SLM-processed MoS2/Mo2S3 nanocomposite for energy conversion/storage applications.

MoS2-based nanocomposites have been widely processed by a variety of conventional and 3D printing techniques. In this study, selective laser melting (SLM) has for the first time successfully been employed to tune the crystallographic structure of bulk MoS2 to a 2H/1T phase and to distribute Mo2S3 nanoparticles in-situ in MoS2/Mo2S3 nanocomposites used in electrochemical energy conversion/storage systems (EECSS). The remarkable results promote further research on and elucidate the applicability of laser-based powder bed processing of 2D nanomaterials for a wide range of functional structures within, e.g., EECSS, aerospace, and possibly high-temperature solid-state EECSS even in space.

High-performance freestanding supercapacitor electrode based on polypyrrole coated nickel cobalt sulfide nanostructures.

In the present work, we report the successful fabrication of dandelion-like Nickel-Cobalt Sulfide@Polypyrrole microspheres through the hydrothermal method and its possible application as a binder-free electrode in supercapacitors. This electrode exhibited low charge transfer resistance with a remarkable specific capacitance of 2554.9 F g-1 at 2.54 A g-1, in addition to considerable cycle life stability. Also, an asymmetric device was prepared using NiCo2S4@PPy/NF as positive and rGO/NF as negative electrodes. This asymmetric supercapacitor exhibited a specific capacitance of 98.9 F g-1 at 1.84 A g-1 and delivered an energy density of 35.17 Wh kg-1 at a power density of 1472 W kg-1. Such a remarkable performance can be originated from the synergy effect of NiCo2S4 and PPy and the direct deposition of the composite on the current collector. Our findings suggest the dandelion-like NiCo2S4@PPy as a promising material for making high-performance supercapacitors.

Determination of carcinoembryonic antigen as a tumor marker using a novel graphene-based label-free electrochemical immunosensor.

In this work, a simple label-free electrochemical immunosensor for the detection of carcinoembryonic antigen (CEA) was developed. At first, the GC electrode was coated with partially reduced graphene oxide (rGO) to form a platform to bind the antibody. After activating the carboxyl groups of rGO through the EDC/NHS linker, the electrode surface was covered with the antibody. Then, the electrochemical behavior of the antibody-modified electrode and the parameters of the interactions of antibody-antigen immune complexes were investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). This immune-complex layer was found to attenuate the electrochemical current which can be used as a good signal to determine the antigen concentration. The proposed immunosensor exhibited a good amperometric response to CEA within a concentration range of 0.1-5 ng mL-1 with a detection limit of 0.05 ng ml-1. Furthermore, the developed method was evaluated for the detection of CEA in the real sample (human blood serum), and the results were comparable with the reference values obtained by the standard enzyme-linked immunosorbent assay (ELISA). Our findings suggest the present immunosensor as a good candidate for application in clinical screening.

Hierarchical H-ZSM5 zeolites based on natural kaolinite as a high-performance catalyst for methanol to aromatic hydrocarbons conversion.

The present work introduces a good prospect for the development of hierarchical catalysts with excellent catalytic performance in the methanol to aromatic hydrocarbons conversion (MTA) process. Hierarchical H-ZSM5 zeolites, with a tailored pore size and different Si/Al ratios, were synthesized directly using natural kaolin clay as a low-cost silica and aluminium resource. Further explored for the direct synthesis of hierarchical HZSM-5 structures was the steam assisted conversion (SAC) with a cost-effective and green affordable saccharide source of high fructose corn syrup (HFCS), as a secondary mesopore agent. The fabricated zeolites exhibiting good crystallinity, 2D and 3D nanostructures, high specific surface area, tailored pore size, and tunable acidity. Finally, the catalyst performance in the conversion of methanol to aromatic hydrocarbons was tested in a fixed bed reactor. The synthesized H-ZSM5 catalysts exhibited superior methanol conversion (over 100 h up to 90%) and selectivity (over 85%) in the methanol conversion to aromatic hydrocarbon products.

Enhancing potassium-ion battery performance by defect and interlayer engineering.

