The Synthesis of Sponge-like V2O5/CNT Hybrid Nanostructures Using Vertically Aligned CNTs as Templates.

The fabrication of sponge-like vanadium pentoxide (V2O5) nanostructures using vertically aligned carbon nanotubes (VACNTs) as a template is presented. The VACNTs were grown on silicon substrates by chemical vapor deposition using the Fe/Al bilayer catalyst approach. The V2O5 nanostructures were obtained from the thermal oxidation of metallic vanadium deposited on the VACNTs. Different oxidation temperatures and vanadium thicknesses were used to study the influence of these parameters on the stability of the carbon template and the formation of the V2O5 nanostructures. The morphology of the samples was analyzed by scanning electron microscopy, and the structural characterization was performed by Raman, energy-dispersive X-ray, and X-ray photoelectron spectroscopies. Due to the catalytic properties of V2O5 in the decomposition of carbonaceous materials, it was possible to obtain supported sponge-like structures based on V2O5/CNT composites, in which the CNTs exhibit an increase in their graphitization. The VACNTs can be removed or preserved by modulating the thermal oxidation process and the vanadium thickness.

Electron Spin-Dependent Electrocatalysis for the Oxygen Reduction Reaction in a Chiro-Self-Assembled Iron Phthalocyanine Device.

The chiral-induced spin selectivity effect (CISS) is a breakthrough phenomenon that has revolutionized the field of electrocatalysis. We report the first study on the electron spin-dependent electrocatalysis for the oxygen reduction reaction, ORR, using iron phthalocyanine, FePc, a well-known molecular catalyst for this reaction. The FePc complex belongs to the non-precious catalysts group, whose active site, FeN4, emulates catalytic centers of biocatalysts such as Cytochrome c. This study presents an experimental platform involving FePc self-assembled to a gold electrode surface using chiral peptides (L and D enantiomers), i.e., chiro-self-assembled FePc systems (CSAFePc). The chiral peptides behave as spin filters axial ligands of the FePc. One of the main findings is that the peptides' handedness and length in CSAFePc can optimize the kinetics and thermodynamic factors governing ORR. Moreover, the D-enantiomer promotes the highest electrocatalytic activity of FePc for ORR, shifting the onset potential up to 1.01 V vs. RHE in an alkaline medium, a potential close to the reversible potential of the O2 /H2 O couple. Therefore, this work has exciting implications for developing highly efficient and bioinspired catalysts, considering that, in biological organisms, biocatalysts that promote O2 reduction to water comprise L-enantiomers.

Lithium Iron Phosphate/Carbon (LFP/C) Composite Using Nanocellulose as a Reducing Agent and Carbon Source.

Lithium iron phosphate (LiFePO4, LFP) is the most promising cathode material for use in safe electric vehicles (EVs), due to its long cycle stability, low cost, and low toxicity, but it suffers from low conductivity and ion diffusion. In this work, we present a simple method to obtain LFP/carbon (LFP/C) composites with different types of NC: cellulose nanocrystal (CNC) and cellulose nanofiber (CNF). Microwave-assisted hydrothermal synthesis was used to obtain LFP with nanocellulose inside the vessel, and the final LFP/C composite was achieved by heating the mixture under a N2 atmosphere. The resulting LFP/C indicated that the NC in the reaction medium not only acts as the reducing agent that aqueous iron solutions need (avoiding the use of other chemicals), but also as a stabiliser of the nanoparticles produced in the hydrothermal synthesis, obtaining fewer agglomerated particles compared to synthesis without NC. The sample with the best coating-and, therefore, the best electrochemical response-was the sample with 12.6% carbon derived from CNF in the composite instead of CNC, due to its homogeneous coating. The utilisation of CNF in the reaction medium could be a promising method to obtain LFP/C in a simple, rapid, and low-cost way, avoiding the waste of unnecessary chemicals.

Synergistic effect of electrotrophic perchlorate reducing microorganisms and chemically modified electrodes for enhancing bioelectrochemical perchlorate removal.

