Porous Texture of CuO Prepared from Copper Oxalate Precursor

The porous texture of CuO obtained from CuC 2 O 4 • 0.5H 2 O as a precursor, as well as the interconnection between the texture of the initial oxalate and that of the copper oxide obtained, has been studied by physisorption, XRD, XPS and SEM methods. The dimensions of the particle aggregates and the crystalline particles were altered as a consequence of the thermal decomposition of CuC 2 O 4 • 0.5H 2 O to CuO, and this led to an increase of ca. 1.5-times in the specific surface of the CuO obtained relative to that of the initial substance. The comparatively non-uniform sizes of the intra-aggregate mesopores in CuC 2 O 4 • 0.5H 2 O were transformed into considerably smaller intra-aggregate mesopores in CuO. A finite increase in the volume of the intra-crystallite pores in CuO was also observed, although this did not change the average size of the intra-crystallite pores in the oxide obtained nor the character of the pore-size distribution with respect to the starting material. In addition, as a result of the thermal decomposition of CuC 2 O 4 • 0.5H 2 O, the mesoporosity of the prepared oxide also developed. However, the CuO component retained the textural type characteristic of the initial CuC 2 O 4 • 0.5H 2 O

High Catalytic Activity in CO Oxidation over MnOx Nanocrystals

Manganese oxides of various stoichiometry were prepared via Mn-oxalate precipitation followed by thermal decomposition in the presence of oxygen. A nonstoichiometric manganese oxide, MnOx (x = 1.61…1.67) was obtained by annealing at 633 K and demonstrated superior CO oxidation activity, i.e. full CO conversion at room temperature and below. The activity gradually decreased with time-on-stream of the reactants but could be easily recovered by heating at 633 K in the presence of oxygen. CO oxidation over MnOx in the absence of oxygen proved to be possible with reduced rates and demonstrated a Mars—van Krevelen—type mechanism to be in operation. A TEM structural analysis showed the MnOx phase to form microrods with large aspect ratio which broke up into nanocrystalline manganese oxide (MnOx) particles with diameters below 3 nm and a BET specific surface area of 525 m2/g. Annealing at 798 K rather than 633 K produced well crystalline Mn2O3 which showed lower CO oxidation activity, i.e. 100% CO conversion at 335 K. The catalytic performance in CO oxidation of various Mn-oxides either studied in this work or elsewhere was compared on the basis of specific reaction rates.info:eu-repo/semantics/publishe

Structural and Optical Properties of Mg and Cd Doped ZnO Nanoclusters

Global optimization and data-mining techniques have been used to generate the structures of Mg and Cd doped ZnO nanoclusters. The energy has been evaluated at three levels: interatomic potentials during the filtering stage, generalized gradient based (PBE) density functional theory during the refinement of structures, and hybrid (PBE0) density functional theory for the final electronic solutions used for the prediction of the cluster optical absorption spectra. The excitonic energies have been obtained using timedependent density functional theory including asymptotic corrections. We considered three characteristic sizes of the host (ZnO)n cluster (n = 4, 6, 8) including all chemically sensible structural types as determined from their relative energy rankings and all possible dopant permutations. Thus, an exhaustive set of the solution structures could be assessed using onfigurational entropic contributions to the cluster free energy, which allowed us to draw a conclusion as to the oxide miscibility at this end of the size scale. With the exception of low temperature magnesium doped n = 4 and 6 nanoclusters, we find a continuous series of stable clusters. The former are predicted to disproportionate to the pure binary structures, which could be attributed to the competition between different structural types adopted by end members. The optical behavior of most stable clusters considered is contrary to the quantum confinement model