Highly active and stable electrocatalysts for hydrogen evolution have been developed on the basis of molybdenum compounds (Mo2C, Mo2N, and MoS2) on carbon nanotube (CNT)-graphene hybrid support via a modified urea-glass route. By a simple modification of synthetic variables, the final phases are easily controlled from carbide, nitride to sulfide with homogeneous dispersion of nanocrystals on the CNT-graphene support. Among the prepared catalysts, Mo2C/CNT-graphene shows the highest activity for hydrogen evolution reaction with a small onset overpotential of 62 mV and Tafel slope of 58 mV/dec as well as an excellent stability in acid media. Such enhanced catalytic activity may originate from its low hydrogen binding energy and high conductivity. Moreover, the CNT-graphene hybrid support plays crucial roles to enhance the activity of molybdenum compounds by alleviating aggregation of the nanocrystals, providing a large area to contact with electrolyte, and facilitating the electron transfer.
Highly efficient tree branch-shaped CuO photocathodes are fabricated using the hybrid microwave annealing process with a silicon susceptor within 10 minutes. The unique hierarchical, one-dimensional structure provides more facile charge transport, larger surface areas, and increased crystallinity and crystal ordering with less defects compared to irregular-shaped CuO prepared by conventional thermal annealing. As a result, the photocathode fabricated with the tree branch-shaped CuO produces an unprecedently high photocurrent density of -4.4 mA cm(-2) at 0 VRHE under AM 1.5 G simulated sunlight compared to -1.44 mA cm(-2) observed for a photocathode fabricated by thermal annealing. It is also confirmed that stoichiometric hydrogen and oxygen are produced from photoelectrochemical water splitting on the tree branch-shaped CuO photocathode and a platinum anode.
Fe- and Cu-codoped ZnO was previously reported as a room-temperature dilute magnetic semiconductor. We have investigated the origin of the ferromagnetism in Zn0.95−xFe0.05CuxO using the zero-field Fe57 nuclear magnetic resonance and neutron diffraction. These measurements reveal that some Fe ions of Zn0.95−xFe0.05CuxO form a secondary phase, ZnFe2O4. Detailed comparison of nuclear magnetic resonance spectra of Zn0.95−xFe0.05CuxO, bulk ZnFe2O4 with normal spinel structure, and nanocrystalline ZnFe2O4 with inverted spinel structure shows that the secondary phase possesses an inverted spinel structure and is ferrimagnetic at room temperature, while normal zinc ferrite is nonmagnetic. The ferromagnetism in Fe- and Cu-codoped ZnO stems from the secondary phase, while the majority of Fe ions substituted into the ZnO lattice appears to remain magnetically inert.
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