Controllable‐Nitrogen Doped Carbon Layer Surrounding Carbon Nanotubes as Novel Carbon Support for Oxygen Reduction Reaction

Novel nitrogen‐doped carbon layer surrounding carbon nanotubes composite (NC‐CNT) (N/C ratio 3.3–14.3 wt.%) as catalyst support has been prepared using aniline as a dispersant to carbon nanotubes (CNTs) and as a source for both carbon and nitrogen coated on the surface of the CNTs, where the amount of doped nitrogen is controllable. The NC‐CNT so obtained were characterized with scanning electron microscopy (SEM), Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and nitrogen adsorption and desorption isotherms. A uniform dispersion of Pt nanoparticles (ca. 1.5–2.0 nm) was then anchored on the surface of NC‐CNT by using aromatic amine as a stabilizer. For these Pt/NC‐CNTs, cyclic voltammogram measurements show a high electrochemical activity surface area (up to 103.7 m² g^–1) compared to the commercial E‐TEK catalyst (55.3 m² g^–1). In single cell test, Pt/NC‐CNT catalyst has greatly enhanced catalytic activity toward the oxygen reduction reaction, resulting in an enhancement of ca. 37% in mass activity compared with that of E‐TEK.     

Design of carbon nanotube fiber microelectrode for glucose biosensing

BACKGROUND: Carbon nanotube (CNT) fiber directly spun from an aerogel has a unique, well‐aligned nanostructure (nano‐pore and nano‐brush), and thus provides high electro‐catalytic activity and strong interaction with glucose oxidase enzyme. It shows great potential as a microelectrode for electrochemical biosensors. RESULTS: Cyclic voltammogram results indicate that post‐synthesis treatments have great influence on the electrocatalytic activity of CNT fibers. Raman spectroscopy and electrical conductivity tests suggest that fibers annealed at 250 °C remove most of the impurities without damaging the graphite‐like structure. This leads to a nano‐porous morphology on the surface and the highest conductivity value (1.1 × 10⁵ S m^?1). Two CNT fiber microelectrode designs were applied to enhance their electron transfer behaviour, and it was found that a design using a 30 nm gold coating is able to linearly cover human physiological glucose level between 2 and 30 mmol L^?1. The design also leads to a low detection limit of 25 µmol L^?1. CONCLUSIONS: The high performance of CNT fibers not only offers exceptional mechanical and electrical properties, but also provides a large surface area and electron transfer pathway. They consequently make excellent bioactive microelectrodes for glucose biosensing, especially for potential use in implantable devices. Copyright © 2011 Society of Chemical Industry     

Preparation of Sn‐doped CdS/TiO2/conducting polymer fiber composites for efficient photocatalytic hydrogen production under visible light irradiation

Sn‐doped CdS/TiO₂ heterojunction was synthesized on the conducting polymer fiber mat by hydrothermal method. The conducting polymer fiber mat was made by electrospinning from polyvinylidene fluoride, styrene‐maleic anhydride copolymer, and nano‐graphites as conducting fillers. The Sn‐doped CdS/TiO₂ heterojunction was characterized by XRD, XPS, SEM, TEM, TGA, and UV–Vis absorption spectra. Under simulated solar light irradiation, a combination of Sn‐doped CdS/TiO₂/conducting polymer was found to be highly efficient for photocatalytic hydrogen evolution from splitting of water. The photocatalytic hydrogen production efficiency was up to 2885 μmol h^?1 g^?1cat. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42300.     

