Michel Trudeau

Current density dependence of peroxide formation in the Li-O2 battery and its effect on charge†

We report a significant difference in the growth mechanism of Li2O2 in Li–O2 batteries for toroidal and thin-film morphologies which is dependent on the current rate that governs the electrochemical pathway. Evidence from diffraction, electrochemical, FESEM and STEM measurements shows that slower current densities favor aggregation of lithium peroxide nanocrystallites nucleated via solution dismutase on the surface of the electrode; whereas fast rates deposit quasi-amorphous thin films. The latter provide a lower overpotential on charge due to their nature and close contact with the conductive electrode surface, albeit at the expense of lower discharge capacity.

Visible light-driven efficient overall water splitting using p -type metal-nitride nanowire arrays

Solar water splitting for hydrogen generation can be a potential source of renewable energy for the future. Here we show that efficient and stable stoichiometric dissociation of water into hydrogen and oxygen can be achieved under visible light by eradicating the potential barrier on nonpolar surfaces of indium gallium nitride nanowires through controlled p-type dopant incorporation. An apparent quantum efficiency of ∼12.3% is achieved for overall neutral (pH∼7.0) water splitting under visible light illumination (400-475 nm). Moreover, using a double-band p-type gallium nitride/indium gallium nitride nanowire heterostructure, we show a solar-to-hydrogen conversion efficiency of ∼1.8% under concentrated sunlight. The dominant effect of near-surface band structure in transforming the photocatalytic performance is elucidated. The stability and efficiency of this recyclable, wafer-level nanoscale metal-nitride photocatalyst in neutral water demonstrates their potential use for large-scale solar-fuel conversion.

Tuning the surface Fermi level on p-type gallium nitride nanowires for efficient overall water splitting

Solar water splitting is one of the key steps in artificial photosynthesis for future carbon-neutral, storable and sustainable source of energy. Here we show that one of the major obstacles for achieving efficient and stable overall water splitting over the emerging nanostructured photocatalyst is directly related to the uncontrolled surface charge properties. By tuning the Fermi level on the nonpolar surfaces of gallium nitride nanowire arrays, we demonstrate that the quantum efficiency can be enhanced by more than two orders of magnitude. The internal quantum efficiency and activity on p-type gallium nitride nanowires can reach ~51% and ~4.0 mol hydrogen h(-1) g(-1), respectively. The nanowires remain virtually unchanged after over 50,000 μmol gas (hydrogen and oxygen) is produced, which is more than 10,000 times the amount of photocatalyst itself (~4.6 μmol). The essential role of Fermi-level tuning in balancing redox reactions and in enhancing the efficiency and stability is also elucidated.

Low Hydrogen Overpotential Nanocrystalline Ni‐Mo Cathodes for Alkaline Water Electrolysis

Nanocrystalline fcc Ni x Mo 1−x (x=0.60, 0.85 atom percent) metallic powders prepared by high energy mechanical alloying were found to possess electrocatalytic activities for the hydrogen evolution reaction in 30 weight percent KOH at 70°C equivalent to that of the best electrocatalysts. The formation process and the structural properties of these nanocrystalline alloys were investigated. The active phase is a metastable solid solution of Mo in fcc Ni whose electrocatalytic activity is associated with the reduction in the size of the crystallites and correlates with the expansion of the Ni lattice

One-step overall water splitting under visible light using multiband InGaN/GaN nanowire heterostructures.

The conversion of solar energy into hydrogen via water splitting process is one of the key sustainable technologies for future clean, storable, and renewable source of energy. Therefore, development of visible light-responsive and efficient photocatalyst material has been of immense interest, but with limited success. Here, we show that overall water splitting under visible-light irradiation can be achieved using a single photocatalyst material. Multiband InGaN/GaN nanowire heterostructures, decorated with rhodium (Rh)/chromium-oxide (Cr2O3) core-shell nanoparticles can lead to stable hydrogen production from pure (pH ∼ 7.0) water splitting under ultraviolet, blue and green-light irradiation (up to ∼560 nm), the longest wavelength ever reported. At ∼440-450 nm wavelengths, the internal quantum efficiency is estimated to be ∼13%, the highest value reported in the visible spectrum. The turnover number under visible light well exceeds 73 in 12 h. Detailed analysis further confirms the stable photocatalytic activity of the nanowire heterostructures. This work establishes the use of metal-nitrides as viable photocatalyst for solar-powered artificial photosynthesis for the production of hydrogen and other solar fuels.

