Thermal stability study of nitrogen functionalities in a graphene network

Catalyst-free vertically aligned graphene nanoflakes possessing a large amount of high density edge planes were functionalized using nitrogen species in a low energy N+ ion bombardment process to achieve pyridinic, cyanide and nitrogen substitution in hexagonal graphitic coordinated units. The evolution of the electronic structure of the functionalized graphene nanoflakes over the temperature range 20-800^{\circ}C was investigated in situ, using high resolution x-ray photoemission spectroscopy. We demonstrate that low energy irradiation is a useful tool for achieving nitrogen doping levels up to 9.6 at.%. Pyridinic configurations are found to be predominant at room temperature, while at 800^{\circ}C graphitic nitrogen configurations become the dominant ones. The findings have helped to provide an understanding of the thermal stability of nitrogen functionalities in graphene, and offer prospects for controllable tuning of nitrogen doping in device applications.Comment: Corresponding author: [email protected]

Electrocatalytic Hydrogen Evolution Reaction on Edges of a Few Layer Molybdenum Disulfide Nanodots

The design and development of inexpensive highly efficient electrocatalysts for hydrogen production, underpins several emerging clean-energy technologies. In this work, for the first time, molybdenum disulfide (MoS2) nanodots have been synthesized by ionic liquid assisted grinding exfoliation of bulk platelets and isolated by sequential centrifugation. The nanodots have a thickness of up to 7 layers (4 nm) and an average lateral size smaller than 20 nm. Detailed structural characterization established that the nanodots retained the crystalline quality and low oxidation states of the bulk material. The small lateral size and reduced number of layers provided these nanodots with an easier path for the electron transport and plentiful active sites for the catalysis of hydrogen evolution reaction (HER) in acidic electrolyte. The MoS2 nanodots exhibited good durability and a Tafel slope of 61 mVdec-1 with an estimated onset potential of -0.09 V vs RHE, which are considered among the best values achieved for 2H phase. It is envisaged that this work may provide a simplistic route to synthesize a wide range of 2D layered nanodots that have applications in water splitting and other energy related technologies. KEYWORDS: MoS2 nanosheets, hydrogen evolution reaction, electrocatalysis, edges, nanodots, ionic liquid exfoliation, water splittingComment: Corresponding author: [email protected]. in ACS Applied Materials and Interfaces, 201

Controllable selective exfoliation of high-quality graphene nanosheets and nanodots by ionic liquid assisted grinding

Bulk quantities of graphene nanosheets and nanodots have been selectively fabricated by mechanical grinding exfoliation of natural graphite in a small quantity of ionic liquids. The resulting graphene sheets and dots are solvent free with low levels of naturally absorbed oxygen, inherited from the starting graphite. The sheets are only two to five layers thick. The graphene nanodots have diameters in the range of 9-29 nm and heights in the range of 1-16 nm, which can be controlled by changing the processing time.Comment: * Corresponding authors: [email protected]; [email protected]

Impedimetric detection of miRNA biomarkers using paper-based electrodes modified with bulk crystals or nanosheets of molybdenum disulfide

