Capacity Optimization Nanotechnologies for Enhanced Energy Storage Systems

Rechargeable lithium-ion battery (LIB) cathodes consist of transition metal oxide material, which reversibly (de)intercalates lithium at a high potential difference versus a carbon anode. Manganese oxide cathode material offers lower cost and toxicity than the normally used cobalt. However, LiMn2O4 suffers from capacity fading, Mn dissolution at high temperatures, and poor high rate capability. Its ultimate performance, however, depends on the morphology and electrochemical properties. In this work, Au alloyed with Fe, Pd, and Pt, respectively, was synthesized and used to improve the microstructure and catalytic activities by functionalizing LiMn2O4 via a coprecipitation calcination method. The pristine LiMn2O4 and modified materials were examined using a combination of spectroscopic and microscopic techniques along with in-detail galvanostatic charge–discharge tests. Microscopic results revealed that the modified composite cathode materials had high phase purity, highly crystallized particles, and more regular morphological structures with narrow size distributions. Galvanostatic charge–discharge testing indicated that the initial discharge capacities of LiMxMn2-xO4 at 0.1 C for M0.02=PtAu, FeAu, and PdAu were 147, 155.5, and 160.2 mAh g−1, respectively. The enhancement of the capacity retention and higher electrode coulombic efficiency of the modified materials were significant, especially at high C rate. At enlarged cycling potential ranges, the Li(M)0.02Mn1.98O4 samples delivered relevant discharge capacities (70, 80, and 90 mAh g-1) compared to LiMn2O4 (45 mAh g-1)

Actuation behaviour of a derivatized pyrrole accordion type polymer

A monomer (Phenazine-2,3-diimino(pyrrole-2-yl)–PDP) derived from the condensation reaction between 2,3-diaminophenazine and a pyrrole derivative has been synthesized as a hinge molecule in the design of a zig-zag polymer. The monomer was polymerized both chemically and electrochemically in order to produce the polymer material, phenazine-2,3-diimino(pyrrole-2-yl (PPDP). During electrochemical polymerization the system was doped using 1,4-napthaquinone sulphonic acid (NQSA) and polyvinylsulfonic acid (PVSA) respectively, to improve conductivity. Characterization of the materials by Fourier transform infrared spectroscopy (FTIR) confirmed the successful linking of the starting materials to produce the hinge molecule and nuclear magnetic resonance spectroscopy (NMR) supported the FTIR data. The electrochemistry of the polymer in the doped and undoped state was evaluated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS)

Carcinoembryonic antigen immunosensor developed with organoclay nanogold composite film

Organoclay nanogold composite were prepared using gold nanoparticles and the natural Cameroonian clay grafted with amino organosilane. The functionnalization of clay provided abundant amino group to assemble gold nanoparticles. A label-free electrochemical immunosensor for the sensitive determination of carcinoembryonic antigen (CEA) was fabricated by immobilizing anti-CEA onto organoclay nanogold composite film modified electrode by the cross-linking method using glutaraldehyde. In addition, the preparation procedure of the immunosensor was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Under optimal conditions, the resulting immunosensor displayed a high sensitivity for the detection of CEA, and responded to the CEA concentration in two ranges from 0.05 to 5.0 ng/mL (R = 0.991) and from 5.0 to 120.0 ng/mL (R = 0.998) with a detection limit of 0.01 ng/mL

Electrochemically reduced graphene oxide pencil-graphite in situ plated bismuth-film electrode for the determination of trace metals by anodic stripping voltammetry

An electrochemical platform was developed based on a pencil-graphite electrode (PGE) modified with electrochemically reduced graphene oxide (ERGO) sheets and in conjunction with an in situ plated bismuth-film (ERGO-PG-BiE). The ERGO-PG-BiE was used as a sensing platform for determining Zn2+, Cd2+ and Pb2+ by square wave anodic stripping voltammetry (SWASV). ERGO sheets were deposited on to pencil-graphite electrodes by cyclic voltammetric reduction from a graphene oxide (GO) solution. The GO, with flake thicknesses varying between 1.78 to 2.10 nm (2 sheets) was characterized using FT-IR, HR-SEM, HR-TEM, AFM, XRD and Raman spectroscopy. Parameters influencing the electroanalytical response of the ERGO-PG-BiE such as, bismuth-film concentration, deposition potential, deposition time and rotation speed were investigated and optimized. The ERGO-PG-BiE gave well-defined, reproducible peaks with detection limits of 0.19 μg L-1, 0.09 μg L-1 and 0.12 μg L-1 for Zn2+, Cd2+ and Pb2+ respectively, at a deposition time of 120 seconds. For real sample analysis, the enhanced voltammetric sensor proved to be suitable for the detection and quantitation of heavy metals below the US EPA prescribed drinking water standards of 5 mg L-1, 5 μg L-1 and 15 μg L-1 for Zn2+, Cd2+ and Pb2+ respectively

Electrochemistry and application of a novel monosubstituted squarate electron-transfer mediator in a glucose oxidase-doped poly(phenol) sensor

