ABSTRACT
The electrochemical dinitrogen reduction reaction (NRR) has recently gained much interest as it can potentially produce ammonia from renewable intermittent electricity and replace the Haber-Bosch process. Previous literature studies report Fe- and Mo-carbides as promising electrocatalysts for the NRR with activities higher than other metals. However, recent understanding of extraneous ammonia and nitrogen oxide contaminations have challenged previously published results. Here, we critically assess the NRR performance of several Fe- and Mo-carbides reported as promising by implementing a strict experimental protocol to minimize the effect of impurities. The successful synthesis of α-Mo2C decorated carbon nanosheets, α-Mo2C nanoparticles, θ-Fe3C nanoparticles, and χ-Fe5C2 nanoparticles was confirmed by X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron and Mössbauer spectroscopy. After performing NRR chronoamperometric tests with the synthesized materials, the ammonia concentrations varied between 37 and 124 ppb and are in close proximity with the estimated ammonia background level. Notwithstanding the impracticality of these extremely low ammonia yields, the observed ammonia did not originate from the electrochemical nitrogen reduction but from unavoidable extraneous ammonia and NO x impurities. These findings are in contradiction with earlier literature studies and show that these carbide materials are not active for the NRR under the employed conditions. This further emphasizes the importance of a strict protocol in order to distinguish between a promising NRR catalyst and a false positive.
ABSTRACT
When cobalt thin films are illuminated with femtosecond laser pulses, we observe the emission of terahertz pulses. For a cobalt film thickness less than about 40 nm, the THz electric field direction rotates when the sample is rotated about the surface normal. This azimuthal angle-dependent emission is consistent with the assumption that laser-induced changes in an in-plane magnetization are responsible for the emission. For thicker layers, however, we observe the development of an azimuthal angle-independent contribution to the THz emission which we attribute to laser-induced changes in an out-of-plane magnetization component. We show that the relative contribution of this component grows when the cobalt film thickness increases. Our observations are supported by magnetic force microscopy measurements which show that for film thicknesses below 40 nm, the magnetization is predominantly in-plane whereas for thicknesses larger than 40 nm, an out-of-plane magnetization component develops.
ABSTRACT
We report on the surprisingly strong, broadband emission of coherent terahertz pulses from ultrathin layers of semiconductors such as amorphous silicon, germanium and polycrystalline cuprous oxide deposited on gold, upon illumination with femtosecond laser pulses. The strength of the emission is surprising because the materials are considered to be bad (amorphous silicon and polycrystalline cuprous oxide) or fair (amorphous germanium) terahertz emitters at best. We show that the strength of the emission is partly explained by cavity-enhanced optical absorption. This forces most of the light to be absorbed in the depletion region of the semiconductor/metal interface where terahertz generation occurs. For an excitation wavelength of 800 nm, the strongest terahertz emission is found for a 25 nm thick layer of amorphous germanium, a 40 nm thick layer of amorphous silicon and a 420 nm thick layer of cuprous oxide, all on gold. The emission from cuprous oxide is similar in strength to that obtained with optical rectification from a 300 µm thick gallium phosphide crystal. As an application of our findings we demonstrate how such thin films can be used to turn standard optical components, such as paraboloidal mirrors, into self-focusing terahertz emitters.