Paper-based electrodes modified with molybdenum disulfide (MoS2) in the form of bulk crystals or exfoliated nanosheets were developed and used as a biosensing platform for the impedimetric detection of miRNAs (miRNA-155 and miRNA-21) related to early diagnosis of lung cancer. For this purpose, MoS2 crystals or nanosheets were used for the modification of the working electrode area of paper-based platform for the first time in this study. The proposed assay offers sensitive and selective detection of microRNAs by electrochemical impedance spectroscopy (EIS) technique. The entire assay, both the electrode modification and the miRNA detection being completed in 30 min and a single sample droplet (5 mu L) was enough to cover working electrode area which enabled analysis in low sample volumes. The limits of detection (LOD) for miRNA-21 and miRNA-155 were calculated both in buffer and fetal bovine serum media. It is found that the LOD is varying between 1 and 200 ng/mL. In comparison to nanosheets, a larger electroactive surface area was obtained with bulk MoS2 resulting in lower LOD values on miRNA detection. The paper-based electrodes showed high specificity towards their target sequences. Moreover, they effectively discriminated single base mismatched non-target sequences. The advantages of these MoS2 paper based electrodes include high sensitivity, and low-cost provide great potential for improved monitoring of miRNA biomarkers even in artificial serum media.Newton-Katip Celebi funding program; Turkish Scientific and Technological Research Council TUBITAK [215Z702]; British Council [216182787]; Turkish Academy of Sciences (TUBITAK); Invest Northern Ireland under a Biodevices grant [RD0714186]; TUBITAK [215Z702]This project was supported by the Newton-Katip Celebi funding program, and authors acknowledge financial support from the Turkish Scientific and Technological Research Council TUBITAK Project no. 215Z702) and the British Council (Newton Fund, Institutional Links, Ref: 216182787). A.E. would also like to express her gratitude to the Turkish Academy of Sciences (TUBA) as a principal member for its partial support. E.Y. and E.E., master's students and PhD, respectively, acknowledge a project scholarship (TUBITAK Project no. 215Z702). Authors also acknowledge to helpful discussion of Assoc. Prof. Yildiz Uludag as the project consultant during project (TUBITAK; Project no. 215Z702). P.P. acknowledges support from Invest Northern Ireland under a Biodevices grant, Ref. RD0714186

Paper-Based Electrochemical Biosensors for Voltammetric Detection of miRNA Biomarkers Using Reduced Graphene Oxide or MoS 2 Nanosheets Decorated with Gold Nanoparticle Electrodes

Paper-based biosensors are considered simple and cost-efficient sensing platforms for analytical tests and diagnostics. Here, a paper-based electrochemical biosensor was developed for the rapid and sensitive detection of microRNAs (miRNA-155 and miRNA-21) related to early diagnosis of lung cancer. Hydrophobic barriers to creating electrode areas were manufactured by wax printing, whereas a three-electrode system was fabricated by a simple stencil approach. A carbon-based working electrode was modified using either reduced graphene oxide or molybdenum disulfide nanosheets modified with gold nanoparticle (AuNPs/RGO, AuNPs/MoS2) hybrid structures. The resulting paper-based biosensors offered sensitive detection of miRNA-155 and miRNA-21 by differential pulse voltammetry (DPV) in only 5.0 µL sample. The duration in our assay from the point of electrode modification to the final detection of miRNA was completed within only 35 min. The detection limits for miRNA-21 and miRNA-155 were found to be 12.0 and 25.7 nM for AuNPs/RGO and 51.6 and 59.6 nM for AuNPs/MoS2 sensors in the case of perfectly matched probe-target hybrids. These biosensors were found to be selective enough to distinguish the target miRNA in the presence of single-base mismatch miRNA or noncomplementary miRNA sequences

Supercritical fluid growth of porous carbon nanocages

Carbon nanocages, with remarkably large mesoporous volumes, have been synthesized by the deposition of p-xylene over a Co/Mo catalyst in supercritical carbon dioxide. Nanocages with diameters ranging between 10 and 60 nm were synthesized at temperatures between 650 and 750 °C. The surface area and pore volume of the nanocages produced was found to depend on the reaction temperature and pressure employed. In particular, carbon nanocages with a pore volume of up to 5.8 cm3 g-1 and a BET surface area of 1240 m2 g-1 were readily synthesized at a temperature of 650 °C and a pressure of 10.34 MPa. The high pore volume and surface area of the carbon nanocages synthesized makes them ideal materials for use as inert adsorbents and catalytic supports

Fire Retardant Action of Layered Double Hydroxides and Zirconium Phosphate Nanocomposites Fillers in Polyisocyanurate Foams