Experimental and neural model analysis of styrene removal from polluted air in a biofilter

BACKGROUND: Biofilters are efficient systems for treating malodorous emissions. The mechanism involved during pollutant transfer and subsequent biotransformation within a biofilm is a complex process. The use of artificial neural networks to model the performance of biofilters using easily measurable state variables appears to be an effective alternative to conventional phenomenological modelling. RESULTS: An artificial neural network model was used to predict the extent of styrene removal in a perlite‐biofilter inoculated with a mixed microbial culture. After a 43 day biofilter acclimation period, styrene removal experiments were carried out by subjecting the bioreactor to different flow rates (0.15–0.9 m³ h^?1) and concentrations (0.5–17.2 g m^?3), that correspond to inlet loading rates up to 1390 g m^?3 h^?1. During the different phases of continuous biofilter operation, greater than 92% styrene removal was achievable for loading rates up to 250 g m^?3 h^?1. A back propagation neural network algorithm was applied to model and predict the removal efficiency (%) of this process using inlet concentration (g m^?3) and unit flow (h^?1) as input variables. The data points were divided into training (115 × 3) and testing set (42 × 3). The most reliable condition for the network was selected by a trial and error approach and by estimating the determination coefficient (R²) value (0.98) achieved during prediction of the testing set. CONCLUSION: The results showed that a simple neural network based model with a topology of 2–4–1 was able to efficiently predict the styrene removal performance in the biofilter. Through sensitivity analysis, the most influential input parameter affecting styrene removal was ascertained to be the flow rate. Copyright © 2009 Society of Chemical Industry     

Mesostructured CeO2 as an Effective Catalyst for Styrene Synthesis by Oxidative Dehydrogenation of Ethylbenzene

A new type of mesostructured ceria material was synthesized via template-assisted precipitation method and tested for the oxidative dehydrogenation (ODH) of ethylbenzene to styrene by molecular oxygen. The effect of calcination temperature on the catalytic performances of the ceria catalysts has been investigated. Among the catalysts tested, the CeO₂-450 sample derived by calcination at 450 °C exhibited the highest ethylbenzene conversion (34%) and styrene selectivity (87%). Comparing the reaction rates for ODH of ethylbenzene (ca. 6.1 mmol ST g _cat ^?1 h^?1 at 450 °C) with the highly active nanostructured carbon-based catalysts in the current literature confirmed the very high activity of these new materials. The superior catalytic performance of the CeO₂-450 sample can be attributed to its high specific surface area and enhanced redox properties as revealed by H₂-TPR measurements.     

Polymerisation of ethylene catalysed by mono‐imine‐2,6‐diacetylpyridine iron/methylaluminoxane (MAO) catalyst system: effect of the ligand on polymer microstructure

The complex, {1‐{6‐[(2,6‐diisopropylphenyl)‐ethaneimidoyl]‐2‐pyridinyl}‐1‐ethanone}iron(II) dichloride ( 2 ), has been synthesised and characterised. Treatment of complex 2 with methylaluminoxane resulted in a very active catalytic system for the preparation of polyethylene (PE). The system shows activities in the order of magnitude 10⁷ g (PE) mol^?1(Fe) h^?1 bar^?1. Characterisation by ¹³C NMR indicated that branched PE was obtained and that experimental conditions affect polymer microstructure. PE produced contained six to eight branches per 100 carbons. © 2002 Society of Chemical Industry     

Evaluation of the Catalytic Effect of the Ozone/Carbon Nanotube (O3/CNT) Process Using para-Chlorobenzoic Acid (pCBA)

The catalytic effects and mechanisms of the ozone/carbon nanotube (O₃/CNT) process using para-chlorobenzoic acid (pCBA) were evaluated. To use pCBA as an O₃-resistant OH? probe compound in a pure water system at pH 7, an adequate amount of scavenger was needed. During the O₃/CNT process, a synergetic catalytic effect by OH? generation on the CNT surface could be evaluated in the condition of excess tert-butyl alcohol (TBA) concentration. The OH? radicals were generated and existed on both the bulk phase and CNT surface. The OH-ct values of the CNT surface and bulk phase in the O₃/CNT process for 10 min were 2.1 × 10^?5 and 2.5 × 10^?5μ M·s, respectively. In modifying CNT evaluation, the catalytic effects were the most apparent in the following order: CNT treated with acid then heat (CNT-T), original untreated CNT (CNT-O), and CNT treated with an acid (CNT-A).     

