Today, Fs defects in MgO as isolated
surface neutral oxygen vacancies
are in the focus of surface science, catalysis research, and emission
coating of microchannel plates. With the 10–4 atom
% content at 750 K and under p
O2
= 10–9 Torr, estimated by us from the known equilibrium T–x and p–T–x diagrams of MgO, Fs defects
remain invisible or difficult-to-detect objects. The MgO(100) →
MgO(100) + Fs + 1/2O2 phase transition
was studied in MgO films deposited by the metal–organic chemical
vapor deposition (MOCVD) procedure from the mixed-ligand Mg precursor
on Si substrates at 725 K in the O2 flow where the nonstoichiometric
phase (MgO/Fs) is formed in the gas medium containing simultaneous
H2, CO, H2O, CO, and O2 species in
unbalanced concentrations. Realization of the above transition was
proven theoretically and experimentally through kinetic–thermodynamic
analysis of the nonequilibrium system with revealing thermodynamic
motive forces, i.e., the positive enthalpy and entropy, as well as
through a new combination of diagnostic methods including the original
differential dissolution method, due to which separate determination
of the point and morphological defects was achieved. It was found
that Fs defects occur when oxygen in the immediate vicinity to the
substrate surface is replaced practically completely by the oxidized
products of the precursor and the resulting oxygen pressure becomes
enough for this process. The 90 mass % of the as-deposited MgO-film-involved
(MgO/Fs) phase; its chemical activity is demonstrated through dissolution
in hot water, while the electron donor activity is through 9 at 750
eV secondary electron yield. A good understanding of gas-phase reactions
between the precursors and oxygen provides the fundamental basis of
the MOCVD process to deposit MgO films that are dense, free from carbon,
and of homogeneous texture. This makes the MOCVD process suitable
also for use as coatings of microchannel plates.
The development of solvent-free methods for the synthesis of catalysts is one of the main tasks of green chemistry. A nickel–alumina catalyst for CO2 methanation was synthesized by solid-state combustion method using hexakis-(imidazole) nickel (II) nitrate complex. Using X-ray Powder Diffraction (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Hydrogen temperature-programmed reduction (H2-TPR), it was shown that the synthesized catalyst is characterized by the localization of easily reduced nickel oxide on alumina surface. This provided low-temperature activation of the catalyst in the reaction mixture containing 4 vol% CO2. In addition, the synthesized catalyst had higher activity in low-temperature CO2 methanation compared to industrial NIAP-07-01 catalyst, which contained almost three times more hard-to-reduce nickel–aluminum spinel. Thus, the proposed approaches to the synthesis and activation of the catalyst make it possible to simplify the catalyst preparation procedure and to abandon the use of solvents, which must be disposed of later on.
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