High-Pressure High-Temperature Synthesis of Mixed Nitridosilicatephosphates and Luminescence of AESiP3N7:Eu2+ (AE=Sr,Ba)

Tetrahedra-based nitrides with network structures have emerged as versatile materials with a broad spectrum of properties and applications. Both nitridosilicates and nitridophosphates are well-known examples of such nitrides that upon doping with Eu²⁺ exhibit intriguing luminescence properties, which makes them attractive for applications. Nitridosilicates and nitridophosphates show manifold structural variability; however, no mixed nitridosilicatephosphates except SiPN₃ and SiP2N4NH have been described so far. The compounds AESiP₃N₇ (AE=Sr, Ba) were synthesized by a high-pressure high-temperature approach using the multianvil technique (8 GPa, 1400–1700 °C) starting from the respective alkaline earth azides and the binary nitrides P₃N₅ and Si₃N₄. The latter were activated by NH₄F, probably acting as a mineralizing agent. SrSiP₃N₇ and BaSiP₃N₇ were obtained as single crystals. They crystallized in the barylite-1O (M=Sr) and barylite-2O structure types (M=Ba), respectively, with P and Si being occupationally disordered. Cation disorder was further supported by solid-state NMR spectroscopy and energy-dispersive X-ray spectroscopy (EDX) mapping of BaSiP₃N₇ with atomic resolution. Upon doping with Eu²⁺, both compounds showed blue emission under UV excitation.     

Click Chemistry in Ultra-high Vacuum – Tetrazine Coupling with Methyl Enol Ether Covalently Linked to Si(001)

The additive-free tetrazine/enol ether click reaction was performed in ultra-high vacuum (UHV) with an enol ether group covalently linked to a silicon surface: Dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate molecules were coupled to the enol ether group of a functionalized cyclooctyne which was adsorbed on the silicon (001) surface via the strained triple bond of cyclooctyne. The reaction was observed at a substrate temperature of 380 K by means of X-ray photoelectron spectroscopy (XPS). A moderate energy barrier was deduced for this click reaction in vacuum by means of density functional theory based calculations, in good agreement with the experimental results. This UHV-compatible click reaction thus opens a new, flexible route for synthesizing covalently bound organic architectures.     

Ionic/electronic conductivity regulation of n-type polyoxadiazole lithium sulfonate conductive polymer binders for high-performance silicon microparticle anodes

Low-cost silicon microparticles(SiMP),as a substitute for nanostructured silicon,easily suffer from cracks and fractured during the electrochemical cycle.A novel n-type conductive polymer binder with excellent electronic and ionic conductivities as well as good adhesion,has been successfully designed and applied for high-performance SiMP anodes in lithium-ion batteries to address this problem.Its unique features are attributed to the stro ng electron-withdrawing oxadiazole ring structure with sulfonate polar groups.The combination of rigid and flexible components in the polymer ensures its good mechanical strength and ductility,which is beneficial to suppress the expansion and contraction of SiMP s during the charge/discharge process.By fine-tuning the monomer ratio,the conjugation and sulfonation degrees of the polymer can be precisely controlled to regulate its ionic and electronic conductivities,which has been systematically analyzed with the help of an electrochemical test method,filling in the gap on the conductivity measurement of the polymer in the doping state.The experimental results indicate that the cell with the developed n-type polymer binder and SiMP(~0.5 μm) anodes achieves much better cycling performance than traditional non-conductive binders.It has been considered that the initial capacity of the SiMP anode is controlled by the synergetic effect of ionic and electronic conductivity of the binder,and the capacity retention mainly depends on its electronic conductivity when the ionic conductivity is sufficient.It is worth noting that the fundamental research of this wo rk is also applicable to other battery systems using conductive polymers in order to achieve high energy density,broadening their practical applications.     