Investigation of the effect of tetrahydrofuran and acetone as cosolvents in acrylonitrile–butadiene–styrene–based nanofiltration membranes

In this study, novel nanofiltration membranes were prepared with acrylonitrile–butadiene–styrene (ABS)–poly(ethylene glycol)–N,N ‐dimethylacetamide–[tetrahydrofuran (THF)–acetone] as a cosolvent. All of the membranes were prepared by the phase‐inversion method and a casting solution technique. The effects of the cosolvent concentration in the casting solution and the evaporation time before the immersion/precipitation step on the membrane performance and properties were investigated. The prepared membranes were characterized through their permeation flux, salt rejection, and phase‐inversion time values. The salt rejection was increased from 53% for the bare ABS membrane to 73% for the membrane prepared with 40 wt % THF as a cosolvent. The water flux was decreased from 4345 to 1121 cc m^?2 h^?1 with the addition of THF to the casting solution. The addition of acetone to the casting solution improved the water flux from 4345 to 5607 cc m^?2 h^?1 and reduced the salt rejection from 53 to 36%. The evaporation time of THF and acetone led to similar effects on flux and rejection. However, with evaporation time, membranes prepared with acetone were denser than those prepared with THF; this was due to the lower boiling point and higher boiling rate of acetone at the same temperatures. This resulted in greater effects on the ABS performance and structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44993.     

Fabrication of Tiron‐doped polypyrrole/MWCNT composite electrodes with high mass loading and enhanced performance for supercapacitors

In this study, the aromatic sulfonate compound Tiron with high charge to mass ratio is used as an anionic dopant for synthesis of polypyrrole (PPy). The fabricated PPy is investigated for electrochemical supercapacitor (ES) application. Testing results show that Tiron allows reduced PPy agglomeration, smaller particle size and improved charge storage properties of PPy. High capacitance and improved capacitive retention at high scan rates are achieved by the fabrication of PPy/multiwalled carbon nanotube (MWCNT) composite electrode using safranin (SAF) as a co‐dispersant. The Tiron‐doped PPy electrode shows the highest capacitance of 7.8 F cm^?2 with a mass of 27 mg cm^?2. The Tiron‐doped PPy/MWCNT composite electrode shows good capacitance retention with a capacitance of 1.0 F cm^?2 at the scan rate of 100 mV s^?1. Symmetric supercapacitor cells are fabricated using PPy based active materials. An energy density of 0.36 mWh cm^?2 is achieved. The energy/power density and capacitance retention of the Tiron‐doped PPy/MWCNT ES is significantly improved in comparison with PPy‐based ES, prepared without Tiron or MWCNT. The Tiron‐doped PPy/MWCNT symmetric supercapacitor presents good cycling performance with 91.4% capacitance retention after 1000 charge–discharge cycles. The PPy/MWCNT composites, prepared using Tiron and SAF co‐dispersant, are promising electrodes for ES. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42376.     

Exploring the spinning and operations of multibore hollow fiber membranes for vacuum membrane distillation

Hollow fiber membranes with a multibore configuration have demonstrated their advantages with high mechanical strength, easy module fabrication, and excellent stability for membrane distillation (MD). In this work, the microstructure of multibore fibers was optimized for vacuum MD (VMD). A microstructure consisting of a tight liquid contact surface and a fully porous cross‐section is proposed and fabricated to maximize the wetting resistance and VMD desalination performance. The new membrane exhibited a high VMD flux of 71.8 L m^?2 h^?1 with a 78°C model seawater feed. Investigations were also carried to examine various effects of VMD operational conditions on desalination performance. The 7‐bore membrane showed higher flux and superior thermal efficiency under the VMD configuration than the direct contact MD configuration. Different from the traditional single‐bore hollow fiber, the VMD flux of multibore membrane at the lumen‐side feed configuration was higher than that of the shell‐side feed due to the additional evaporation surface of multibore geometry. © 2013 American Institute of Chemical Engineers AIChE J, 60: 1078–1090, 2014     

Bismuth metal–organic frameworks derived bismuth selenide nanosheets/nitrogen–doped carbon hybrids as anodes for Li–ion batteries with improved cyclic performance

