites. Surface structures and groups of modified HNTs and CFs were characterized systematically. The uniform distributions of the introduced DTPA and HNTs helped to increase fiber polarity, surface energy, and wettability. As a consequence, significant enhancements of interfacial properties and hydrothermal aging resistance of composites were achieved, and interfacial reinforcing mechanisms have also been studied. Moreover, the storage modulus showed a 17.95% improvement, and the glass transition temperature was enhanced by 17°C by dynamic mechanical analysis testing.     

A Sensor for Serotonin and Dopamine Detection in Cancer Cells Line Based on the Conducting Polymer−Pd Complex Composite

An electrochemical sensor based on the conducting polymer composite with a palladium complex (Pd(C₂H₄N₂S₂)₂) was developed for the detection of serotonin and dopamine simultaneously in the breast cancer cell and human plasma samples. The proposed sensor was fabricated using the Pd(C₂H₄N₂S₂)₂ complex‐anchored poly2,2 : 5,2‐terthiophene‐3‐(p‐benzoic acid) (pTBA) layer on the AuNPs decorated reduced graphene oxide (AuNPs@rGO) substrate, which revealed the enhanced anodic current of the target species. The sensor probe was characterized by electrochemical and surface analysis methods. The experimental parameters affecting the sensor performance were optimized, in terms of AuNPs@rGO concentration, the number of electropolymerization cycle for pTBA, immobilization time of Pd(C₂H₄N₂S₂)₂, and pH. The dynamic ranges for serotonin and dopamine were obtained from 0.02 to 200 μM, and from 0.1 to 200 μM with the detection limit of 2.5, and 24.0 nM, respectively. The reliability of proposed sensor was evaluated using cancer cell lines for the clinical applications.     

Molecularly Imprinted Impedimetric Sensor for Determination of Mycotoxin Zearalenone

The mycotoxin zearalenone (ZEA) prompts reproductive toxicity due to its strong estrogenic effects. In this work, an electrochemical sensor for determination of ZEA was developed by electropolymerization of a molecularly imprinted poly (o‐phenylenediamine) (PPD) film on screen‐printed gold electrode (SPGE) surface. The sensor was examined by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) using K₃[Fe(CN)₆]/K₄[Fe(CN)₆] as redox probe. The molecularly imprinted polymer (MIP) sensor showed a wide determination range from 2.50 to 200.00 ngmL^?1 for ZEA. The Limit of detection (LOD) was calculated to be 0.20 ngmL^?1, based on the signal to noise (S/N) ratio equal to 3.0. The sensor displayed good repeatability, with RSD values≤4.6 %, and maintained 93.2 % of its initial response after storage for 10 days in air at room temperature. The developed method was successfully applied for the determination of ZEA in corn flakes with mean recoveries ranged from 96.2 % to 103.8 % and RSDs within the interval of 2.1 % to 3.8 %.     

Synthesis of an Alternated Heterobimetallic Supramolecular Polymer Based on Ru(II) and Fe(II)

A heterobimetallic supramolecular polymer (polyRuFe) with alternately complexed Ru(II) and Fe(II) is prepared following a stepwise synthetic route through harnessing first the strongly binding metal ion Ru(II) and then the weakly binding metal ion Fe(II). A high yield of product is achieved in each step. The heterometal ions are incorporated into the polymer chain in identical coordination environments formed by two 2,2′:6′,2″-terpyridine moieties. Characterization is accomplished by NMR spectroscopy, MALDI–TOF mass spectrometry, UV–Vis spectroscopy, and cyclic voltammetry. PolyRuFe shows a wide optical window (λ = 311–577 nm) and a broad distinct reversible redox nature of two types, originated from the coupling of the two heterometallic segments into the polymer chain. Such characteristics of polyRuFe suggest its potential for various electrochemical and electro-optical applications.