Electrosynthetic poly(phenol) nanofilms were deposited in situ on platinum electrodes in the presence and absence of glucose oxidase. The synthesis charges and currents of the nonconducting polymer films were recorded at various applied potentials for films grown from 25–100 mM phenol concentrations. Film parameters such as the standard rate constant for film deposition, film thickness, and surface concentration of the poly(phenol) films were evaluated from the cyclic and step voltammograms of the polymerization process. A novel electron-transfer mediator consisting of monosubstituted 4-hydroxycyclobut-3-ene-1,2-dione (squarate) was used as a mediator for Pt/poly(phenol) nano-film/GOx amperometric glucose biosensors. Amperometric responses for 3-diphenylamino-4-hydroxycyclobut-3-ene-1,2- dione (diphenylaminosquarate: E°′ = of +328 mV/Ag-AgCl at pH 7.0)-mediated systems were measured by both steady-state amperometric and cyclic voltammetry. The sensor sensitivity was calculated to be 558 nA cm –2 (µM) –1

Metallo-Graphene Nanocomposite Electrocatalytic Platform for the Determination of Toxic Metal Ions

A Nafion-Graphene (Nafion-G) nanocomposite solution in combination with an in situ plated mercury film electrode was used as a highly sensitive electrochemical platform for the determination of Zn2+, Cd2+, Pb2+ and Cu2+ in 0.1 M acetate buffer (pH 4.6) by square-wave anodic stripping voltammetry (SWASV). Various operational parameters such as deposition potential, deposition time and electrode rotation speed were optimized. The Nafion-G nanocomposite sensing platform exhibited improved sensitivity for metal ion detection, in addition to well defined, reproducible and sharp stripping signals. The linear calibration curves ranged from 1 μg L−1 to 7 μg L−1 for individual analysis. The detection limits (3σ blank/slope) obtained were 0.07 μg L−1 for Pb2+, Zn2+ and Cu2+ and 0.08 μg L−1 for Cd2+ at a deposition time of 120 s. For practical applications recovery studies was done by spiking test samples with known concentrations and comparing the results with inductively coupled plasma mass spectrometry (ICP-MS) analyses. This was followed by real sample analysis

Few-layer binder free graphene modified mercury film electrode for trace metal analysis by square wave anodic stripping voltammetry

A binding agent free graphene modified glassy carbon electrode in combination with an in situ plated mercury film electrode (Gr-GC-HgFE) was used as a highly sensitive electrochemical platform for the determination of Zn2+, Cd2+ and Pb2+ in 0.1 M acetate buffer (pH 4.6) by square-wave anodic stripping voltammetry (SWASV). Instrumental parameters such as deposition potential, deposition time and electrode rotation speed were optimized. The Gr-GC-HgFE sensing platform exhibited improved sensitivity for metal ion detection, in addition to well defined, reproducible and sharp stripping signals. Two linear calibration curves ranging from 0 –10 μg L−1 and 0 – 60 μg L−1 were identified yielding detection limits of 0.08 μg L−1, 0.05 μg L−1 and 0.14 μg L−1 for Zn2+, Cd2+ and Pb2+, respectively, for simultaneous analysis and 0.04 μg L−1, 0.11 μg L−1 and 0.14 μg L−1 for Zn2+, Cd2+ and Pb2+, respectively, for individual analysis when using a deposition time of 120 s. For practical applications recovery studies using tap water samples spiked with target metal ions gave recoveries within 10% of the spiked amount. Much better recoveries were obtained for the individual analysis in comparison with simultaneous analysis.Web of Scienc

Chlorido{N-[2-(diphenylphosphanyl)- benzylidene]-2-(2-thienyl)ethanamine-ĸ²N,P}methylpalladium(II) dichloromethane hemisolvate

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Enhanced photovoltaic effects of microwave-assisted polyolsynthesized Cu2(Pd/Zn)SnS4 kesterite nanoparticles

Kesterite materials show excellent optical and semiconductive properties for use as petype absorber layer in photovoltaic (PV) applications, but they have a high open circuit voltage deficit (Voc,def) due to high antisite defect and secondary phase formation, resulting in poor device performance. This work reports a PV cell composed of Cu2PdSnS4 (CPTS) nanoparticles as an absorber layer yielding highly improved Voc of 900 mV, which is two times that of fabricated pristine Cu2ZnSnS4 (CZTS) PV cell. Improved PV cell parameters such as fillefactor (FF) of 83.4% and power conversion efficiency (PCE) of 1.01% were obtained for CPTS devices which are 3efold that of pristine CZTS devices. Optical studies revealed enhanced redshift absorption for CPTS nanoparticles. Electrochemical studies show improved current production, high electron mobility and low charge resistance for CPTS nanoparticles. This study shows that the improved photovoltaic properties can be attributed to enhancement in the bulk properties when Zn atoms are replaced by Pd atoms in kesterite nanomaterials as absorber layer material for PV applications

Polyester Sulphonic Acid Interstitial Nanocomposite Platform for Peroxide Biosensor

A novel enzyme immobilization platform was prepared on a platinum disk working electrode by polymerizing aniline inside the interstitial pores of polyester sulphonic acid sodium salt (PESA). Scanning electron microscopy study showed the formation of homogeneous sulphonated polyaniline (PANI) nanotubes (∼90 nm) and thermogravimetric analysis (TGA) confirmed that the nanotubes were stable up to 230 °C. The PANI:PESA nanocomposite showed a quasi-reversible redox behaviour in phosphate buffer saline. Horseradish peroxidase (HRP) was immobilized on to this modified electrode for hydrogen peroxide detection. The biosensor gave a sensitivity of 1.33 μA (μM)-1 and a detection limit of 0.185 μM for H2O2. Stability experiments showed that the biosensor retained more than 64% of its initial sensitivity over four days of storage at 4 °C