Electrochemical synthesis of a novel poly(2,5-dimethoxy aniline) nanorod for ultrasensitive glucose biosensor application

We report for the first time a rapid electrochemical synthesis of one-dimensional poly(2,5-dimethoxyaniline) nanorods (PDMA-NR) in the presence of surfactant. FE-SEM and TEM images confirm the PDMA-NR formation and the average diameter of single rod sizes in the range of ∼200–300 nm. An enzymatic glucose biosensor was fabricated through immobilizing glucose oxidase (GOx) into PDMA-NR matrix. The amperometric current response of PDMA-NR/GOx to glucose is linear in the concentration range between 1 and 10 μM with a detection limit of 0.5 μM (S/N = 3). The PDMA-NR/GOx electrode possesses high sensitivity (5.03 μA/μM), selectivity, stability, and reproducibility toward glucose.     

Hydrothermal synthesis and activation of graphene-incorporated nitrogen-rich carbon composite for high-performance supercapacitors

Graphene-incorporated nitrogen-rich carbon composite with nitrogen content of ca. 10 wt.% has been synthesized by an effective yet simple hydrothermal reaction of glucosamine in the presence of graphene oxide (GO). The nitrogen content of carbon composite is nearly twice as high as that of hydrothermal carbon without graphene. GO is favorable for the high nitrogen doping in the carbon composite by the reaction between the glucosamine-released ammonia and GO. The hydrothermal carbon composite is further activated by KOH, and graphene in the activated carbon composite demonstrates a positive effect of increasing specific surface area, pore volume and electrical conductivity, resulting in superior electrochemical performance. The activated carbon composite with higher specific surface area and micropore volume possesses higher specific capacitance with a value of 300 F g⁻¹ at 0.1 A g⁻¹ in 6 M KOH aqueous solution in the two electrode cell. Larger mesopore volume and higher conductivity of the activated carbon composite will provide fast ion and electron transfer, thus leading to higher rate capacity with a capacitance retention of 76% at 8 A g⁻¹ in comparison to the activated hydrothermal carbon without graphene.     

Exceptional electrochemical performance of nitrogen-doped porous carbon for lithium storage

Crumpled nitrogen-doped porous carbon sheets are successfully fabricated via chemical activation of polypyrrole-functionalized graphene sheets with KOH (APGs). The obtained APGs with nitrogen doping, high surface area, porous and crumpled structure exhibit exceptional electrochemical performances as the electrode material for LIBs, including a superhigh reversible specific capacity of 1516.2 mAh g⁻¹, excellent cycling stability over 10,000 cycles, and good rate capability (133.2 mAh g⁻¹ even at a very high current density of 40 A g⁻¹). The chemical activation synthesis strategy might open new avenues for the design of high-performance carbon-based anode materials.     

Preparation and one-step activation of microporous carbon nanofibers for use as supercapacitor electrodes

Microporous carbon nanofibers were prepared by electrospinning from resole-type phenolic resin, followed by one-step activation. KOH was utilized to tune the fiber diameter and improve porous texture. By adjusting KOH content in the spinning solution, the fiber diameter could be controlled in the range of 252–666 nm and the microporous volume and specific surface area could be greatly improved. The electrochemical measurements in 6 M KOH aqueous solution showed that the microporous carbon nanofibers possessed high specific capacitance, considerable rate performance, and superior specific surface capacitance to conventional microporous carbons. The maximal specific capacitance of 256 F g⁻¹ and high specific surface capacitance of 0.51 F m⁻² were achieved at 0.2 A g⁻¹. Furthermore, the specific capacitance could still remain 170 F g⁻¹ at 20 A g⁻¹ with the retention of 67%. Analysis showed that the high specific surface capacitance of the resultant carbons was mainly attributed to optimized pore size (0.7–1.2 nm) and the excellent rate performance should be principally due to the reduced ion transportation distance derived from the nanometer-scaled fibers.     

