Synthesis and characterization of MXene (Ti3C2Tx)/Iron oxide composite for ultrasensitive electrochemical detection of hydrogen peroxide.

Due to the widespread usage of hydrogen peroxide (H2O2) in various consumer and industrial products (Examples: fuel cells and antibacterial agents), it became important to accurately detect H2O2 concentration in environmental, medical and food samples. Herein, titanium carbide Ti3C2Tx (MXene) was synthesized by using Ti, Al and C powders at high-temperature. Then, nanocrystalline iron oxide (α-Fe2O3) was obtained from a single solid-phase method. Using Ti3C2Tx and Fe2O3 powders, Ti3C2Tx-Fe2O3 nanocomposite was prepared by ultrasonication. As-synthesized, Ti3C2Tx-Fe2O3 composite had been characterized by UV-Visible (UV-Vis), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and Raman spectroscopy. The Fe2O3 nanoparticles (NPs) were decorated on the surface of Ti3C2Tx as observed by high resolution scanning electron microscopy (HR-SEM) and high resolution transmission electron microscopy (HR-TEM). The Ti3C2Tx nanosheets were formed with the average size of 400-500 nm. HR-SEM images of α-Fe2O3 showed that the coral-like particles with the average length ~5 µm were obtained. The electrochemical properties of the individual (Ti3C2Tx and α-Fe2O3) and composite materials (Ti3C2Tx-Fe2O3) were investigated by cyclic voltammetry (CV). Ti3C2Tx-Fe2O3 nanocomposite modified electrode had exhibited potent electro-catalytic activity for H2O2 reduction by reducing the overpotential about 320 mV and a linear response was recorded from 10 nM to 1 µM H2O2. The optimization of various parameters such as material composition ratio, amount of catalyst, effects of pH, scan rate and interference effects with other biomolecules were carried out. In addition, the kinetic parameters such as rate constant, diffusion coefficient and the active surface area of the electrodes were calculated. Moreover, the Ti3C2Tx-Fe2O3 composite modified electrode was used successfully to detect H2O2 in food and urine samples. We believe that Ti3C2Tx-Fe2O3 composite based materials could be used for the fabrication of non-enzymatic H2O2 sensors for medical diagnosis, food safety and environmental monitoring applications.

Biocompatible MXene (Ti3C2Tx) Immobilized with Flavin Adenine Dinucleotide as an Electrochemical Transducer for Hydrogen Peroxide Detection in Ovarian Cancer Cell Lines.

Flavin adenine dinucleotide (FAD) is a coenzyme and acts as a redox cofactor in metabolic process. Owing to such problems as poor electron transfer properties, unfavorable adsorption, and lack of stability on rigid electrodes, the bio-electrochemical applications of FAD have been limited. Herein, a novel fabrication method was developed for the immobilization process using 2D MXene (Ti3C2Tx), which enhanced the redox property of FAD and improved the electro-catalytic reduction of hydrogen peroxide (H2O2) in neutral medium. The FAD-immobilized Ti3C2Tx electrode (FAD/Ti3C2Tx) was studied by UV-Visible and Raman spectroscopies, which confirmed the successful adsorption of FAD on the Ti3C2Tx surface. The surface morphology and the elemental composition of Ti3C2Tx were investigated by high resolution transmission electron microscopy and the energy dispersive X-ray analysis. The redox property of the FAD/Ti3C2Tx modified glassy carbon electrode (FAD/Ti3C2Tx/GCE) was highly dependent on pH and exhibited a stable redox peak at -0.455 V in neutral medium. Higher amounts of FAD molecules were loaded onto the 2D MXene (Ti3C2Tx)-modified electrode, which was two times higher than the values in the reported work, and the surface coverage (á´¦FAD) was 0.8 × 10-10 mol/cm2. The FAD/Ti3C2Tx modified sensor showed the electrocatalytic reduction of H2O2 at -0.47 V, which was 130 mV lower than the bare electrode. The FAD/Ti3C2Tx/GCE sensor showed a linear detection of H2O2 from 5 nM to 2 µM. The optimization of FAD deposition, amount of Ti3C2Tx loading, effect of pH and the interference study with common biochemicals such as glucose, lactose, dopamine (DA), potassium chloride (KCl), ascorbic acid (AA), amino acids, uric acid (UA), oxalic acid (OA), sodium chloride (NaCl) and acetaminophen (PA) have been carried out. The FAD/Ti3C2Tx/GCE showed high selectivity and reproducibility. Finally, the FAD/Ti3C2Tx modified electrode was successfully applied to detect H2O2 in ovarian cancer cell lines.