H2 Storage Materials (22KJ/mol) Using Organometallic Ti Fragments as σ-H2 Binding Sites

Low-coordinate Ti (III) fragments with controlled geometries designed specifically for sigma-H2 binding were grafted onto mesoporous silica using tri- and tetrabenzyl Ti precursors. The hydrogen storage capacity was tested as a function of precursor and precursor loading level. At an optimal loading level of 0.2 mol equiv tetrabenzyl Ti the total storage capacity at -196 degrees C was 21.45 wt % and 34.10 kg/m(3) at 100 atm, and 3.15 wt % and 54.49 kg/m(3) for a compressed pellet under the same conditions. The adsorption value of this material was 1.66 wt %, which equates to an average of 2.7 H2 per Ti center. The adsorption isotherms did not reach saturation at 60 atm, suggesting that the theoretical maximum of 5 H2 per Ti in this system may be reached at higher pressures. The binding enthalpies rose with surface coverage to a maximum of 22.15 kJ/mol, which is more than double that of the highest recorded previously and within the range predicted for room temperature performance. The adsorption values of 0.99 at -78 degrees C and 0.69 at 25 degrees C demonstrate retention of 2.4 H2 and 1.1 H2 per Ti at these temperatures, respectively. These findings suggest that Kubas binding of H2 may be exploited at ambient temperature to enhance the storage capacities of high-pressure cylinders currently used in hydrogen test vehicles.

Structural and magnetic characterization of granular Y 1 Ba 2 Cu 3 O 7−δ nanocrystalline powders

High energy ball milling has been used to produce nanocrystalline Y 1 Ba 2 Cu 3 O 7 -δ powders. These powders are being used as starting materials for manufacturing superconducting textured wires by a solid state recrystallization process. Magnetic and microstructural characterizations were performed as a function of milling time. The milling reduces the average crystal size and creates low and high-angle grain boundaries which increase the granularity of the superconductor. As a result, the long-range order on the oxygen sublattice and on the yttrium and barium sites is destroyed. A transition from orthorhombic to tetragonal and finally to a cubic metastable phase is observed. Total loss of superconductivity occurs after about 1 h of milling. Prior to this time, superconductivity can partially be restored by room-temperature aging. High-temperature heat treatment of the nanocrystalline phase produces a tetragonal structure with c = 3 a .

Amorphous and nanocrystalline Fe-Ti prepared by ball milling

Nanocrystalline FeTi has been prepared in two ways: by ball milling the intermetallic compound and mechanically alloying a mixture of the elemental powders. The materials obtained in each case are identical. The reaction proceeds via the formation of interfacial β–Ti(Fe) which then grows to include all of the material present. Oxygen levels above 3 at. % suppress this reaction and lead to the formation of amorphous Fe–Ti.

Nanostructured polymer microcomposites: A distinct class of insulating materials

Experimental evidence was produced and gathered to demonstrate the distinct nature of nanostructured polymer microcomposites. The case of a polymer composite consisting of a high-content of micrometric quartz with a small adjunct of nanoclay is discussed. Emphasis is put on dielectric behavior studies while some results on thermal characteristics are presented. Overall results strongly support the potential of this class of insulating material for electrotechnical applications.

Nanocrystalline materials in catalysis and electrocatalysis : Structure tailoring and surface reactivity

Abstract The last few years have seen a growing interest in the study of materials based on crystals having an average size on the nanometer range. In many aspects these materials (and their understanding) could be at the basis of a revolutionary development in the field of catalysis and electrocatalysis. One reason for these improved or new properties relates to the large number of atoms placed at the surface of crystals which imply an increased number of active sites. Also, the large number of grain boundaries result in an enhanced reaction kinetics. Finally, what is fundamental is that these new nanostructured materials offer the possibilities to design crystalline surface nearly on an atomic scale. It is then possible to tailor a specific microstructure for catalytic materials to achieve improvements on a given catalytic process. Examples of new nanocrystalline catalytic and electrocatalytic materials are presented in this paper to demonstrate their impressive potential.