Search

N-doped carbon (N-C) materials are increasingly popular in different electrochemical and catalytic applications. Due to the structural and stoichiometric diversity of these materials, however, the role of different functional moieties is still controversial. We have synthesized a set of N-C catalysts, with identical morphologies (∼27 nm pore size). By systematically changing the precursors, we have varied the amount and chemical nature of N-functions on the catalyst surface. The CO2 reduction (CO2R) properties of these catalysts were tested in both electrochemical (EC) and thermal catalytic (TC) experiments (i.e., CO2 + H2 reaction). CO was the major CO2R product in all cases, while CH4 appeared as a minor product. Importantly, the CO2R activity changed with the chemical composition, and the activity trend was similar in the EC and TC scenarios. The activity was correlated with the amount of different N-functions, and a correlation was found for the -NO x species. Interestingly, the amount of this species decreased radically during EC CO2R, which was coupled with the performance decrease. The observations were rationalized by the adsorption/desorption properties of the samples, while theoretical insights indicated a similarity between the EC and TC paths.

The synthesis of the copper-poor and aluminum-rich layered double hydroxides (LDHs) of the CuAl4 type was optimized in detail in this work, by applying an intense mechanochemical treatment to activate the gibbsite starting reagent. The phase-pure forms of these LDHs were prepared for the first time; using copper nitrate and perchlorate salts during the syntheses turned out to be the key to avoiding the formation of copper hydroxide sideproducts. Based on the use of the optimized syntheses parameters, the preparation of layered triple and multiple hydroxides was also attempted using Ni(II), Co(II), Zn(II) and even Mg(II) ions. These studies let us identify the relative positions of the incorporating cations in the well-known selectivity series as Ni2+ >> Cu2+ >> Zn2+ > Co2+ >> Mg2+. The solids formed were characterized by using powder X-ray diffractometry, UV–Vis diffuse reflectance spectroscopy, Fourier-transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. The catalytic potential of the samples was investigated in carbon monoxide oxidation reactions at atmospheric pressure, supported by an in situ diffuse reflectance infrared spectroscopy probe. All solids proved to be active and the combination of the nickel and cobalt incorporation (which resulted in a NiCoAl8 layered triple hydroxide) brought outstanding benefits regarding low-temperature oxidation and increased carbon monoxide conversion values. [ABSTRACT FROM AUTHOR]

In an attempt to model occupational and environmental Mn exposures and their possible interaction, young male Wistar rats were exposed to Mn by oral administration in dissolved form (MnCl(2)·4H(2)O, 14.84 and 59.36 mg/kg b.w.) and by intratracheal application of MnO(2) nanoparticles (2.63 mg/kg b.w.). After 3 and 6 weeks oral, or 3 weeks oral plus 3 weeks intratracheal, exposure, general toxicological, and electrophysiological tests were done. Body weight gain was significantly reduced after 6 and 3 plus 3 weeks exposure, but the effect of the latter on the pace of weight gain was stronger. Organ weights signalized systemic stress and effect on lungs. Changes in evoked electrophysiological responses (cortical sensory evoked potential and nerve action potential) indicated that the 3 plus 3 weeks combined exposure caused equal or higher changes in the latency of these responses than 6 weeks of exposure, although the calculated summed Mn dose in the former case was lower. The results showed the importance of the physicochemical form of Mn in determining the toxic outcome, and suggested that neurofunctional markers of Mn action may indicate the human health effect better than conventional blood Mn measurement.