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CNTs were grown on iron-modified mesoporous graphitized carbon aerogel (GCA) at 700 °C, 800 °C and 900 °C using catalytic CVD method. Resultant CNT/GCA materials composition, morphology and structure were studied to understand their electrochemical stability and performance for oxygen reduction reaction (ORR) in acidic medium. CNT growth was increased from 700 °C to 800 °C, dominated by MWCNTs formation. In the temperature range from 800 °C to 900 °C, the growth was reduced by forming nanofiber/nanoribbon structures accompanied by MWCNTs. Mesoporosity of CNT/GCA composites declined at 700 °C and 800 °C due to MWCNT formation. However, CNT/GCA growth at 900 °C improved mesoporosity with substantial increase in pore volume (∼3 times of GCA) due to formation of nanofibers and nanoribbons. The structure of CNT/GCA materials revealed nitrogen doping and dispersion of FeN x phase. A synergistic contribution of CNT/GCA material structure and morphology to ORR activity was noticed. Among CNT/GCA materials, CNT-800 °C/GCA material showed ORR activity at lowest onset potential of 0.5 V. However, CNT-900 °C/GCA exhibits the highest ORR mass activity, with a half-wave onset potential difference of 120 mV with Pt (40 wt.%)/C. Moreover, CNT-900 °C/GCA demonstrates high selectivity (>3.97) to 4 electron ORR path, excellent methanol tolerance and electrochemical durability which makes it a potential DMFC cathode candidate. [ABSTRACT FROM AUTHOR]

Abstract: A newly developed electrospun polyimide nanofiber mat/membrane along with three commercial 0.22µm microfiltration membranes have been investigated for applications within a renewable biorefinery to complete solid–liquid clarification at two locations: (1) following enzymatic hydrolysis (pre-fermentation) and (2) post-ethanol fermentation. Performance was assessed by evaluating process flux, reversible and irreversible fouling, and the ability to completely remove insoluble solids. Lignin (the primary insoluble solid following enzymatic hydrolysis of a biomass feedstock), yeast cells, and cell debris (following fermentation to ethanol), along with soluble phenolic compounds, all being very hydrophobic in nature, caused extensive fouling, which led to permanent irreversible flux decline for the three commercial membranes. In addition, all three commercial membranes showed a small amount of insoluble solids in the permeate, indicating incomplete removal of the insoluble solids. In contrast, the polyimide nanofiber membrane showed virtually no irreversible fouling and complete retention of insoluble solids, suggesting the tremendous potential for biorefinery applications. [Copyright &y& Elsevier]

Highlights: [•] Electrospun carbon nanofiber mats were prepared from a natural product of lignin. [•] The freestanding mats were flexible with BET specific surface area of ∼583 m2/g. [•] The mats were surface-deposited with Ag nanoparticles via the scCO2 method. [•] Novel electrocatalytic systems of Ag/ECNFs exhibited high activities towards ORR. [ABSTRACT FROM AUTHOR]

Abstract: Mechanically flexible mats consisting of electrospun carbon nanofibers (ECNFs) were prepared by first electrospinning aqueous mixtures containing a natural product of alkali lignin together with polyvinyl alcohol (PVA) into composite nanofiber mats followed by stabilization in air and carbonization in an inert environment. Morphological and structural properties, as well as specific surface area, total pore volume, average pore size, and pore size distribution, of the lignin-based ECNF mats were characterized; and their electrochemical performances (i.e., capacitive behaviors) were evaluated by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The lignin-based ECNF mats exhibited outstanding performance as free-standing and/or binder-free electrodes of supercapacitors. For example, the ECNFs made from the composite nanofibers with mass ratio of lignin/PVA being 70/30 (i.e., ECNFs (70/30)) had the average diameter of ∼100 nm and the Brunauer–Emmett–Teller (BET) specific surface area of ∼583 m2 g−1. The gravimetric capacitance of ECNFs (70/30) electrode in 6 M KOH aqueous electrolyte exhibited 64 F g−1 at current density of 400 mA g−1 and 50 F g−1 at 2000 mA g−1. The ECNFs (70/30) electrode also exhibited excellent cycling durability/stability, and the gravimetric capacitance merely reduced by ∼10% after 6000 cycles of charge/discharge. [Copyright &y& Elsevier]

