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1.
ACS Appl Mater Interfaces ; 9(34): 28695-28703, 2017 Aug 30.
Article in English | MEDLINE | ID: mdl-28795573

ABSTRACT

The electrochemical performance of anodes made of transition metal oxides (TMOs) in lithium-ion batteries (LIBs) often suffers from their chemical and mechanical instability. In this research, a novel electrode with a hierarchical current collector for TMO active materials is successfully fabricated. It consists of porous nickel as current collector on a copper substrate. The copper has vertically aligned microchannels. Anatase titanium dioxide (TiO2) nanoparticles of ∼100 nm are directly synthesized and cast on the porous Ni using a one-step process. Characterization indicates that this electrode exhibits excellent performance in terms of capacity, reliable rate, and long cyclic stability. The maximum insertion coefficient for the reaction product of LixTiO2 is ∼0.85, a desirable value as an anode of LIBs. Cross-sectional SEM and EDS analysis confirmed the uniform and stable distribution of nanosized TiO2 nanoparticles inside the Ni microchannels during cycling. This is due to the synergistic effect of nano-TiO2 and the hierarchical Cu/Ni current collector. The advantages of the Cu/Ni/TiO2 anode include enhanced activity of electrochemical reactions, shortened lithium ion diffusion pathways, ultrahigh specific surface area, effective accommodation of volume changes of TiO2 nanoparticles, and optimized routes for electrons transport.

2.
Nat Chem ; 9(8): 810-816, 2017 08.
Article in English | MEDLINE | ID: mdl-28754945

ABSTRACT

The conversion of oxygen-rich biomass into hydrocarbon fuels requires efficient hydrodeoxygenation catalysts during the upgrading process. However, traditionally prepared CoMoS2 catalysts, although efficient for hydrodesulfurization, are not appropriate due to their poor activity, sulfur loss and rapid deactivation at elevated temperature. Here, we report the synthesis of MoS2 monolayer sheets decorated with isolated Co atoms that bond covalently to sulfur vacancies on the basal planes that, when compared with conventionally prepared samples, exhibit superior activity, selectivity and stability for the hydrodeoxygenation of 4-methylphenol to toluene. This higher activity allows the reaction temperature to be reduced from the typically used 300 °C to 180 °C and thus allows the catalysis to proceed without sulfur loss and deactivation. Experimental analysis and density functional theory calculations reveal a large number of sites at the interface between the Co and Mo atoms on the MoS2 basal surface and we ascribe the higher activity to the presence of sulfur vacancies that are created local to the observed Co-S-Mo interfacial sites.

3.
Sci Rep ; 6: 20527, 2016 Feb 09.
Article in English | MEDLINE | ID: mdl-26856760

ABSTRACT

Incorporation of Zn atoms into a nanosize Cu lattice is known to alter the electronic properties of Cu, improving catalytic performance in a number of industrially important reactions. However the structural influence of Zn on the Cu phase is not well studied. Here, we show that Cu nano-clusters modified with increasing concentration of Zn, derived from ZnO support doped with Ga(3+), can dramatically enhance their stability against metal sintering. As a result, the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol, an important reaction well known for deactivation from copper nanoparticle sintering, can show greatly enhanced activity and stability with the CuZn alloy catalysts due to no noticeable sintering. HRTEM, nano-diffraction and EXAFS characterization reveal the presence of a small beta-brass CuZn alloy phase (body-centred cubic, bcc) which appears to greatly stabilise Cu atoms from aggregation in accelerated deactivation tests. DFT calculations also indicate that the small bcc CuZn phase is more stable against Cu adatom migration than the fcc CuZn phase with the ability to maintain a higher Cu dispersion on its surface.

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