Direct electron transfer in a mediator-free glucose oxidase-based carbon nanotube-coated biosensor

A novel biosensor was prepared by immobilizing glucose oxidase on multi-walled carbon nanotube (MWCNT)-coated electrospun gold fibers. Homogeneous coating of the electrospun gold fibers by MWCNTs was achieved by electrophoretic deposition at 20 V (40 V cm^?1), a deposition time of 30 s and a solution concentration of 0.25 mg mL^?1. Scanning electron microscopy confirmed the complete coverage of MWCNTs on the fiber surface. The carboxylated MWCNTs on the gold fibers provided an anchor for covalent immobilization of glucose oxidase (GOX). GOX covalently coupled to conductive carbon nanotubes demonstrated direct electron transfer between the enzyme and the electrode surface without the need for a redox active mediator. Electrochemical characterization of the fabricated sensor by cyclic voltammetry revealed that the immobilized GOX exhibited a surface-confined reversible two-electron and two-proton reaction, with an electron transfer rate constant, k_s, of 1.12 s^?1 and a surface coverage of 1.1 × 10^?12 mol cm^?2. The sensor produced a linear response to glucose concentration up to 30.0 mM with a sensitivity of 0.47 μA mM^?1 cm^?2 and a detection limit of 4 μM.     

Dense carbon monoliths for supercapacitors with outstanding volumetric capacitances

A commercially available dense carbon monolith (CM) and four carbon monoliths obtained from it have been studied as electrochemical capacitor electrodes in a two-electrode cell. CM has: (i) very high density (1.17 g cm⁻³), (ii) high electrical conductivity (9.3 S cm⁻¹), (iii) well-compacted and interconnected carbon spheres, (iv) homogeneous microporous structure and (v) apparent BET surface area of 957 m²g⁻¹. It presents interesting electrochemical behaviors (e.g., excellent gravimetric capacitance and outstanding volumetric capacitance). The textural characteristics of CM (porosity and surface chemistry) have been modified by means of different treatments. The electrochemical performances of the starting and treated monoliths have been analyzed as a function of their porous textures and surface chemistry, both on gravimetric and volumetric basis. The monoliths present high specific and volumetric capacitances (292 F g⁻¹ and 342 F cm⁻³), high energy densities (38 Wh kg⁻¹ and 44 Wh L⁻¹), and high power densities (176 W kg⁻¹ and 183 W L⁻¹). The specific and volumetric capacitances, especially the volumetric capacitance, are the highest ever reported for carbon monoliths. The high values are achieved due to a suitable combination of density, electrical conductivity, porosity and oxygen surface content.     

Sulfur-doped mesoporous carbon from surfactant-intercalated layered double hydroxide precursor as high-performance anode nanomaterials for both Li-ion and Na-ion batteries

We describe a preparation of sulfur-doped mesoporous amorphous carbon (SMAC) from a commercially available alkyl surfactant sulfonate anion-intercalated NiAl-layered double hydroxide precursor via thermal decomposition and subsequent acid leaching. The resultant amorphous carbon is endowed with the integrated advantage of featuring high reversible capacity and long cycling stability: intrinsic doping of sulfur, large specific area, and broad mesopore size distribution. Electrochemical evaluation shows that the SMAC electrode exhibits highly enhanced electrochemical performances, compared with the electrode of non-doped mesoporous and amorphous carbon prepared by using a different surfactant (sodium laurate). A high reversible capacity of 958 mA h g⁻¹ is achieved for the SMAC electrode after 110 cycles at 200 mA g⁻¹, and especially a superlong cycle life with a reversible capacity of 579 mA h g⁻¹ after 970 cycles at 500 mA g⁻¹. Moreover, the SMAC electrode can facilitate the reversible insertion/extraction of Na ion, owing to the proper specific area and mesopore size distribution, as well as the improved electronic conductivity resulted from doping of sulfur.     

A hybrid photocatalytic and enzymatic process using glucose oxidase immobilized on TiO2/polyurethane for removal of a dye

A rectangular recycling photo-bioreactor using glucose oxidase (GOx) immobilized on TiO₂/polyurethane (PU) was developed as a novel coupling of photodegradation and enzymatic process. This method was tested for removal of Acid Orange 7 (AO7), as a model pollutant. High efficiency of decolorization (>99%) was achieved after 22 min using the GOx/TiO₂/PU photo-biocatalyst. Roles of various processes including photodegradation (TiO₂/PU), enzymatic process (GOx/PU) and a coupling of photocatalytic–enzymatic (GOx/TiO₂/PU) process were investigated in the presence and absence of UV light. All the experiments were performed in a circulation photoreactor equipped with a 6 W UV lamp with rate of 5 mL/min.     

