Density functional theory calculations of copper-doped rutile crystals: Local structural, electronic, optical, and electron paramagnetic resonance properties.

The local structural, electronic, optical, and electron paramagnetic resonance (EPR) properties are uniformly studied for Cu2+ -doped rutile (TiO2 ) crystals by using the density functional theory (DFT) calculations. The local cation-oxygen bond lengths and planar bond angle, band gap, Mulliken charge and overlapping population, density of state (DOS), and UV-Vis absorption spectra are calculated for pure and copper-doped rutile. The smaller overlapping population of Cu-O bonds in the doped system than Ti-O bonds in pure rutile reflects weaker orbital admixtures or covalency of the former. Compared with pure rutile, Cu2+ doping leads to significant redshift of the UV-Vis absorption band and the narrow impurity band in visible and near-infrared regions arising from the Cu2+ d-d transitions and narrowing of the band gap by about 0.636 eV, possibly suggesting enhancement of visible light activity. The Cu dopant induces a spin magnetic moment of 0.74 µB for the doped rutile. The calculated UV-Vis absorption spectra and spin Hamiltonian parameters for copper-doped rutile show reasonable agreement with the experimental data and some improvement related to the previous perturbation formula calculations. Present systematic studies would be helpful to understand the mechanisms of the enhancement in the optical and magnetic properties of this material with transition-metal (especially Cu2+ ) dopants.

Exploring promising gas sensing and highly active catalysts for CO oxidation: transition-metal (Fe, Co and Ni) adsorbed Janus MoSSe monolayers.

From first-principles calculations, the transition-metal (TM) atom (Fe, Co and Ni) adsorbed Janus MoSSe monolayer, toxic gas molecules (CO, NH3 and H2S) adsorbed on the Ni-MoSSe monolayer and CO catalytic oxidation on the Fe-MoSSe monolayer are systematically investigated. An increasing order (Fe-MoSSe < Co-MoSSe < Ni-MoSSe) is found for the stability and band gap of the TM atom adsorbed Janus MoSSe monolayer. These toxic gas molecules are found to be weakly physisorbed and strongly chemisorbed on the pristine and Ni-MoSSe monolayers, respectively. The electronic structure and gas molecular adsorption properties of the Janus MoSSe monolayer can be modulated by adsorbing different TM atoms and gas molecules. Particularly, the CO catalytic oxidation can be realized on the Fe-MoSSe monolayer in light of the more preferable Eley-Rideal (ER) mechanism with the two-step route (CO + O2 → OOCO → CO2 + Oads, CO + Oads → CO2) with highly exothermic processes in each step. The adsorption of TM atoms which may greatly enhance gas sensing performance and catalytic performance of CO oxidation based on the Janus MoSSe monolayer is further discussed.