Boost of Charge Storage Performance of Graphene Nanowall Electrodes by Laser-Induced Crystallization of Metal Oxide Nanostructures.

Major research efforts are being carried out for the technological advancement to an energetically sustainable society. However, for the full commercial integration of electrochemical energy storage devices, not only materials with higher performance should be designed and manufactured but also more competitive production techniques need to be developed. The laser processing technology is well extended at the industrial sector for the versatile and high throughput modification of a wide range of materials. In this work, a method based on laser processing is presented for the fabrication of hybrid electrodes composed of graphene nanowalls (GNWs) coated with different transition-metal oxide nanostructures for electrochemical capacitor (EC) applications. GNW/stainless steel electrodes grown by plasma enhanced chemical vapor deposition were decorated with metal oxide nanostructures by means of their laser surface processing while immersed in aqueous organometallic solutions. The pseudocapacitive nature of the laser-induced crystallized oxide materials prompted an increase of the GNW electrodes' capacitance by 3 orders of magnitude, up to ca. 28 F/cm3 at 10 mV/s, at both the positive and negative voltages. Finally, asymmetric aqueous and solid-state ECs revealed excellent stability upon tens of thousands of charge-discharge cycles.

Enhancement of the supercapacitive properties of laser deposited graphene-based electrodes through carbon nanotube loading and nitrogen doping.

Several technological routes are being investigated for improving the energy storage capability and power delivery of electrochemical capacitors. In this work, ternary hybrid electrodes composed of conducting graphene/reduced graphene oxide (rGO), which store charge mainly through electric double-layer mechanisms, covered by NiO nanostructures, for adding pseudocapacitance, were fabricated through a matrix assisted pulsed laser evaporation technique. The incorporation of multiwall carbon nanotubes (MWCNTs) provokes an increase of the porosity and thus, a substantial enhancement of the electrodes' capacitance (from 4 to 20 F cm-3 at 10 mV s-1). Volumetric capacitances of 34 F cm-3 were also obtained with electrodes containing just carbon nanotubes coated with NiO nanostructures. Moreover, the use of nitrogen containing precursors (ammonia, urea) for laser-induced N-doping of the nanocarbons also provokes a notable increase of the capacitance. Remarkably, N-containing groups in rGO-MWCNTs mainly add electric double layer charge storage, pointing to an increase of electrode porosity, whereas redox reactions contribute with a minor diffusion fraction. It was also observed that the loading of carbon nanotubes leads to an increase of diffusion-controlled charge storage mechanisms versus capacitive ones in rGO-based electrodes, the opposite effect being observed in graphene electrodes.

Super-Capacitive Performance of Manganese Dioxide/Graphene Nano-Walls Electrodes Deposited on Stainless Steel Current Collectors.

Graphene nano-walls (GNWs) are promising materials that can be used as an electrode in electrochemical devices. We have grown GNWs by inductively-coupled plasma-enhanced chemical vapor deposition on stainless steel (AISI304) substrate. In order to enhance the super-capacitive properties of the electrodes, we have deposited a thin layer of MnO2 by electrodeposition method. We studied the effect of annealing temperature on the electrochemical properties of the samples between 70 °C and 600 °C. Best performance for supercapacitor applications was obtained after annealing at 70 °C with a specific capacitance of 104 F g-1 at 150 mV s-1 and a cycling stability of more than 14k cycles with excellent coulombic efficiency and 73% capacitance retention. Electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge measurements reveal fast proton diffusion (1.3 × 10-13 cm²·s-1) and surface redox reaction after annealing at 70 °C.

Selective Laser-Assisted Synthesis of Tubular van der Waals Heterostructures of Single-Layered PbI2 within Carbon Nanotubes Exhibiting Carrier Photogeneration.