Bipolar Electrochemiluminescence Imaging: A Way to Investigate the Passivation of Silicon Surfaces

This work depicts the original combination of electrochemiluminescence (ECL) and bipolar electrochemistry (BPE) to map in real-time the oxidation of silicon in microchannels. We fabricated model silicon-PDMS microfluidic chips, optionally containing a restriction, and monitored the evolution of the surface reactivity using ECL. BPE was used to remotely promote ECL at the silicon surface inside microfluidic channels. The effects of the fluidic design, the applied potential and the resistance of the channel (controlled by the fluidic configuration) on the silicon polarization and oxide formation were investigated. A potential difference down to 6 V was sufficient to induce ECL, which is two orders of magnitude less than in classical BPE configurations. Increasing the resistance of the channel led to an increase in the current passing through the silicon and boosted the intensity of ECL signals. Finally, the possibility of achieving electrochemical reactions at predetermined locations on the microfluidic chip was investigated using a patterning of the silicon oxide surface by etched micrometric squares. This ECL imaging approach opens exciting perspectives for the precise understanding and implementation of electrochemical functionalization on passivating materials. In addition, it may help the development and the design of fully integrated microfluidic biochips paving the way for development of original bioanalytical applications.     

Molecularly imprinted polymer-carbon paste electrode (MIP-CPE)-based sensors for the sensitive detection of organic and inorganic environmental pollutants: A review

The rapidly growing existence of a number of contaminants (i.e. heavy metals, dye compounds, explosives and pesticides etc.) in environment is an alarming concern not only due to their harmful impacts for the environment bur also due to their potential high risk for human health. Thus, the careful and sensitive detection of these environmental contaminants is ver crucial. Electrochemical sensors combined with molecularly imprinted polymers (MIPs) become an attractive area for environmental monitoring. Benefiting from their great features such as high chemical and physical stability, cheap preparation process, excellent selectivity, sensitivity and fast response towards the target compound/s.This review paper aims to present and highlight the latest progresses in the design and development of novel electrochemical sensor systems composed of MIPs and carbon paste electrodes (CPEs) for the sensitive detection of pollutants in environmental samples.     

Three-dimensional bundle-like multiwalled carbon nanotubes composite for supercapacitor electrode application

Bundle-type mutil-walled carbon nanotubes (MWCNTs) composite electrode is the first investigation and publication for the supercapacitor application. According to the thermogravimetric analysis results, as-synthesized BCNTs are considered as the electrode materials for supercapacitors and electrochemical double-layer capacitor in this study. The Brunauer–Emmett–Teller specific surface area of as-prepared bundled carbon nanotubes (BCNTs) is 95.29 m²/g given to a type III isotherm and H3 hysteresis loops. Slow scanning rates promote and enhance to achieve high C_b because of the superior conductivity of CNT bundles and one side close-layered Ni/Mg/Mo alloy inside the BCNT-based electrode and facile electron diffusivity between electrolyte and electrode. The specific capacitance C_s (1,560 F/g) is nearly equal to the maximum specific capacitance, which the BCNT-based composite electrode can actually be able to charge or fill in. The maximum energy density value is 195 Wh/kg with corresponding power density values of 0.21 kW/kg. Furthermore, the active 3D BCNTs material fabricated electrode enhances to contact the electrolyte directly and decreases the ion diffusion limitation. Electrochemical impedance spectroscopy spectrum summarized as the low-frequency area controls by mass transfer limitation, and the high-frequency area dominates by charge transfer of kinetic control. After 2,000 consecutive cyclic voltammetry sacnings and galvanostatic charge-discharge cycles at a current density of 1.67 A/g performs, the specific capacitance retentions of 3D BCNTs electrodes achieved 128.2 and 77.3%, respectively. Three-dimensional BCNT composite electrodes exhibit good conductivity and low charge transfer resistance, which is beneficial to fast charge transfer between the BCNTs electrode materials and electrolytes.     

Molecularly engineered graphene surfaces for sensing applications: A review

Graphene is scientifically and commercially important because of its unique molecular structure which is monoatomic in thickness, rigorously two-dimensional and highly conjugated. Consequently, graphene exhibits exceptional electrical, optical, thermal and mechanical properties. Herein, we critically discuss the surface modification of graphene, the specific advantages that graphene-based materials can provide over other materials in sensor research and their related chemical and electrochemical properties. Furthermore, we describe the latest developments in the use of these materials for sensing technology, including chemical sensors and biosensors and their applications in security, environmental safety and diseases detection and diagnosis.     