Aqueous slurry of S-doped carbon nanotubes as conductive additive for lithium ion batteries

S-doped carbon nanotubes (SCNTs) obtained by a post treatment approach are used as conductive additive for LiFePO₄ (LFP) cathodes in Lithium ion batteries (LIBs). The SCNTs exhibit higher specific surface area, higher conductivity and better hydrophily as compared to the pristine CNTs because of S doping. Thus the SCNTs can be stably dispersed in water, forming an aqueous conductive slurry. The LFP cathode using the aqueous SCNTs slurry as conductive additive exhibits excellent electrochemical performances in terms of capacity (143 mA h g⁻¹ at 2 C), rate capability and cycling stability (99.6% of initial capacity after 200 cycles) due to the uniform dispersibility of SCNTs in the bulk of electrodes forming a continuous conductive network. The full cell configuration with graphite as anode, affords a high reversible capability (150 mA h g⁻¹ at 0.2 C), good cycling stability (capacity retention of 87.6% at 2 C), ultrahigh energy density of 163.7 W h kg⁻¹ and power density of 296.8 W kg⁻¹. Our results provide an easy approach to prepare high performance LIB cathodes using water as solvent, thus leading to lower cost and more secure for the electrode production.     

Plasma-activated immobilization of biomolecules onto graphite-encapsulated magnetic nanoparticles

We describe the amino group surface functionalisation of graphite-encapsulated iron compound nanoparticles by radio frequency (RF) plasma processing followed by oxidized dextran immobilization. We have found that surface treatment using plasma represents an important step before biomolecules immobilization. After plasma treatment, the dispersion property of nanoparticles in dextran solution in water was significantly improved. The successful dextran immobilization was confirmed by X-ray photoelectron spectroscopy (XPS) and high resolution-transmission electron microscopy (HR-TEM) analyses followed by amino group derivatization using 4-(trifluoromethyl)-benzaldehyde (TFBA). As an evidence for covalent bonding between nanoparticles and dextran, the area percentage of deconvoluted CN peak at ～389.6 eV increased from 0% to 10.53 ± 1.30% with increasing the dextran concentration. The result is consistent with the evidenced decreasing of the free amino group percentage from 68.09 ± 5.10% to 14.73 ± 5.89% on the nanoparticle surface after dextran immobilization.     

Effect of phosphoric acid treatment on kaolinite supported ferrioxalate catalyst for the degradation of amoxicillin in batch photo-Fenton process

The effects of phosphoric acid treatment on kaolinite (Kaol) as catalyst support were investigated in this study. The results showed that as the acid concentration was increased from 5 to 10 M, there was increment in the specific surface area from 18.78 in Kaol to 36.0 and 145.5 m² g^− 1 in 5 M acid treated Kaol supported catalyst (5 M-AT-KaolCat) and 10 M acid treated Kaol supported catalyst (10 M-AT-KaolCat), respectively. Characterization results showed that 10 M-AT-KaolCat has higher percentage of Fe than the 5 M-AT-KaolCat due to the effect of acid treatment which provided larger surface area for its anchoring. Consequently, degradation efficiency is comparably faster in 10 M-AT-KaolCat with about 99% of 40 ppm amoxicillin degraded in 8 min without pH adjustments while it takes 12 min using 5 M-AT-KaolCat. The degradation process showed initial enhanced degradation efficiency with increase in the catalyst loadings which later decreased due to the scavenging effect of excess catalyst loading on the reactive hydroxyl radical. The catalysts showed high resistance to leaching due to the presence of the ferrioxalate (FeOx) ligands and the effect of phosphoric acid modification which introduces monolayer of phosphate functional group on the catalyst support through which the FeOx ligands were properly anchored.     

One-pot hydrothermal synthesis and supercapacitive performance of nitrogen and MnO co-doped hierarchical porous carbon monoliths

Nitrogen and MnO co-doped hierarchical porous carbon monolith (N-MnO-HPCM) materials were synthesized through a facile one-pot hydrothermal method. The resulting N-MnO-HPCM materials had hierarchical porous structure, high BET surface area (606 m²/g), large pore volume (0.33 cm³/g), and contained evenly dispersed MnO nanoparticles of about 6 nm in the carbon matrix. Their electrochemical performances as electrodes for supercapacitors were investigated. N-MnO-HPCM material exhibited an excellent electrochemical performance with a specific capacitance of 261.7 F/g at a current density of 1 A/g. It also showed a good rate capability with 74% capacity retention at high current density (5 A/g), indicating its potential applications in supercapacitors.     