The electronic and optical properties of two-dimensional layered materials allow the miniaturization of nanoelectronic and optoelectronic devices in a competitive manner. Even larger opportunities arise when two or more layers of different materials are combined. Here, we report on an ultrafast energy efficient strategy, using laser irradiation, which allows bulk synthesis of crystalline single-layered lead iodide in the cavities of carbon nanotubes by forming cylindrical van der Waals heterostructures. In contrast to the filling of van der Waals solids into carbon nanotubes by conventional thermal annealing, which favors the formation of inorganic nanowires, the present strategy is highly selective toward the growth of monolayers forming lead iodide nanotubes. The irradiated bulk material bearing the nanotubes reveals a decrease of the resistivity as well as a significant increase in the current flow upon illumination. Both effects are attributed to the presence of single-walled lead iodide nanotubes in the cavities of carbon nanotubes, which dominate the properties of the whole matrix. The present study brings in a simple, ultrafast and energy efficient strategy for the tailored synthesis of rolled-up single-layers of lead iodide (i.e., single-walled PbI2 nanotubes), which we believe could be expanded to other two-dimensional (2D) van der Waals solids. In fact, initial tests with ZnI2 already reveal the formation of single-walled ZnI2 nanotubes, thus proving the versatility of the approach.

Nanosecond Laser-Assisted Nitrogen Doping of Graphene Oxide Dispersions.

N-doped reduced graphene oxide (RGO) has been prepared in bulk form by laser irradiation of graphene oxide (GO) dispersed in an aqueous solution of ammonia. A pulsed Nd:YAG laser with emission wavelengths in the infrared (IR) 1064 nm, visible (Vis) 532 nm, and ultraviolet (UV) 266 nm spectral regions was employed for the preparation of the N-doped RGO samples. Regardless of the laser energy employed, the resulting material presents a higher fraction of pyrrolic nitrogen compared to nitrogen atoms in pyridinic and graphitic coordination. Noticeably, whereas increasing the laser fluence of UV and Vis wavelengths results in an increase in the total amount of nitrogen, up to 4.9 at. % (UV wavelength at 60 mJ cm-2 fluence), the opposite trend is observed when the GO is irradiated in ammonia solution through IR processing. The proposed laser-based methodology allows the bulk synthesis of N-doped reduced graphene oxide in a simple, fast, and cost efficient manner.

Biomedical properties and preparation of iron oxide-dextran nanostructures by MAPLE technique.

BACKGROUND: In this work the chemical structure of dextran-iron oxide thin films was reported. The films were obtained by MAPLE technique from composite targets containing 10 wt. % dextran with 1 and 5 wt.% iron oxide nanoparticles (IONPs). The IONPs were synthesized by co-precipitation method. A KrF* excimer laser source (λ = 248 nm, τFWHM≅25 ns, ν = 10 Hz) was used for the growth of the hybrid, iron oxide NPs-dextran thin films. RESULTS: Dextran coated iron oxide nanoparticles thin films were indexed into the spinel cubic lattice with a lattice parameter of 8.36 Å. The particle sized calculated was estimated at around 7.7 nm. The XPS shows that the binding energy of the Fe 2p3/2 of two thin films of dextran coated iron oxide is consistent with Fe3+ oxides. The atomic percentage of the C, O and Fe are 66.71, 32.76 and 0.53 for the films deposited from composite targets containing 1 wt.% maghemite and 64.36, 33.92 and 1.72 respectively for the films deposited from composite targets containing 5 wt.% maghemite. In the case of cells cultivated on dextran coated 5% maghemite γ-Fe2O3, the number of cells and the level of F-actin were lower compared to the other two types of thin films and control. CONCLUSIONS: The dextran-iron oxide continuous thin films obtained by MAPLE technique from composite targets containing 10 wt.% dextran as well as 1 and 5 wt.% iron oxide nanoparticles synthesized by co-precipitation method presented granular surface morphology. Our data proved a good viability of Hep G2 cells grown on dextran coated maghemite thin films. Also, no changes in cells morphology were noticed under phase contrast microscopy. The data strongly suggest the potential use of iron oxide-dextran nanocomposites as a potential marker for biomedical applications.

Biomolecular papain thin films growth by laser techniques.

Papain thin films were synthesised by matrix assisted and conventional pulsed laser deposition (PLD) techniques. The targets submitted to laser radiation consisted on a frozen composite obtained by dissolving the biomaterials in distilled water. For the deposition of the thin films by conventional PLD pressed biomaterial powder targets were submitted to laser irradiation. An UV KrF* excimer laser source was used in the experiments at 0.5 J/cm(2) incident fluence value, diminished one order of magnitude as compared to irradiation of inorganic materials. The surface morphology of the obtained thin films was studied by atomic force profilometry and atomic force microscopy. The investigations showed that the growth mode and surface quality of the deposited biomaterial thin films is strongly influenced by the target preparation procedure.