Nanohybrids have significant potential in improving the performance of Li–ion batteries (LIBs). Herein, bismuth selenide nanosheets/nitrogen–doped carbon hybrids (Bi₂Se₃@NC) are prepared by selenylation of bismuth (III) metal–organic frameworks (Bi–MOFs), which are obtained by solvothermal reaction in a mixed solvent of N, N–dimethylformamide and methanol. When served as anodes for Li–ion batteries, it was found that the post–treatment temperature of Bi–MOFs has a powerful impact on Li storage performance. Compared to Bi₂Se₃@NC–500 and Bi₂Se₃@NC–600 hybrids, Bi₂Se₃@NC–400 hybrids deliver large specific capacity, outstanding rate performance, and good cyclic stability. 410.6 mAh g^?1 of capacity is gained after 50 cycles at 100?mA?g^?1. Even at 500?mA?g^?1, 335.8 mAh g^?1 is achieved after 400 cycles. The superior Li storage feature of Bi₂Se₃@NC–400 hybrids is ascribed to the synergetic effect between Bi₂Se₃ nanosheets and N–doped nanocarbon. Bi₂Se₃@NC–400 hybrids is a promising anode material for LIBs.     

CuBr2‐induced charge screening on photoactive nanocolloidal polypyrrole:poly(styrene sulfonate) composite multilayer thin‐film counter electrodes for high‐efficiency dye‐sensitized solar cells

Nanocolloidal polypyrrole (PPy):poly(styrene sulfonate) (PSS) particles were synthesized by chemical oxidative polymerization using 15 wt% of PSS. The highly processable polymer composite (PPy:PSS) was spin‐coated at 4000 rpm on fluorine‐doped tin oxide glass and subsequently employed as a counter electrode (CE) for dye‐sensitized solar cells (DSCs). PPy:PSS multilayer (one, three, five) CEs were treated with CuBr₂ salt, which enhances the efficiency of the DSCs. Optical studies reveal that a bulkier counterion hinders interchain interactions of PPy which on salt treatment shows a moderate redshift in absorption maxima. Salt‐treated PPy:PSS films exhibit lower charge transfer resistance, higher surface roughness and better catalytic performance for the reduction of I₃^?, when compared with untreated films. The improved catalytic performance of salt‐treated PPy:PSS multilayer films is attributed to charge screening and conformational change of PPy, along with the removal of excess PSS. Under standard AM 1.5 sunlight illumination, salt treatment is shown to boost the efficiency of multilayer PPy:PSS composite film‐based DSCs, leading to enhanced power conversion efficiency of 6.18, 6.33 and 6.37% for one, three and five layers, respectively. These values are significantly higher (ca 50%) than those for corresponding devices without CuBr₂ salt treatment (3.48, 2.90 and 2.01%, respectively). © 2016 Society of Chemical Industry     

Development of stable and active PVA‐PSSA/SA‐PVA catalytic composite membrane for esterification enhancement

An active and stable catalytic composite membrane (CCM), poly(vinyl alcohol)–poly(styrene sulfonic acid)/sodium alginate–poly(vinyl alcohol) (PVA‐PSSA/SA‐PVA), was prepared to enhance the esterification of ethanol and propionic acid. The morphologies and crystal structures of the CCMs were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, and X‐ray diffraction. The effects of catalytic layer thickness, mass ratio of PVA to PSSA, concentration of catalytic layer solution, ratio of reaction volume to membrane area, and molar ratio of propionic acid to ethanol were discussed. The pervaporation results showed that the flux of CCM increased from 118 to 320 g m^?2 h^?1 compared with the SA‐PVA membrane because of the close affinity and low resistance of PSSA to water. After crosslinking with 3‐aminopropylmethyldiethoxysilane, the CCMs had good catalytic activities. The acid conversion reached 92.8% at 75 °C in 12 h, and the stabilization of the CCM was greatly improved. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46514.     