Robust growth of herringbone carbon nanofibers on layered double hydroxide derived catalysts and their applications as anodes for Li-ion batteries

Herringbone carbon nanofibers (CNFs) were efficiently produced by chemical vapor deposition on Ni nanoparticles derived from layered double hydroxide (LDH) precursors. The as-obtained CNFs with a diameter ranging from 40 to 60 nm demonstrated herringbone morphologies when they grew on Ni/Al LDH derived catalysts both in the fixed-bed and fluidized-bed reactor. The Ni/Mg/Al, Ni/Cu/Al, as well as Ni/Mo/Mg/Al catalysts were also effective to grow herringbone CNFs. The diameter and specific surface area of the as-obtained CNFs highly depended on the catalyst composition and the growth temperature. When CNFs were grown at 550 °C on Ni/Al catalyst, the as-obtained products had an outer diameter of ca. 50 nm and a specific surface area of 242 m² g⁻¹, possessed a discharge capacity of 330 mAh g⁻¹ as the electrode in a two-electrode coin-type cell. With the increase of the surface area, the discharge capacity increased at a rate of 0.90 mAh cm⁻², while the initial coulombic efficiency decreased gradually on nanocarbon anodes. This is attributed to the fact that CNFs with higher surface area afford smaller sp² carbon layer that facilitated more Li ions to extract from the anodes.     

Low-temperature synthesis of copper oxide (CuO) nanostructures with temperature-controlled morphological variations

We demonstrate low-temperature formation of copper oxide (CuO) nanostructures as well as temperature-controlled variation of morphology by applying hydrothermal methods with copper(II) acetate Cu(CH₃COO)₂·H₂O and 2-piperidinemethanol (2PPM) as starting materials. Monoclinic CuO nanostructures produced at 25 °C were of dendritic morphology with short nanorod-like substructures and exhibited a consequently large surface area (179 m² g⁻¹). Cyclic voltammetry measurements confirmed pseudocapacitive behavior of these dendritic CuO nanostructures giving specific capacitance ca. 28.2 F g⁻¹ at a scan rate of 5 mV s⁻¹. Oxide nanomaterials prepared in this investigation were characterized using powder X-ray diffraction, scanning and transmission electron microscopies, and nitrogen adsorption/desorption techniques. It is expected that these materials exhibit improved sensing and catalytic properties due to the increased availability of surface adsorption sites.     

Combustion synthesis of ZnAl2O4 powders with tuned surface area

Zinc aluminate powders with tuned surface area were prepared by solution combustion synthesis, using different oxidizer-fuel ratios. As the amount of urea increased, standard heat of reaction and standard Gibbs free energy decreased, whilst adiabatic temperature increased. The larger amount of energy released during combustion facilitated grain growth and sintering, causing the decrease of specific surface area from 156 to 27 m² g⁻¹. The particle size estimated from TEM increased from 8 to 40 nm. The adsorption capacity of zinc aluminate powders with respect to methyl orange was highly dependent on the specific surface area. For an adsorbent dose of 3 g L⁻¹ the removal efficiency of methyl orange was much larger (86 versus 18%) in the case of the sample with larger surface area. The adsorption kinetics followed a pseudo-second-order model and the equilibrium data were correlated with the Freundlich isotherm.     

Entrapment of Saccharomyces cerevisiae cells in u.v. crosslinked hydroxyethylcellulose/poly(ethylene oxide) double-layered gels

Double-layered gels, consisting of hydroxyethylcellulose cryogel core and poly(ethylene oxide) hydrogel shell, were synthesized with u.v. irradiation, using the same photoinitiator, (4-benzoylbenzyl) trimethylammoniumchloride (BBTMAC) for the both layers. The gels were characterized by measuring their rheological parameters, gel fraction yield, the degree of equilibrium swelling and diffusion coefficient. The diffusion coefficients for glucose and ethanol through the hydroxyethylcellulose cryogel were 3.9 × 10^?6 cm²/s and 0.97 × 10^?5 cm²/s, respectively. The applicability of these double-layered gels as carriers for immobilization was investigated by entrapment of Saccharomyces cerevisiae cells. The immobilization efficiency and cell retention were determined in batch fermentation for ethanol production from glucose. The operational stability of the gels was evaluated in batch fermentation with three consecutive runs. The ethanol yield was in the range from 60% to 77% of the theoretical yield.     