Electrochemical sensors and biosensors based on redox polymer/carbon nanotube modified electrodes: A review

The aim of this review is to present the contributions to the development of electrochemical sensors and biosensors based on polyphenazine or polytriphenylmethane redox polymers together with carbon nanotubes (CNT) during recent years. Phenazine polymers have been widely used in analytical applications due to their inherent charge transport properties and electrocatalytic effects. At the same time, since the first report on a CNT-based sensor, their application in the electroanalytical chemistry field has demonstrated that the unique structure and properties of CNT are ideal for the design of electrochemical (bio)sensors. We describe here that the specific combination of phenazine/triphenylmethane polymers with CNT leads to an improved performance of the resulting sensing devices, because of their complementary electrical, electrochemical and mechanical properties, and also due to synergistic effects. The preparation of polymer/CNT modified electrodes will be presented together with their electrochemical and surface characterization, with emphasis on the contribution of each component on the overall properties of the modified electrodes. Their importance in analytical chemistry is demonstrated by the numerous applications based on polymer/CNT-driven electrocatalytic effects, and their analytical performance as (bio) sensors is discussed.     

A novel electrochemical immunosensor using β-cyclodextrins functionalized silver supported adamantine-modified glucose oxidase as labels for ultrasensitive detection of alpha-fetoprotein

In this work, a novel sandwich-type electrochemical immunosensor based on host-guest interaction was fabricated for the detection of alpha-fetoprotein (AFP). Due to the large specific surface area of multiwalled carbon nanotubes and the unique supramolecular recognition ability of β-cyclodextrins, ferrocenecarboxylic acid (Fc) was incorporated into this sensor platform by host-guest interaction to generate an electrochemical signal. And β-cyclodextrins functionalized silver supported adamantine-modified glucose oxidase (GOD-CD-Ag), was used as a label to improve the analytical performance of the immunosensor by the dual amplification strategy. The obtained GOD-CD-Ag conjugates could convert glucose into gluconic acid with the formation of hydrogen peroxide (H₂O₂). And then silver nanoparticles could in situ catalyze the reduction of the generated H₂O₂, dramatically improving the oxidation reaction of Fc. The developed immunosensor shows a wide linear calibration range from 0.001 to 5.0 ng/mL with a low detection limit (0.2 pg/mL) for the detection of AFP. The method, with ideal reproducibility and selectivity, has a wide application prospect in clinical research.     

The Cu-MOF-199/single-walled carbon nanotubes modified electrode for simultaneous determination of hydroquinone and catechol with extended linear ranges and lower detection limits

A novel electrochemical sensor based on Cu-MOF-199 [Cu-MOF-199 = Cu₃(BTC)₂ (BTC = 1,3,5-benzenetricarboxylicacid)] and SWCNTs (single-walled carbon nanotubes) was fabricated for the simultaneous determination of hydroquinone (HQ) and catechol (CT). The modification procedure was carried out through casting SWCNTs on the bare glassy carbon electrode (GCE) and followed by the electrodeposition of Cu-MOF-199 on the SWCNTs modified electrode. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were performed to characterize the electrochemical performance and surface characteristics of the as-prepared sensor. The composite electrode exhibited an excellent electrocatalytic activity with increased electrochemical signals towards the oxidation of HQ and CT, owing to the synergistic effect of SWCNTs and Cu-MOF-199. Under the optimized condition, the linear response range were from 0.1 to 1453 μmol L⁻¹ (R_HQ = 0.9999) for HQ and 0.1–1150 μmol L⁻¹ (R_CT = 0.9990) for CT. The detection limits for HQ and CT were as low as 0.08 and 0.1 μmol L⁻¹, respectively. Moreover, the modified electrode presented the good reproducibility and the excellent anti-interference performance. The analytical performance of the developed sensor for the simultaneous detection of HQ and CT had been evaluated in practical samples with satisfying results.