Selective Chemistry-Based Separation of Semiconducting Single-Walled Carbon Nanotubes and Alignment of the Nanotube Array Network under Electric Field for Field-Effect Transistor Applications.

Semiconducting single-walled carbon nanotubes (s-SWCNTs) are considered as a replacement for silicon in field-effect transistors (FETs), solar cells, logic circuits, and so forth, because of their outstanding electronic, optical, and mechanical properties. Herein, we have studied the reaction of pristine SWCNTs dispersed in a pluronic F-68 (PF-68) polymer solution with para-amino diphenylamine diazonium sulfate (PADDS) to separate nanotubes based on their metallicity. The preferential selectivity of the reactions was monitored by changes in the semiconducting (S22 and S33) and metallic (M11) bands by ultraviolet-visible-near infrared spectroscopy. Metallic selectivity depended on the concentrations of PADDS, reaction time, and the solution pH. Furthermore, separation of pure s-SWCNTs was confirmed by Raman spectroscopy and Fourier-transform infrared spectroscopy. After the removal of metallic SWCNTs, direct current electric field was applied to the pure s-SWCNT solution, which effectively directed the nanotubes to align in one direction as nanotube arrays with a longer length and high density. After that, electrically aligned s-SWCNT solution was cast on a silicon substrate, and the length of the nanotube arrays was measured as ∼2 to ∼14 µm with an areal density of ∼2 to ∼20 tubes/µm of s-SWCNTs. Next, electrically aligned s-SWCNT arrays were deposited on the channel of the FET device by drop-casting. Field-emission scanning electron microscopy and electrical measurements have been carried out to test the performance of the aligned s-SWCNTs/FETs. The fabricated FETs with a channel length of 10 µm showed stable electrical properties with a field-effect mobility of 30.4 cm2/Vs and a log10 (I on/I off) current ratio of 3.96. We envisage that this new chemical-based separation method and electric field-assisted alignment could be useful to obtain a high-purity and aligned s-SWCNT array network for the fabrication of high-performance FETs to use in digital and analog electronics.

Recent trends in the applications of thermally expanded graphite for energy storage and sensors - a review.

Carbon nanomaterials such as carbon dots (0D), carbon nanotubes (1D), graphene (2D), and graphite (3D) have been exploited as electrode materials for various applications because of their high active surface area, thermal conductivity, high chemical stability and easy availability. In addition, due to the strong affinity between carbon nanomaterials and various catalysts, they can easily form metal carbides (examples: ionic, covalent, interstitial and intermediate transition metal carbides) and also help in the stable dispersion of catalysts on the surface of carbon nanomaterials. Thermally expanded graphite (TEG) is a vermicular-structured carbon material that can be prepared by heating expandable graphite up to 1150 °C using a muffle or tubular furnace. At high temperatures, the thermal expansion of graphite occurred by the intercalation of ions (examples: SO4 2-, NO3 -, Li+, Na+, K+, etc.) and oxidizing agents (examples: ammonium persulfate, H2O2, potassium nitrate, potassium dichromate, potassium permanganate, etc.) which helped in the exfoliation process. Finally, the obtained TEG, an intumescent form of graphite, has been used in the preparation of composite materials with various conducting polymers (examples: epoxy, poly(styrene-co-acrylonitrile), polyaniline, etc.) and metal chlorides (examples: FeCl3, CuCl2, and ZnCl2) for hydrogen storage, thermal energy storage, fuel cells, batteries, supercapacitors, sensors, etc. The main features of TEG include a highly porous structure, very lightweight with an apparent density (0.002-0.02 g cm-3), high mechanical properties (10 MPa), thermal conductivity (25-470 W m-1 K-1), high electrical conductivity (106-108 S cm-1) and low-cost. The porosity and expansion ratio of graphite layers could be customized by controlling the temperature and selection of intercalation ions according to the demand. Recently, TEG based composites prepared with metal oxides, chlorides and polymers have been demonstrated for their use in energy production, energy storage, and electrochemical (bio-) sensors (examples: urea, organic pollutants, Cd2+, Pb2+, etc.). In this review, we have highlighted and summarized the recent developments in TEG-based composites and their potential applications in energy storage, fuel cells and sensors with hand-picked examples.