Defect and interlayer engineering is applied to exploit the large van der Waals gaps of transition metal dichalcogenides for potassium-ion batteries (KIBs). As a demonstrator, MoS2 nanoflowers with expanded interlayer spacing and defects in the basal planes are used as KIB anodes in the voltage range of 0.5-2.5 V, where an intercalation reaction rather than a conversion reaction takes place to store K-ions in the van der Waals gaps. The nanoflowers show enhanced K-storage performance compared to the defect-free counterpart that has a pristine interlayer spacing. Kinetic analysis verifies that the K-ion diffusion coefficient and surface charge storage are both enhanced in the applied voltage range of the intercalation reaction. The collective effects of expanded interlayer spacing and additionally exposed edges induced by the in-plane defects enable facile K-ion intercalation, rapid K-ion transport and promoted surface K-ion adsorption simultaneously.

Facile Synthesis of Mixed Metal-Organic Frameworks: Electrode Materials for Supercapacitors with Excellent Areal Capacitance and Operational Stability.

Electrode materials with high surface area, tailored pore size, and efficient capability for ion insertion and enhanced transport of electrons and ions are needed for advanced supercapacitors. In the present study, a mixed metal-organic framework (MOF) (cobalt- and manganese-based MOF) was synthesized through a simple one-pot solvothermal method and employed as the electrode material for the supercapacitor. Notably, a Co-Mn MOF electrode displayed a large surface area and excellent cycling stability (over 95% capacitance retention after 1500 cycles). Also, superior pseudocapacitive behavior was observed for the Co-Mn MOF electrode in the KOH electrolyte with an exceptional areal capacitance of 1.318 F cm-2. Moreover, an asymmetric supercapacitor was assembled using Co-Mn MOF and activated carbon electrode as positive and negative electrodes, respectively. The fabricated supercapacitor showed a specific capacitance of 106.7 F g-1 at a scan rate of 10 mV s-1 and delivered a maximum energy density of 30 W h kg-1 at 2285.7 W kg-1. Our studies suggest the Co-Mn MOF as promising electrode materials for supercapacitor applications.

Porous graphene oxide nanostructure as an excellent scaffold for label-free electrochemical biosensor: Detection of cardiac troponin I.

Herein, we report the fabrication of a novel label-free impedimetric biosensor employing porous graphene oxide (PrGO) nanostructures for the specific detection of cardiac troponin-I (cTnI) to establish the myocardial infarction (MI). This nano-immunosensor demonstrates an outstanding selectivity and high sensitivity towards the human-cTnI analyte. An excellent detection limit of 0.07ngmL(-1) and dynamic linear range of 0.1-10ngmL(-1) were calculated for anti-cTnI/PrGO/GC. Finally, this biosensor was employed to check the concentration of the MI biomarker in real clinical samples and the results are in good agreement with standard enzyme-linked fluorescence assay (ELFA) method.

Non-Faradaic electrochemical impedance spectroscopy as a reliable and facile method: Determination of the potassium ion concentration using a guanine rich aptasensor.

In this article we report the application of non-Faradaic mode of electrochemical impedance spectroscopy (EIS) for determination of potassium ion (K(+)) concentration using a guanine rich K(+)-selective aptasensor (K(+)-aptasensor). This is a simple, electroactive probe free, sensitive and reproducible method allowing determination of K(+) ion concentration without any disturbance from electroactive probes used in similar works based on the Faradaic EIS method. Herein, a wide linear range of K(+) ion concentrations (1 µM-0.1mM) with a 200 nM limit of detection was achieved which is better than most of the previously reported Faradaic biosensing methods. The proposed method maintains valuable applications when it is used for K(+) determination in the presence of potentially important interferences in biological media. Thus, application of the non-Faradaic EIS method for sensing the concentration of K(+) ion with the presented K(+)-aptasensor can find an important role in clinical assay.

Graphene-gold nanoparticle composite: application as a good scaffold for construction of glucose oxidase biosensor.