Modern day energy codes are driving the design and multi-layered configuration of exterior wall systems with a significant emphasis on achieving high performance insulation towards improving energy performance of building envelopes. Use of highly insulating polyisocyanurate (PIR) based materials enhanced with eco-friendly lamellar inorganic fillers reinforces energy performance requirements, environmental challenges and cost reduction without compromising the overall building fire safety. The current work assessed the fire behaviour of PIR modified with three layered fillers, namely MgAlCO3 (PIR-LDH1), MgAl Stearate (PIR-LDH2) and Zirconium Phosphate octadecylamine (PIR-ZrP3). For each of the fillers, three loadings (2, 4 and 6% by weight) were used. Optical analysis by X-ray diffraction patterns (XRD), cone calorimeter (CC), thermogravimetric (TGA) analysis, post-burning morphological evaluation using field emission scanning electron microscope (FESEM) and diffuse reflectance infrared spectroscopy (DRIFT) analysis, were performed. The results indicated that fire reaction properties and thermal stability of foam samples were enhanced with all three different lamellar inorganic smart fillers. The initial degradation temperature of PIR-layered filler samples was increased, demonstrating that incorporation of flame retardants decelerated the degradation of the PIR foam and contributed to significant char formation, from 19.5% in pure PIR samples to 33% in PIR-6%LDH1 samples. Increasing the filler content also resulted in improved char properties and decreased peak Heat Release Rates (HRR) in the cone calorimeter. Due to the development of a stable char layer, samples containing 6% of ZrP3 did not ignite at 20 kW/m2 and a reduction of up to 40% in the peak HRR was achieved in PIR-2%ZrP3 samples

The Effects of Exfoliation, Organic Solvents and Anodic Activation on Catalytic Hydrogen Evolution Reaction of Tungsten Disulfide

International audienceThe rational design of transition metal dichalcogenide electrocatalysts for efficiently catalyzing hydrogen evolution reaction (HER) is believed to lead to the generation of a renewable energy carrier. To this end our work has made three main contributions. At first, we have demonstrated that exfoliation via ionic liquid assisted grinding combined with gradient centrifugation is an efficient method to exfoliate bulk WS2 to nanosheets with a thickness of a few atomic layers and lateral size dimensions in the range of 100 nm to 2 nm. These WS2 nanosheets decorated with scattered nanodots exhibited highly enhanced catalytic performance for HER with an onset potential of-130 mV vs. RHE, an overpotential of 337 mV at 10 mA cm-2 and a Tafel slope of 80 mV dec-1 in 0.5 M H2SO4. Secondly, we found a strong aging effect on the electrocatalytic performance of WS2 stored in high boiling point organic solvents such as dimethylformamide (DMF). Importantly, the HER ability could be recovered by removing the organic (DMF) residues, which obstructed the electron transport, with acetone. Thirdly, we established that the HER performance of WS2 nanosheets/nanodots could be significantly enhanced, by activating the electrode surface at a positive voltage for a very short time (60 s), decreasing the kinetic overpotential by more than 80 mV at 10 mA cm-2. The performance enhancement was found to arise primarily from the ability of a formed proton-intercalated amorphous tungsten trioxide (a-WO3) to provide additional active sites and favourably modify the immediate chemical environment of the WS2 catalyst, rendering it more favorable for local proton delivery and/or transport to the active edge site of WS2. Our results provide new insights into the effects of organic solvents and electrochemical activation on the catalytic performance of two-dimensional WS2 for HER

Platinum Integrated Graphene for Methanol Fuel Cells

Uniform and porous graphene nanoflake films (GNFs) have been investigated as a support for catalytic Pt nanoclusters in direct methanol electro-oxidation. Pt nanoclusters of varying thickness are deposited on GNFs using magnetron sputtering, and their effects on the electrocatalytic activity for oxidizing methanol are systemically studied. GNF supported Pt nanoclusters with ultralow catalyst loading exhibit high performance for methanol electrocatalytic oxidation with a large mass-specific peak current density and a ratio of forward to backward peak currents up to 1.4. These characteristics compare favorably to the majority of Pt−C based electrodes, except for those of carbon nanotubes with Pt decoration on both the inner and the outer wall surfaces. The results obtained are ascribed to a highly coupled network made of high-density 2−4 nm Pt monolayer nanoclusters on both the basal and edge planes of each nanoflakes of graphene. GNFs are a promising support material for developing next-generation advanced Pt based fuel cells and their relevant electrodes in the field of energy