Abstract: Electrospun polyacrylonitrile (PAN) copolymer nanofibers with diameters of ∼0.3 μm were prepared as highly aligned bundles. The as-electrospun nanofiber bundles were then stretched in steam at ∼100 °C into 2, 3, and 4 times of the original lengths. Subsequently, characterizations and evaluations were carried out to understand morphological, structural, and mechanical properties using SEM, 2D WAXD, polarized FT−IR, DSC, and mechanical tester; and the results were compared to those of conventional PAN copolymer microfibers. The study revealed that: (1) the macromolecules in as-electrospun nanofibers were loosely oriented along fiber axes; although such an orientation was not high, a small extent of stretching could effectively improve the orientation and increase the crystallinity; (2) most of macromolecules in the crystalline phase of as-electrospun and stretched nanofibers possessed the zig-zag conformation instead of the helical conformation; and (3) the post-spinning stretching process could substantially improve mechanical properties of the nanofiber bundles. To the best of our knowledge, this study represented the first successful attempt to stretch electrospun nanofibers; and we envisioned that the highly aligned and stretched electrospun PAN copolymer nanofibers could be an innovative type of precursor for the development of continuous nano-scale carbon fibers with superior mechanical strength. [ABSTRACT FROM AUTHOR]

Abstract: Carbon nanofibers with diameters of 200–300nm were developed through stabilization and carbonization of aligned electrospun polyacrylonitrile (PAN) nanofiber bundles. Prior to the oxidative stabilization in air, the electrospun PAN nanofiber bundle was tightly wrapped onto a glass rod, so that tension existed during the stabilization. We also investigated several carbonization procedures by varying final carbonization temperatures in the range from 1000 to 2200°C. The study revealed that: (1) with increase of the final carbonization temperature, the carbon nanofibers became more graphitic and structurally ordered; (2) the carbon nanofiber bundles possessed anisotropic electrical conductivities, and the differences between the parallel and perpendicular directions to the bundle axes were over 20 times; and (3) the tensile strengths and Young''s moduli of the prepared carbon nanofiber bundles were in the ranges of 300–600MPa and 40–60GPa, respectively. [Copyright &y& Elsevier]

Abstract: Graphitic carbon nanofibers (GCNFs) with diameters of approximately 300 nm were developed using bundles of aligned electrospun polyacrylonitrile (PAN) nanofibers containing phosphoric acid (PA) as the innovative precursors through thermal treatments of stabilization, carbonization, and graphitization. The morphological, structural, and mechanical properties of GCNFs were systematically characterized and/or evaluated. The GCNFs made from the electrospun PAN precursor nanofibers containing 1.5 wt.% of PA exhibited mechanical strength that was 62.3% higher than that of the GCNFs made from the precursor nanofibers without PA. The molecules of PA in the electrospun PAN precursor nanofibers initiated the cyclization and induced the aromatization during stabilization, as indicated by the FT-IR and TGA results. The stabilized PAN nanofibers possessed regularly oriented ladder structures, which facilitated the further formation of ordered graphitic structures in GCNFs during carbonization and graphitization, as indicated by the TEM, XRD, and Raman results. [Copyright &y& Elsevier]

Biomaterials are being extensively used in various biomedical fields; however, they are readily infected with microorganisms, thus posing a serious threat to the public health care. We herein presented a facile route to the antibacterial modification of an important A-B-A type biomaterial using poly (ethylene glycol) methyl ether (mPEG)- poly(ε-caprolactone) (PCL)-mPEG as a typical model. Inexpensive, commercial bis(2-hydroxyethyl) methylammonium chloride (DMA) was adopted as an antibacterial unit. The effective synthesis of the antibacterial copolymer mPEG-PCL-∼∼∼-PCL-mPEG (where ∼∼∼ denotes the segment with DMA units) was well confirmed by FTIR and 1 H NMR spectra. At an appropriate modification extent, the DMA unit could render the copolymer mPEG-PCL-∼∼∼-PCL-mPEG highly antibacterial, but did not largely alter its fascinating intrinsic properties including the thermosensitivity ( e.g. , the body temperature-induced sol-gel transition), non-cytotoxicity, and controlled drug release. A detailed study on the sol-gel-sol transition behavior of different copolymers showed that an appropriate extent of modification with DMA retained a sol-gel-sol transition, despite the fact that a too high extent caused a loss of sol-gel-sol transition. The hydrophilic and hydrophobic balance between mPEG and PCL was most likely broken upon a high extent of quaternization due to a large disturbance effect of DMA units at a large quantity (as evidenced by the heavily depressed PCL segment crystallinity), and thus the micelle aggregation mechanism for the gel formation could not work anymore, along with the loss of the thermosensitivity. The work presented here is highly expected to be generalized for synthesis of various block copolymers with immunity to microorganisms. Light may also be shed on understanding the phase transition behavior of various multiblock copolymers. [ABSTRACT FROM AUTHOR]