Perchlorate has been described as an emerging pollutant that compromises water sources and human health. In this study, a new electrotrophic perchlorate reducing microorganism (EPRM) isolated from the Atacama Desert, Dechloromonas sp. CS-1, was evaluated for perchlorate removal in water in a bioelectrochemical reactor (BER) with a chemically modified electrode. BERs were operated for 17 days under batch mode conditions with an applied potential of -500 mV vs. Ag/AgCl. Surface analysis (i.e., SEM, XPS, FT-IR, RAMAN spectroscopy) on the modified electrode demonstrated heterogeneous transformation of the carbon fibers with the incorporation of nitrogen functional groups and the oxidation of the carbonaceous material. The BERs with the modified electrode and the presence of the EAM reached high cathodic efficiency (90.79 ± 9.157%) and removal rate (0.34 ± 0.007 mol m-3-day) compared with both control conditions. The observed catalytic enhancement of CS-1 was confirmed by a reduction in the charge transfer resistance obtained by electrochemical impedance spectroscopy (EIS). Finally, an electrochemical kinetic study revealed an eight-electron perchlorate bioreduction reaction at -638.33 ± 24.132 mV vs. Ag/AgCl. Therefore, our results show the synergistic effect of EPRM and chemically modified electrodes on perchlorate removal in a BER.

CVD Growth of Hematite Thin Films for Photoelectrochemical Water Splitting: Effect of Precursor-Substrate Distance on Their Final Properties.

The development of photoelectrode materials for efficient water splitting using solar energy is a crucial research topic for green hydrogen production. These materials need to be abundant, fabricated on a large scale, and at low cost. In this context, hematite is a promising material that has been widely studied. However, it is a huge challenge to achieve high-efficiency performance as a photoelectrode in water splitting. This paper reports a study of chemical vapor deposition (CVD) growth of hematite nanocrystalline thin films on fluorine-doped tin oxide as a photoanode for photoelectrochemical water splitting, with a particular focus on the effect of the precursor-substrate distance in the CVD system. A full morphological, structural, and optical characterization of hematite nanocrystalline thin films was performed, revealing that no change occurred in the structure of the films as a function of the previously mentioned distance. However, it was found that the thickness of the hematite film, which is a critical parameter in the photoelectrochemical performance, linearly depends on the precursor-substrate distance; however, the electrochemical response exhibits a nonmonotonic behavior. A maximum photocurrent value close to 2.5 mA/cm2 was obtained for a film with a thickness of around 220 nm under solar irradiation.

Tunable Low Crystallinity Carbon Nanotubes/Silicon Schottky Junction Arrays and Their Potential Application for Gas Sensing.

Highly ordered nanostructure arrays have attracted wide attention due to their wide range of applicability, particularly in fabricating devices containing scalable and controllable junctions. In this work, highly ordered carbon nanotube (CNT) arrays grown directly on Si substrates were fabricated, and their electronic transport properties as a function of wall thickness were explored. The CNTs were synthesized by chemical vapor deposition inside porous alumina membranes, previously fabricated on n-type Si substrates. The morphology of the CNTs, controlled by the synthesis parameters, was characterized by electron microscopies and Raman spectroscopy, revealing that CNTs exhibit low crystallinity (LC). A study of conductance as a function of temperature indicated that the dominant electric transport mechanism is the 3D variable range hopping. The electrical transport explored by I-V curves was approached by an equivalent circuit based on a Schottky diode and resistances related to the morphology of the nanotubes. These junction arrays can be applied in several fields, particularly in this work we explored their performance in gas sensing mode and found a fast and reliable resistive response at room temperature in devices containing LC-CNTs with wall thickness between 0.4 nm and 1.1 nm.

Comparison of Different Synthetic Routes of Hybrid Hematite-TiO2 Nanotubes-Based Electrodes.

Nowadays, green hydrogen is an important niche of interest in which the search for a suitable composite material is indispensable. In this sense, titanium oxide nanotubes (TiO2 nanotube, TNTs) were prepared from double anodic oxidation of Ti foil in ethylene glycol electrolyte. The morphology of the nanotubes was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Once characterized, nanotubes were used as templates for the deposition of hematite. The use of three synthetic procedures was assayed: Chemical Vapor Deposition (CVD), Successive Ionic Layer Adsorption and Reaction (SILAR), and electrochemical synthesis. In the first case, CVD, the deposition of hematite onto TiO2 yielded an uncovered substrate with the oxide and a negative shift of the flat band potential. On the other hand, the SILAR method yielded a considerable amount of hematite on the surface of nanotubes, leading to an obstruction of the tubes in most cases. Finally, with the electrochemical synthesis, the composite material obtained showed great control of the deposition, including the inner surface of the TNT. In addition, the impedance characterization showed a negative shift, indicating the changes of the interface electrode-electrolyte due to the modification with hematite. Finally, the screening of the methods showed the electrochemical synthesis as the best protocol for the desired material.

Nickel Nanopillar Arrays Electrodeposited on Silicon Substrates Using Porous Alumina Templates.