Hybrid factors influencing wet grip and rolling resistance properties of solution styrene‐butadiene rubber composites

Influencing factors on wet grip and rolling resistance properties of solution styrene ? butadiene rubber (SBR) composites were investigated in terms of main hybrid components of the microstructure and crosslink density. Influence of the molecular weight and oil extension on the wet grip and rolling resistance properties was also examined. The styrene and 1,2‐unit contents of SBR affected the wet grip and rolling resistance properties. The influence of hybrid factors on the wet grip and rolling resistance properties was examined using 3D plots of the microstructure and crosslink density. The wet grip property was influenced by the hybrid microstructure of the styrene and 1,2‐unit as well as the crosslink density. The rolling resistance property was found to be mainly affected by not only the styrene content but also the crosslink density. It was found that SBR with appropriate styrene content (15 ? 18 mol%), relatively high 1,2‐unit content (45 ? 50 mol%) and relatively high crosslink density (over 1.5 × 10^?4 mol cm^?3) might be good for improvement of both the wet grip and rolling resistance properties. © 2017 Society of Chemical Industry     

Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu‐MCM‐41 catalysts

The synthesis and utilization of mesoporous Cu‐MCM‐41 catalysts for hydrogenation of dimethyl oxalate to ethylene glycol is described in this article. Physicochemical properties of these Cu‐MCM‐41 catalysts have been investigated by N₂‐physisorption, X‐ray diffraction, inductively coupled plasma, N₂O titration, transmission electron microscopy, temperature programmed reduction, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. It was found that the copper loading significantly influenced the pore structure and copper surface area of the catalyst. High catalytic performance is obtained over a 20Cu‐MCM‐41 catalyst with a full DMO conversion and EG yield of 92% at a LHSV of 3.0 h^?1. The catalytic performance of optimized 20Cu‐MCM‐41 catalyst could be attributed to the fine copper dispersion and large copper surface areas. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2530–2539, 2013     

Influence of the metal centers of 2,6‐bis(imino)pyridyl transition metal complexes on ethylene polymerization/ oligomerization catalytic activities

Much work on bis(imino)pyridyl complexes with Fe(II) and Co(II) as ethylene polymerization catalysts has been reported in terms of designing new analogous ligands, while little work has been dedicated to the study of the effect of the metal center on catalyst performance. A series of bis(imino)pyridyl‐MCl₂ (M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II)) transition metal complexes were synthesized, for which single crystals of the Co(II) and Cu(II) complexes were obtained. The crystal structures indicated that these complexes had similar coordination geometries. Being applied to ethylene polymerization at 25 °C and employing 500 equiv. of methylaluminoxane as co‐catalyst, the complexes with Fe(II), Co(II) and Ni(II) centers showed, respectively, catalytic activities of 1.25 × 10⁶ g (mol Fe)^?1 h^?1 Pa for ethylene polymerization, and 3.98 × 10⁵ g (mol Co)^?1 h^?1 Pa and 5.13 × 10³ g (mol Ni)^?1 h^?1 Pa for ethylene oligomerization. In contrast, the complexes with Cu(II) and Zn(II) centers were inactive. Crystal structure data showed that the coordination interactions provided a comparatively reliable quantification of the selectivity of the bis(imino)pyridyl ligand for the studied metal ions, which was in reasonable agreement with the Irving–Williams list. Moreover, for the Ni(II) and Cu(II) complexes, the strong coordination bonds and small N(imino)? M? N(imino) angles were unfavorable for several steps in the mechanism, such as ethylene coordination to the metal center, ethylene migratory insertion and olefin chain growth. All of these will reduce the speed of the overall reaction, indicating a decrease of catalytic efficiency in a given period. The poor activity of the Zn(II) complex for ethylene polymerization may be related to the reduction process by the alkylating agent. Copyright © 2010 Society of Chemical Industry     

Hierarchical SnO2 nanosheets@SiC nanofibers for enhanced photocatalytic water splitting

Producing eco‐friendly hydrogen (H₂) as a renewable energy by solar‐driven water splitting has triggered considerable interests. In this paper, we reported the in situ growth of ultrathin tin oxide nanosheets (SnO₂ NSs) on the surface of mesoporous silicon carbide nanofibers (SiC NFs) using a simple hydrothermal method to form a core‐shell structures. The H₂ production rate of the sample was 471.8 μmol g^?1 h^?1 under solar‐light illumination without any noble metals as catalysts, which was almost 1.25 and 3 times higher than pure SiC NFs and pure SnO₂ NSs, respectively. The synergistic effect of the SnO₂‐SiC heterojunction between the core‐shell microstructure played an important role in the superior performance of this photocatalyst.     

