We combine theoretical and experimental X-ray absorption near-edge spectroscopy (XANES) to probe the local environment around cationic sites of bulk spinel cobalt tetraoxide (Co${}_3$O${}_4$). Specifically, we analyse the oxygen K-edge spectrum. We find an excellent agreement between our calculated spectra based on the density functional theory and the projector augmented wave method, previous calculations as well as with the experiment. The oxygen K-edge spectrum shows a strong pre-edge peak which can be ascribed to dipole transitions from O $1s$ to O $2p$ states hybridized with the unoccupied $3d$ states of cobalt atoms. Also, since Co${}_3$O${}_4$ contains two types of Co atoms, i.e., Co${}^{3+}$ and Co${}^{2+}$, we find that contribution of Co${}^{2+}$ ions to the pre-edge peak is solely due to single spin-polarized $t_{2\mathrm{g}}$ orbitals ($d_{xz}$, $d_{yz}$, and $d_{xy}$) while that of Co${}^{3+}$ ions is due to spin-up and spin-down polarized $e_{\mathrm{g}}$ orbitals ($d_{x^2-y^2}$ and $d_{z^2}$). Furthermore, we deduce the magnetic moments on the Co${}^{3+}$ and Co${}^{2+}$ to be zero and 3.00 ${\mu }_B$ respectively. This is consistent with an earlier experimental study which found that the magnetic structure of Co${}_3$O${}_4$ consists of antiferromagnetically ordered Co${}^{2+}$ spins, each of which is surrounded by four nearest neighbours of oppositely directed spins.

Recent low-energy electron diffraction experiments concerning submonolayer Mn coverage on Co/Cu(001) substrates displayed a well-defined ${\mathrm{Mn}}_{0.5}{\mathrm{Co}}_{0.5}$ surface-ordered alloy. Through the magneto-optic Kerr effect and x-ray magnetic circular dichroism a ferromagnetic coupling between Mn and Co was obtained. Ab initio density functional theory within a generalized gradient approximation is able to explain these results.

This study assesses the bioenergy potential of two types of aquatic biomass found in the Republic of Congo: the green macroalgae Ulva lactuca (UL) and Ledermanniella schlechteri (LS). Their combustion behaviour was assessed using elemental and biochemical analysis, TGA, bomb calorimetry and metal analysis. Their anaerobic digestion behaviour was determined using biochemical methane potential (BMP) tests. The average HHV for LS is 14.1 MJ kg⁻¹, whereas UL is lower (10.5 MJ kg⁻¹). Both biomasses have high ash contents and would be problematic during thermal conversion due to unfavourable ash behaviour. Biochemical analysis indicated high levels of carbohydrate and protein and low levels of lipids and lignin. Although the lipid profile is desirable for biodiesel production, the levels are too low for feasible extraction. High levels of carbohydrates and protein make both biomasses suitable for anaerobic digestion. BMP tests showed that LS and UL have an average of 262 and 161 mL CH₄ gVS⁻¹, respectively. The biodegradability (BI) of LS and UL had an average value of 76.5% and 43.5%, respectively. The analysis indicated that these aquatic biomasses are unsuitable for thermal conversion and lipid extraction; however, conversion through anaerobic digestion is promising.

Theoretical investigations of oxygen vacancy effects in nickel-doped zirconia from ab initio XANES spectroscopy at the oxygen K-edge

Graphene oxide (GO) is considered as a promising adsorbent material for the removal of metal from aqueous environments. Here, we have used the density functional theory (DFT) approach and a combination of parameters to characterise the interactions of GO with lead (Pb) and cadmium (Cd), i.e., typical harmful metals often found in water. Our model systems consist of a singly and doubly adsorbed neutral (${\mathrm{Pb}}^0$, ${\mathrm{Cd}}^0$) and charged (${\mathrm{Pb}}^{2+}$, ${\mathrm{Cd}}^{2+}$) atoms adsorbed on the GO nanoparticle of the chemical formula ${\mathrm{C}}_{30}$${\mathrm{H}}_{14}$${\mathrm{O}}_{15}$. We show that a single charged metal ion binds more strongly than a neutral atom of the same type. Moreover, to determine the possibility of multiple adsorptions of the GO nanoparticle, two metal atoms of the same species were co-adsorbed on its surface. We found a site-dependent adsorption energy such that when two atoms of the same specie are adsorbed at sites ${\mathrm{S}}_i$ and ${\mathrm{S}}_j$, the binding energy per atom depends on whether one of the two atoms is adsorbed firstly on the ${\mathrm{S}}_i$ or ${\mathrm{S}}_j$ sites. Furthermore, the binding energy per atom for the two co-adsorbed atoms of the same specie (i.e., neutral or charged) is less than the binding energy of a singly adsorbed atom. This suggests that atoms may become less likely to be adsorbed on the GO nanoparticle when their concentration increases. We adduce the origin of this observation to be interplay between the metal–metal interaction on the one hand and GO–metal on the other, with the former resulting in less binding for the charged adsorbed metals in particular, due to repulsive interaction between two positively charged ions. The frontier molecular orbitals analysis and the calculated global reactivity descriptors of the respective GO–metal complexes revealed that all the GO–metal complexes have a smaller HOMO–LUMO gap (HLG) relative to that of pristine metal-free GO nanoparticle. This may indicate that although the GO–metal complexes are stable, they are less stable compared to metal-free GO nanoparticles. The negative values of the chemical potentials obtained for all the GO–metal complexes further confirm their stability. Our work differs from previous experimental studies in that those lacked details of the interaction mechanisms between GO, Pb and Cd, as well as previous theoretical studies which used limited numbers of parameters to characterise the GO–metal interactions. Rather, we present a set of parameters or descriptors which provide comprehensive physical and electronic characterisation of GO–metal systems as obtained via the DFT calculations. These parameters, along with those reported in previous studies, may find applications in rational design and high-throughput screening of graphene-based materials for water purification, as an example.