Nickel nanopillar arrays were electrodeposited onto silicon substrates using porous alumina membranes as a template. The characterization of the samples was done by scanning electron microscopy, X-ray diffraction, and alternating force gradient magnetometry. Ni nanostructures were directly grown on Si by galvanostatic and potentiostatic electrodeposition techniques in three remarkable charge transfer configurations. Differences in the growth mechanisms of the nanopillars were observed, depending on the deposition method. A high correlation between the height of the nanopillars and the charge synthesis was observed irrespective of the electrochemical technique. The magnetization measurements demonstrated a main dependence with the height of the nanopillars. The synthesis of Ni nanosystems with a controllable aspect ratio provides an effective way to produce well-ordered networks for wide scientific applications.

Gold nanoparticles grown inside carbon nanotubes: synthesis and electrical transport measurements.

The hybrid structures composed of gold nanoparticles and carbon nanotubes were prepared using porous alumina membranes as templates. Carbon nanotubes were synthesized inside the pores of these templates by the non-catalytic decomposition of acetylene. The inner cavity of the supported tubes was used as nanoreactors to grow gold particles by impregnation with a gold salt, followed by a calcination-reduction process. The samples were characterized by transmission electron microscopy and X-ray energy dispersion spectroscopy techniques. The resulting hybrid products are mainly encapsulated gold nanoparticles with different shapes and dimensions depending on the concentration of the gold precursor and the impregnation procedure. In order to understand the electronic transport mechanisms in these nanostructures, their conductance was measured as a function of temperature. The samples exhibit a 'non-metallic' temperature dependence where the dominant electron transport mechanism is 1D hopping. Depending on the impregnation procedure, the inclusion of gold nanoparticles inside the CNTs can introduce significant changes in the structure of the tubes and the mechanisms for electronic transport. The electrical resistance of these hybrid structures was monitored under different gas atmospheres at ambient pressure. Using this hybrid nanostructures, small amounts of acetylene and hydrogen were detected with an increased sensibility compared with pristine carbon nanotubes. Although the sensitivity of these hybrid nanostructures is rather low compared to alternative sensing elements, their response is remarkably fast under changing gas atmospheres.

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes.

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors.

Growth of carbon nanostructures using a Pd-based catalyst.

Carbon nanostructures were synthesized by decomposition of different carbon sources over an alumina supported palladium catalyst via Chemical Vapor Deposition (CVD). Several experimental conditions were varied to verify their influence in the synthesis products: temperature ramping rate, pre-annealing conditions, hydrogen pre-treatment, synthesis temperature and time, together with the use of different carbon sources. Depending on the experimental conditions carbon nanotubes and nanofibers with different shapes and structural characteristics were obtained. Straight, coiled and branched morphologies are the most common. Among our findings, the addition of hydrogen plays a significant role in the structure of the carbonaceous products. For example, the decomposition of acetylene on palladium catalysts at 800 degrees C in the absence of hydrogen produces only carbon micro- spheres as synthesis products. The incorporation of increasing amounts of hydrogen modifies the outcome, from thick fibers to carbon nanotubes. To verify the level of graphitization of the synthesis products we have used high resolution transmission electron microscopy (HRTEM) in addition to Raman spectroscopy. Our results, based on these complementary techniques, indicate the decomposition of acetylene on a palladium based catalyst, produces the best degree of graphitization in carbon nanotubes for a temperature of 800 degrees C and 100 cc/min of hydrogen flow. Similar hydrogen flows on the same catalyst, produced highly graphitized nanofibers by the decomposition of methane at 850 degrees C.

Growth morphology and spectroscopy of multiwall carbon nanotubes synthesized by pyrolysis of iron phthalocyanine.

Carbon nanotubes (CNTs) were synthesized by Chemical Vapor Deposition (CVD) from the pyrolytic decomposition of Iron Phthalocyanine (FePc) molecules, on SiO2/Si(111) substrates in the presence of a hydrogen flow. FePc molecules contribute simultaneously both to the formation of the precursor Fe nanoparticles and also as a Carbon source. Different experimental conditions were examined. Samples were characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and inverse photoemission. The resulting samples are highly oriented multiwall carbon nanotubes films, with heights in the range between: 4 and 20 microm. The tubes diameter is strongly dependent on growth temperature. Our experimental results show evidence of a transition in the growth mechanism, from a tip growth to a base growth mode, as the decomposition temperature is increased. Preliminary spectroscopic measurements performed on these MWCNTs, show the unoccupied density of states has several resonances close to Fermi level, related both to the graphene electronic structure and the formation of the tube.