Synthesis of high‐density polyethylene/rGO‐CNT‐Fe nanocomposites with outstanding magnetic and electrical properties

Semi‐conducting polyethylene (PE) nanocomposites with outstanding magnetic properties at room temperature were synthesized. These exceptional properties, for a diamagnetic and insulating matrix as PE, were obtained by polymerizing ethylene in the presence of a catalytic system formed by a metallocene catalyst supported on a mixture of reduced graphene oxide (rGO) and carbon nanotubes with encapsulated iron (CNT‐Fe). It was used a constant and very low amount of CNT‐Fe, obtained by vapor chemical deposition using ferrocene. The percolation threshold, to achieve conductivity, was obtained using a variable amount of rGO. The nanocomposites were semiconductors with the addition of 2.8 wt % and 6.0 wt % of the filler, with electrical conductivities of 4.99 × 10^?6 S cm^?1 and 7.29 × 10^?4 S cm^?1, respectively. Very high coercivity values of 890–980 Oe at room temperature were achieved by the presence of only 0.04–0.06 wt % of iron in the nanocomposites. The novelty of this work is the production of a thermoplastic with both, magnetic and electric properties at room temperature, by the use of two fillers, that is rGO and CNT‐Fe. The use of a small amount of CNT‐Fe to produce the magnetic properties and variable amount of rGO to introduce the electrical conductivity in PE matrix let to balance both properties. The encapsulation strategy used to obtain Fe in CNT, protect Fe from easy oxidation and aggregation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45382.     

Enhanced Thermoelectric Performance of PEDOT:PSS Films by Sequential Post‐Treatment with Formamide

This paper reports a series of sequential post‐treatments using a polar solvent formamide to enhance the thermoelectric performance of poly(3,4‐ethylenedioxythiophene) doped with poly(styrene sulfonate) anions (PEDOT:PSS). The electrical conductivity of PEDOT:PSS films significantly increases from 0.33 S cm^?1 for the pristine film to ≈2929 S cm^?1 for the treated film and meanwhile the Seebeck coefficient maintains as high as 17.4 µV K^?1, resulting in a power factor of 88.7 µW m^?1 K^?2. Formamide is a polar solvent with a high boiling point of 210 °C and high dielectric constant of 109, and PSS has a good solubility in it. Post‐treatment with formamide causes not only the phase segregation of PEDOT and PSS but also the removal of insulating PSS, therefore leading to the reorientation of PEDOT chains and enhancement in mobility without altering the doping level considerably. The cross‐plane thermal conductivity also reduces from 0.54 to 0.19 W m^?1 K^?1 after the post‐treatment, leading to a figure of merit (ZT) value of 0.04 at room temperature.     

Teflon AF2400/Ultem composite hollow fiber membranes for alcohol dehydration by high‐temperature vapor permeation

High‐temperature vapor permeation has a stringent requirement of membrane stability under harsh feed environments. This work reports the design of Teflon AF2400/Ultem composite hollow fiber (HF) membranes for alcohol dehydration via vapor permeation. Fabrication parameters such as Teflon concentration and coating time were systematically investigated. Interestingly, the fabricated composite HF membranes possess an unusual surface with honeycomb‐like microstructure patterns. Owing to the Teflon protective layer, the newly developed composite HF shows a promising and stable separation performance with a flux of 4265 gm^?2 h^?1 and a separation factor of 383 for 95% isopropanol dehydration at 125°C. The composite HF also performs well under extreme vapor feed compositions from 87 to 99 wt % isopropanol. In addition, it exhibits impressive separation performance for the dehydration of ethanol and n‐butanol. This work may provide useful insights of designing thermal‐stable and high‐performance composite polymeric membranes for vapor permeation. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1747–1757, 2016