In the present work we report a facile method for fabrication of glucose oxidase immobilized on the partially reduced graphene-gold nanocomposite (PRGO-AuNPs/GOx) as a novel biosensor for determination of glucose concentration. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to study the morphology of PRGO and PRGO-AuNPs. Also, fast Fourier transformation infrared spectroscopy (FTIR) and UV-Vis spectroscopy were used to confirm formation of graphene and graphene-gold composite. Then, the electrochemical behavior of PRGO-AuNPs/GOx modified electrode was studied by cyclic voltammetry (CV). Our electrochemical studies, especially chronoamperometry (CA), showed that the PRGO-AuNPs/GOx modified electrode has excellent electrocatalytic activity towards the glucose. The limit of detection and sensitivity towards glucose were estimated as 0.06µM and 15.04mAmM(-1), respectively.

The role of nano-sized manganese oxides in the oxygen-evolution reactions by manganese complexes: towards a complete picture.

Eighteen Mn complexes with N-donor and carboxylate ligands have been synthesized and characterized. Three Mn complexes among them are new and are reported for the first time. The reactions of oxygen evolution in the presence of oxone (2KHSO5·KHSO4·K2SO4) and cerium(iv) ammonium nitrate catalyzed by these complexes are studied and characterized by UV-visible spectroscopy, X-ray diffraction spectrometry, dynamic light scattering, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, scanning electron microscopy, membrane-inlet mass spectrometry and electrochemistry. Some of these complexes evolve oxygen in the presence of oxone as a primary oxidant. CO2 and MnO4(-) are other products of these reactions. Based on spectroscopic studies, the true catalysts for oxygen evolution in these reactions are different. We proposed that for the oxygen evolution reactions in the presence of oxone, the true catalysts are both high valent Mn complexes and Mn oxides, but for the reactions in the presence of cerium(iv) ammonium nitrate, the active catalyst is most probably a Mn oxide.

pH-regulated release of dopamine from well-ordered self-assembled monolayers: electrochemical studies.

In the present work, gold electrode modified with novel aldehyde-terminated self-assembled monolayers (SAMs) was used for controllable load and release of dopamine molecules by pH triggering. Electrochemical techniques including cyclic voltammetry (CV) and electrochemcial impedance spectroscopy (EIS) were employed to investigate the SAMs characteristic on the gold electrode surface. The electrochemical experiments indicated Faradaic behavior for the electrode surface after its modification with dopamine. Notably, it was observed that decreasing the conditioning pH, results in a decrease of peak currents, presumably due to the hydrolysis of the terminal imine bonds and releasing the dopamine moiety into the solution. Moreover, the preliminary kinetics studies were done for dopamine release from the SAMs surface as a model to design future drug delivery systems. Finally, the rate constant of dopamine release from the SAMs modified surface estimated to be 0.167 day(-1) at pH=3.

Impedance studies of a nano-structured conducting polymer and its application to the design of reliable scaffolds for impedimetric biosensors.

Electrochemical impedance spectroscopy (EIS) as a powerful, non-invasive and informative technique was used to obtain important information about kinetics of doping process in conducting polymers. Polypyrrole (PPy) and its derivatives can form conducting polymer films which represent excellent charge transfer behaviors during doping processes. It can also have a wide range of applications in bioelectrochemistry. In the present study the conducting polymer of alpha-carboxy pyrrole (alpha-COOH-PPy), appended onto the underlying film of PPy, was prepared by electrochemical methods and its behavior was analyzed using EIS. From highly accurate fitting of impedance results it was found that the charging mechanism is governed by the diffusion process. In addition, the impedance analyses provided values for the bulk polymer parameters including diffusion coefficient (D), equilibrium capacitance (C(0)) and diffusion resistance (R(0)). The surface morphology of the polymeric film was characterized using scanning electron microscopy (SEM). The film was then used to immobilize the cytochrome C (cyt-C) and to perform its electrochemical studies. The modified cyt-C/alpha-COOH-PPy electrode was used for electrocatalytic reduction of H(2)O(2) in solution and its viability as a new impedimetric biosensor was examined. Based on the calibration curve obtained for the proposed impedimetric biosensor, the limit of detection and relative standard deviation were evaluated as 0.25 micromolL(-1) and 7%, respectively. Finally, the prolonged stability test was performed and high stability and reproducibility of the new biosensor was confirmed.