Using alkaline pH adjustment, the reaction between graphene oxide and l-ascorbic acid led to the formation of a carbocatalyst film with numerous graphene edges protruding out of basal planes, which had a markedly enhanced carbocatalytic activity for conversion of 4-nitrophenol to 4-aminophenol, as compared to that of the carbocatalyst counterpart without involving pH mediation. [ABSTRACT FROM AUTHOR]

A novel smart stimuli responsive surface can be fabricated by the subsequent self-assembly of the graphene monolayer and the TiO2 nanofilm on various substrates, that is, fabrics, Si wafers, and polymer thin films. Multiscale application property can be achieved from the interfacial interaction between the hierarchical graphene/TiO2 surface structure and the underlying substrate. The smart surface possesses superhydrophobic property as a result of its hierarchical micro- to nanoscale structural roughness. Upon manipulating the UV induced hydrophilic conversion of TiO2 on graphene/TiO2 surface, smart surface features, such as tunable adhesiveness, wettability, and directional water transport, can be easily obtained. The existence of graphene indeed enhances the electron-hole pair separation efficiency of the photo-active TiO2, as the time required for the TiO2 superhydrophilic conversion is largely reduced. Multifunctional characteristics, such as gas sensing, droplet manipulation, and self-cleaning, are achieved on the smart surface as a result of its robust superhydrophobicity, tunable wettability, and high photo-catalytic activity. It is also revealed that the superhydrophilic conversion of TiO2 is possibly caused by the atomic rearrangement of TiO2 under UV radiation, as a structural transformation from {101} to {001} is observed after the UV treatment. [ABSTRACT FROM AUTHOR]

Carbon nanofibers with diameters that fall into submicron and nanometer range have attracted growing attention in recent years due to their superior chemical, electrical, and mechanical properties in combination with their unique 1D nanostructures. Unlike catalytic synthesis, electrospinning polyacrylonitrile (PAN) followed by stabilization and carbonization has become a straightforward and convenient route to make continuous carbon nanofibers. This paper is a comprehensive and state-of-the-art review of the latest advances made in development and application of electrospun PAN-based carbon nanofibers. Our goal is to demonstrate an objective and overall picture of current research work on both functional carbon nanofibers and high-strength carbon nanofibers from the viewpoint of a materials scientist. Strategies to make a variety of carbon nanofibrous materials for energy conversion and storage, catalysis, sensor, adsorption/separation, and biomedical applications as well as attempts to achieve high-strength carbon nanofibers are addressed. [ABSTRACT FROM AUTHOR]

Abstract: Electrospun anatase-phase TiO2 nanofibers with desired morphological structure and relatively high specific surface area are expected to outperform other nanostructures (e.g., powder and film) of TiO2 for various applications (particularly dye-sensitized solar cell and photo-catalysis). In this study, systematic investigations were carried out to prepare and characterize electrospun anatase-phase TiO2 nanofibers with different morphological structures (e.g., solid, hollow/tubular, and porous) and specific surface areas. The TiO2 nanofibers were generally prepared via electrospinning of precursor nanofibers followed by pyrolysis at 500°C. For making hollow/tubular TiO2 nanofibers, the technique of co-axial electrospinning was utilized; while for making porous TiO2 nanofibers, the etching treatment in NaOH aqueous solution was adopted. The results indicated that the hollow/tubular TiO2 nanofibers (with diameters of ∼300–500nm and wall-thickness in the range from tens of nanometers to ∼200nm) had the BET specific surface area of ∼27.3m2/g, which was approximately twice as that of the solid TiO2 nanofibers (∼15.2m2/g) with diameters of ∼200–300nm and lengths of at least tens of microns. Porous TiO2 nanofibers made from the precursor of Al2O3/TiO2 composite nanofibers had the BET specific surface area of ∼106.5m2/g, whereas porous TiO2 nanofibers made from the precursor of ZnO/TiO2 composite nanofibers had the highest BET specific surface area of ∼148.6m2/g. [Copyright &y& Elsevier]

Abstract: A series of high molecular weight PI precursors, poly(p-phenylene biphenyltetracarboxamide acid), were synthesized from 3,4,3′,4′-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) by using intense mechanical stirring at −15 to 0°C for 48–72h. The as-synthesized PI precursor solution was used to make BPDA/PDA polyimide thin films and electrospun nanofibers. IR, Ostward Viscometer, CMT-8102 Electromechanical Universal Testing Machine and scanning electron microscope (SEM) were used for the characterizations of the as-synthesized PI precursor, PI films and nanofiber sheets. The high molecular weight BPDA/PDA PI thin films and electrospun nanofiber sheets possess excellent mechanical properties of up to 900MPa tensile strength with up to 18.0GPa E-modulus and up to 210MPa tensile strength with up to 2.5GPa E-modulus, respectively. [Copyright &y& Elsevier]