Rose-like CuO nanostructures for highly sensitive glucose chemical sensor application

This paper reports the synthesis, characterization and glucose chemical sensing applications of well-crystalline rose-like CuO nanostructures. The rose-like CuO nanostructures were synthesized by facile hydrothermal process at low-temperature and characterized in detail in terms of their morphological, compositional, structural, optical and sensing properties. The detailed characterizations revealed that the synthesized rose-like CuO nanostructures are nanocrystalline and possessing monoclinic structure. Further, the synthesized nanostructures were used as efficient electron mediator to fabricate non-enzymatic glucose sensor. The fabricated glucose chemical sensor shows a very high sensitivity of ~4.640 μA mM⁻¹ cm⁻² and an experimental detection limit of ~0.39 mM with correlation coefficient (R) of 0.9498. The observed linear dynamic range for the fabricated chemical sensor was from 0.78 mM to 100 mM. The presented work demonstrates that simply prepared CuO nanomaterials can efficiently be used to fabricate reliable and reproducible glucose chemical sensors.     

Process intensification in small scale extraction columns for counter-current operations

This article describes a study to investigate the intensified liquid–liquid extraction by a novel, millistructured, stirred-pulsed column. The column has an inner diameter of 15 mm and is modularly designed with sections of 220 mm height consisting of 10 stirred cells. Experimental investigations were carried out in a column with five sections. The stirred cells enable high energy input, and therefore high specific surface and good extraction efficiencies. The backflow was minimized with narrow plates between the cells. Hence, the dispersed phase coalesces at the plates that separate the stirred cells. The coalescence area is destroyed by continuous pulsation of the fluid column, which transports the dispersed phase into the next stirred cell. The hydrodynamic and mass transfer inside the column was characterized with the EFCE – test system water (continuous)/acetone/n-butylacetate (dispersed). We achieved a dispersed phase hold up inside the active extraction part up to 50%, and a specific surface of over 3000 m²/m³. The extraction efficiency was measured to 17 and 25 stages per meter for the mass transfer direction (d → c) and (c → d), respectively. The comparison with other conventional pilot plant columns shows high extraction efficiency, but also a loss in total throughput.     

Highly mesoporous LaNiO3/NiO composite with high specific surface area as a battery-type electrode

This study reports the fabrication and characterization of mesoporous LaNiO₃/NiO composite with a very high specific surface area for a battery-type electrode. The mesoporous LaNiO₃/NiO composite was synthesized via a sol–gel method by using silica gel as a template, the colloidal silica gel was obtained by the hydrolysis and polymerization of tetraethoxysilane in the presence of La and Ni salts. We investigated the structure and the electrochemical properties of mesoporous LaNiO₃/NiO composite in detail. The mesoporous composite sample showed a specific surface area of 372 m² g⁻¹ with 92.7% mesoporous area and displayed remarkable electrochemical performance as a battery-type electrode material for supercapacitor. The specific capacity values were found to be 237.2 mAh g⁻¹ at a current density of 1 A g⁻¹ and 128.6 mAh g⁻¹ at a high current density of 20 A g⁻¹ in 1 M KOH aqueous electrolyte. More importantly, this mesoporous composite also showed an excellent cycling performance with the retention of 92.6% specific capacitance after 60,000 charging and discharging cycles.     

Graphitic carbon nitride nanosheet-assisted preparation of N-enriched mesoporous carbon nanofibers with improved capacitive performance

N-enriched mesoporous carbon nanofibers (NMCNFs) were prepared by an electrospinning technique using graphitic carbon nitride (g-C₃N₄) nanosheets both as sacrificial template and N-doping source. The resultant NMCNF film has a high N-doping level of 8.6 wt% and a high specific surface area of 554 m² g⁻¹. When directly used as the electrode material for supercapacitor, the free-standing NMPCNF film shows a significantly improved capacitive performance including a higher specific capacitance (220 F g⁻¹ at 0.2 A g⁻¹) and a better rate capability (∼70% retention at 20 A g⁻¹) than those of microporous carbon nanofiber film prepared using the same process without using g-C₃N₄ nanosheets (145 F g⁻¹ at 0.2 A g⁻¹ and ∼45% retention at 20 A g⁻¹). Moreover, the NMCNFs show superior stability with only a ∼3% decrease of its initial capacitance after 1000 cycles at a high current density of 10 A g⁻¹. More significantly, the energy density of a symmetrical supercapacitor (SC) based on the NMPCNF film can reach 12.5 Wh kg⁻¹ at a power density of 72 W kg⁻¹.