Ni Oxidation State and Ligand Saturation Impact on the Capability of Octaazamacrocyclic Complexes to Bind and Reduce CO2

Two 15-membered octaazamacrocyclic nickel(II) complexes are investigated by theoretical methods to shed light on their affinity forwards binding and reducing CO2. In the first complex 1[NiIIL]0, the octaazamacrocyclic ligand is grossly unsaturated (π-conjugated), while in the second 1[NiIILH]2+ one, the macrocycle is saturated with hydrogens. One and two-electron reductions are described using Mulliken population analysis, quantum theory of atoms in molecules, localized orbitals, and domain averaged fermi holes, including the characterization of the Ni-CCO2 bond and the oxidation state of the central Ni atom. It was found that in the [NiLH] complex, the central atom is reduced to Ni0 and/or NiI and is thus able to bind CO2 via a single σ bond. In addition, the two-electron reduced 3[NiL]2− species also shows an affinity forwards CO2.

Nickel Phosphide Catalysts as Efficient Systems for CO2 Upgrading via Dry Reforming of Methane

This work establishes the primordial role played by the support’s nature when aimed at the constitution of Ni2P active phases for supported catalysts. Thus, carbon dioxide reforming of methane was studied over three novel Ni2P catalysts supported on Al2O3, CeO2 and SiO2-Al2O3 oxides. The catalytic performance, shown by the catalysts’ series, decreased according to the sequence: Ni2P/Al2O3 > Ni2P/CeO2 > Ni2P/SiO2-Al2O3. The depleted CO2 conversion rates discerned for the Ni2P/SiO2-Al2O3 sample were associated to the high sintering rates, large amounts of coke deposits and lower fractions of Ni2P constituted in the catalyst surface. The strong deactivation issues found for the Ni2P/CeO2 catalyst, which also exhibited small amounts of Ni2P species, were majorly associated to Ni oxidation issues. Along with lower surface areas, oxidation reactions might also affect the catalytic behaviour exhibited by the Ni2P/CeO2 sample. With the highest conversion rate and optimal stabilities, the excellent performance depicted by the Ni2P/Al2O3 catalyst was mostly related to the noticeable larger fractions of Ni2P species established.

A Thermodynamic Investigation of Ni on Thin-Film Titanates (ATiO3)

Thin, ~1-nm films of CaTiO3, SrTiO3, and BaTiO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and then studied as catalyst supports for ~5 wt % of Ni that was added to the perovskite thin films by Atomic Layer Deposition. Scanning Transmission Electron Microscopy demonstrated that both the Ni and the perovskites uniformly covered the surface of the support following oxidation at 1073 K, even after redox cycling, but large Ni particles formed following a reduction at 1073 K. When compared to Ni/MgAl2O4, the perovskite-containing catalysts required significantly higher temperatures for Ni reduction. Equilibrium constants for Ni oxidation, as determined from Coulometric Titration, indicated that the oxidation of Ni shifted to lower PO2 on the perovskite-containing materials. Based on Ni equilibrium constants, Ni interactions are strongest with CaTiO3, followed by SrTiO3 and BaTiO3. The shift in the equilibrium constant was shown to cause reversible deactivation of the Ni/CaTiO3/MgAl2O4 catalyst for CO2 reforming of CH4 at high CO2 pressures, due to the oxidation of the Ni.

Unexpected phase separation in Li1−xNi0.5Mn1.5O4 within a porous composite electrode

The Ni oxidation state in Li1−xNi0.5Mn1.5O4 within a composite electrode mapped by scanning transmission X-ray microscopy (STXM) has shown unexpected variations in phase separation among and within individual battery particles, which has been experimentally correlated to both their morphology and interface structure.

The oxidation kinetics of thin nickel films between 250 and 500 °C

Diffusion controlled Ni oxidation is enhanced by fast grain boundary diffusion in growing nanocrystalline NiO films.

Effect of inhomogeneous re-oxidation on Ni-based SOFC oxidation resistance

Inhomogeneous re-oxidation, which causes graded NiO content along anode thickness, has been confirmed to be a key reason for Ni-based cell cracking during redox progress. In this paper, an analytical model is developed to estimate the impact of inhomogeneous re-oxidation on Ni-based solid oxide fuel cell (SOFC) oxidation resistance. And experiments, in which the SOFC was partially re-oxidized, were implemented for model trial. Model results show that electrolyte internal stress can be significantly reduced (from 367 MPa to 135 MPa, when the oxidation degree is 60%), and the electrolyte can remain intact even when the oxidation degree reaches about 70%, if the anode was re-oxidized uniformly. This impact of inhomogeneous re-oxidation on stress in the electrolyte decreases as the anode thickness increases. Scanning electron microscopic (SEM) images of partially oxidized anode cross-sections confirmed that Ni oxidation was inhomogeneous, in which the outer regions of the anode became almost fully oxidized, while the inner regions remained metallic. And the inhomogeneity increases with the redox times. Consequently, it is important to avoid gradients in NiO content during oxidation progress to prevent cell cracking.